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17th INTERNATIONAL ZEOLITE CONFERENCE
Moscow, Russia, 7-12 July 2013
“Zeolites and ordered porous materials:
bridging the gap between nanoscience and technology”
BOOK OF ABSTRACTS
FOREWORD
It is our great pleasure to introduce the BOOK OF ABSTRACTS of the 17th
International Zeolite Conference (17th IZC) held from July 7 to July 12, 2013 in Moscow
(Russia). The Abstracts cover all aspects of the science and technology associated with
ordered porous materials, starting from traditional zeolites and mesostructured materials
and leading to novel porous hybrid solids. The Book is subdivided into 14 thematic subtopics going from the design of various porous nanomaterials to the development of their
applications via fundamental understanding of their structure and properties. This
subdivision reflects the main concept of the conference:
“Zeolites and ordered porous materials:
bridging the gap between nanoscience and technology”
In order to gather all the communications in a handly document the Book contains only
Short Summaries; the Extended Abstracts are available on the CD. The contents of the
Book include 5 plenary lectures, 14 keynote lectures, 155 oral and 509 poster
communications, which are organized thematically according to the sub-topics.
These contributions have been selected among 750 submissions received from 56
countries. The evaluation was accomplished by the timely and efficient refereeing by more
than 100 recognized researchers. The work was coordinated by 30 Topical Chairs, whose
outstanding input is greatly acknowledged, since the high level of the Conference would
have been hardly possible without their contribution. Besides that, a heavy task involved
formatting of the abstracts, since high percentage of the material submitted did not meet the
required format. Therefore we would like to namely acknowledge Stanislav Konnov and
Ivan Kasyanov, who did this job.
We also would like to thank our partners and sponsors for their generous support
and all the contributors for sharing their science. Finally we address a special
acknowledgement to all the staff of the Laboratories of Kinetics and Catalysis and Catalysts
of Petrochemical Processes from Moscow State University and Institute of Petrochemical
Synthesis for their dedication to the Conference organization.
This is the first time that the International Zeolite Conference is organized in
Russia and we sincerely hope that the delegates will enjoy their stay and will come home
with unforgettable impressions.
Acad. Salambek Khadzhiev
Prof. Irina Ivanova
Co-chairs of the Organizing Commiittee
of 17th IZC
Moscow, June 2013
2
ORGANIZING COMMITTEE
Co-chairpersons:
Salambek N. Khadzhiev
Irina I. Ivanova
National Organizing Committee Chairs:
Sergey M. Aldoshin
Michael P. Egorov
Valery V. Lunin
Valentin N. Parmon
Paper Selection Committee Chairs:
Girolamo Giordano
Eduardo Falabella
Vladimir M. Kapustin
Boris V. Romanovsky
Scientific Secretary:
Elena E. Knyazeva
Funds Raising:
Francois Fajula
Jean-Pierre Gilson
Sergey V. Kaluzhnyi
Ekaterina A. Kraeva
Treasurer:
Andrey V. Smirnov
Technical Secretary:
Leonid A. Logvin
Grants and Fellowships:
Yury G. Kolyagin
Publication:
Stanislav V. Konnov
Ivan A. Kasyanov
Communication:
Liudmila I. Rodionova
Maria A. Nikitina
Professional Conference Organizer:
Evgenia U. Malinina (KraftInfo Ltd.)
3
TOPICS AND TOPICAL CHAIRS
Topic Sub-topic Topical Chairs
1. Ordered porous materials: synthesis and modification
1.1. Zeolites and zeotypes J. Yu , G. Echevsky
P. Wu, O. Kikhtyanin
1.2. Natural zeolites C. Colella ,V. Il’in
1.3. Mesoporous materials and
hierarchical porous structures
T. Bein, E. Knyazeva
1.4. Hybrid and composite materials
(MOF, POM, ZIF, Porous carbons, etc)
C. Serre, L. Kustov
1.5. Zeolite and MOF membranes and
films
F. Kapteijn, D. Fedosov
2. Advances in fundamental understanding of structure and properties
2.1. Theory and modeling E. Pidko, G. Zhidomirov
2.2. Advanced characterization
techniques
Fr. Taulelle, V. Bukhtiyarov
2.3. Mechanistic studies; impact of insitu and operando techniques
F. Thibault-Starzyk, A. Stepanov
3. Industrial and emerging applications
3.1. Oil refinery and petrochemistry J. Santiesteban, M. Levinbuk
3.2. Non-oil fossil feedstocks into end
products
N. Nesterenko, N. Kolesnichenko
3.3. Environmental catalysis and
conversion of biomass
N. Kumar, A. Stakheev
3.4. Chemicals and fine chemicals B. Sels, A. Maksimov
3.5 Adsorption and separation M. Thommes, A. Toktarev
3.6. Novel applications (health,
electronics, sensors)
K. B. Yoon, A. Smirnov
4
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TABLE OF CONTENT
FOREWORD ................................................................................................................................1
ORGANIZING COMMITIE ........................................................................................................2
TOPICS AND TOPICAL CHAIRS ..............................................................................................3
PROGRAMME OVERVIEW.......................................................................................................4
PLENARY LECTURES..............................................................................................................47
PL-01 New Directions in Zeolite Synthesis .............................................................................49
Svetlana Mintova and Valentin Valtchev
PL-02 Methanol-to-Olefin: from fundamental to commercialization ....................................50
Zhongmin Liu, Yingxu Wei, Peng Tian, Lei Xu
PL-03 New Insights into Porous Materials from Advanced Characterization .......................51
R.F. Lobo
PL-04 Chemistry and application of porous coordination polymers (PCPs)/metal organic
frameworks(MOFs) ................................................................................................................52
Susumu Kitagawa
PL-05 Designing zeolites for specific applications ...................................................................53
Avelino Corma
KEYNOTE LECTURES.............................................................................................................55
KN-1.1 Simple Synthesis of Zeolites: New directions without the use of OSDAs....................56
Tatsuya Okubo and Keiji Itabashi
KN-1.2 The IZA Handbook of Natural Zeolites: a tool of knowledge of the most important
family of porous minerals ........................................................................................................56
Carmine Colella
KN-1.3 Monoliths with hierarchical porosity to enhance efficiency and productivity of
heterogeneous catalysts............................................................................................................57
Anne Galarneau
KN-1.4 Beyond the pure inorganic framework of zeolites: the Eni Carbon Silicates..............57
Roberto Millini
KN-1.5Zeolite and MOF Molecular Sieve Membranes – Quo Vadis? ....................................58
J. Caro
KN-2.1 Structure and properties of zeolite and metal organic framework nanosheets...........58
B. Slater
KN-2.2 Automated electron Diffraction Tomography (ADT) for solving structures of beam
sensitive nanoporous materials................................................................................................59
U. Kolb, E. Mugnaioli
KN-2.3 Life and Death of a Fluid Catalytic Cracking Particle ...............................................59
B.M. Weckhuysen
KN-3.1 Recent Advances and Current Challenges in Fluid Catalytic Cracking: Flexible Pilot
Plant Can Evaluate Unconventional Feedstocks and Processes ..............................................60
Kenneth Bryden, Gordon Weatherbee, and E. Thomas Habib, Jr.
KN-3.2 Direct methane transformations into valuable products in zeolites. Is there any
chance for the methane co-conversion with higher hydrocarbons? ........................................61
V. N. Parmon, A.G. Stepanov
8
KN-3.3 Depolymerization of wood components: role of zeolites .............................................61
Dmitry Yu. Murzin
KN-3.4 Clean Synthesis of Oximes and Amides over Titanosilicate Catalysts........................62
Peng Wu
KN-3.5 Recent Advances in Adsorptive Separation Science & Technology............................62
Joeri F.M Denayer and Gino V. Baron
KN-3.6 Nanoscale Manipulation of Zeolites and MOFs for Novel Bulk Scale. Applications:
Tunable Photoluminescence to Nuclear Waste Remediation ..................................................63
T.M. Nenoff, D. F. Sava, L. E. S. Rohwer, M. A. Rodriguez, P. Crozier, J. A. Greathouse, K. W.
Chapman, P. J. Chupas
ORAL COMMUNICATIONS.....................................................................................................64
SECTION 1. Ordered porous materials: synthesis and modification.........................................65
SECTION 1.1. Zeolites and zeotypes...........................................................................................66
O-1.1-01 Direct crystallization of CHA-type aluminosilicate zeolite without using OSDA from
amorphous aluminosilicate gel ................................................................................................66
Toshiyuki Yokoi, Hiroyuki Imai, Nozomu Hayashida, Junko N. Kondo and Takashi Tatsumi
O-1.1-02 Alternate Synthesis Route for the Crystallization of CHA Zeolite: OSDAContaining Aluminosilicate Colloids .......................................................................................66
Ahmad Moini, Ivan Petrovic, and Subramanian Prasad
O-1.1-03 A New aminophosphonium based Route for Synthesis of a zeolite related to
STF/SFF family .......................................................................................................................66
R. Simancas, M.T. Navarro, A. Cantín, N. Velamazán, J.A. Vidal, J.L. Jordá, T. Blasco, F. Rey, A.
Corma
O-1.1-04 Crystallization Mechanism of UZM-5 Zeolite in the Organic-Inorganic Mixed-SDA
System......................................................................................................................................67
M.B. Park, C.P. Nicholas, G.J. Lewis, S.B. Hong
O-1.1-05 New Molecular Sieves with ABC 6-Net Structures...................................................67
Gregory J. Lewis, Robert W. Broach, Stuart R. Miller, Lisa M. Knight, Paulina Jakubczak, Justin
Stanczyk, and Nanette Greenlay
O-1.1-06 Synthesis of a new extra-large pore zeotype with 16-ring openings by using proton
sponges as organic structure directing agents .........................................................................68
M. Moliner, R. Martínez-Franco, Y. Yun, W. Wan, X. Zou, A. Corma
O-1.1-07 A Heteroatom-Containing Aluminophosphate with New Zeolite Structure and
Tunable Luminescent Property...............................................................................................68
Yanyan Wang, Jiyang Li and Jihong Yu
O-1.1-08 Synthesis of SUZ-4 zeolite with TEA salts ................................................................68
A. V. Toktarev, G. V. Echevsky
O-1.1-09 Synthesis of beta zeolite in the absence of alkali cations...........................................69
Xiaomei Jia, Shaobing Yu, Fengmei Zhang, Xuhong Mu
O-1.1-10 Synthesis of Zeolite ZSM-5 with novel bamboo morphology....................................69
Kun Jiao, Zhengjia Li, Xiaoqiang Yao, Xiangyu Xu, Jiaqing Song, Zhaofei Li, Qian Wang, Lijun
Yan, and Mingyuan He
O-1.1-11 1ST Synthesis of New Frameworks by Unprecedented Top-Down Method, ADOR,
from Zeolite Precursor Mono-layers .......................................................................................69
W. J. Roth, P. Chlubna, R. E. Morris, P. Nachtigall, O. Shvets, J. Čejka
9
O-1.1-12 Design of zeolite by inverse sigma transformation ...................................................70
Elke Verheyen, Lennart Joos, Kristof Van Havenbergh, Eric Breynaert, Nataliia Kasian, Elena
Gobechiya, Kristof Houthoofd, Charlotte Martineau, Manuel Hinterstein, Francis Taulelle,
Veronique Van Speybroeck, Michel Waroquier, Sara Bals, Gustaaf Van Tendeloo, Christine E. A.
Kirschhock & Johan A. Martens
O-1.1-13 Interlayer expansion of RUB-36 with iron(III)chloride to obtain active alkylation
catalysts ...................................................................................................................................70
T. De Baerdemaeker, B. Yilmaz, M. Feyen, U. Müller, D. De Vos
O-1.1-14 Ultrafast framework stabilization of a Ge-rich zeolite by low-temperature plasma
treatment .................................................................................................................................71
Mohamad El-Roz, Frederic Thibault-Starzyk and Valentin Valtchev
O-1.1-15 Formation of a secondary phase during Ni2+ exchange of Faujasite: influence of
conditions and study by electron microscopies........................................................................71
T. Onfroy, F. Aubrit, S. Casale, L. Gaberova, P. Massiani
O-1.1-16 Bimetallic Cu/Au-MCM-22 zeolite – surface properties and catalytic performance in
total oxidation of methanol and carbon monoxide ..................................................................71
P. Kaminski, I. Sobczak, P. Decyk, M. Ziolek, W. J. Roth, B. Campo, M. Daturi
O-1.1-17 Silver encapsulated in Silicalite-1 .............................................................................72
G. Pacheco-Malagon, N.A. Sánchez-Flores, P. Pérez-Romo, A. García-Borquez, E. Diaz-Valdes,
V. Meza-Laguna, J.J. Fripiat
SECTION 1.2. Natural zeolites ...................................................................................................73
O-1.2-01 Natural Zeolites from Ethiopia: Stilbite ...................................................................73
Isabel Díaz, Yonas Chebude, Raquel García, Luis Gómez-Hortigüela, Joaquín Pérez-Pariente,
Asfawossen Asrat, Solomon Tadesse, and Ana B. Pinar
O-1.2-02 Single and Binary Adsorption of Cadmium(II) and Copper(II) from Aqueous
Solution onto Mordenite..........................................................................................................73
R. Leyva-Ramos, J. Mendoza-Barron, E. Padilla-Ortega and R.M. Guerrero-Coronado
O-1.2-03 Zn+2, Cu+2, Pb+2 and NH4+ Ion-Exchange on Clinoptilolites from Turkey and
Romania...................................................................................................................................74
A. Sirkecioglu, M.G. Ahunbay, M.F. Yardim, H. Atakul
O-1.2-04 Modified, natural clinoptilolites from Slovakia and Mexico as catalysts for liquidphase isomerization of α-pinene ..............................................................................................74
A. Dziedzicka, B. Sulikowski
O-1.2-05 Characteristics of Indonesian Natural Zeolites and Their Utilization for Increasing
Crop Production......................................................................................................................75
Suwardi
SECTION 1.3. Mesoporous materials and hierarchical porous structures.................................76
O-1.3-01 Mesoporous Tungsten-Zirconium Composite Oxides - Preparation with a Wall IonExchange Method and Activity for Acidic Catalysis ...............................................................76
Masashi Tanaka, Kohei Kabeya, Insuhk Suh, Haruro Ishitani, and Masakazu Iwamoto
O-1.3-02 A general strategy for the synthesis of micelle-templated mesoporous metal
carbonates and metal oxides....................................................................................................76
Björn Eckhardt, Erik Ortel, Denis Bernsmeier, Peter Strasser, Ulla Vainio, Jörg Polte, Franziska
Emmerling, Ralph Kraehnert
O-1.3-03 New mesoporous silica-titania catalysts by biotemplating – towards green catalyst
preparation..............................................................................................................................77
A. Sachse, E. Belamie, N. Marcotte, K. Kostov, V. Hulea, B. Alonso
10
O-1.3-04 A Spheric Mesoporous Sulfated Zirconia Material with High Catalytic Activity in
Acetylation...............................................................................................................................77
Feng Yu, Min Guo, Wenbo Zhang, Yuming Yi, and Ruifeng Li
O-1.3-05 Photocatalytic reduction of CO2 over modified Ti-TUD-1: Forward vs. Backward
reactions...................................................................................................................................77
Mohamed S. Hamdy, Bastian Mei, Jennifer Strunk, Guido Mul1
O-1.3-06 The view on synthesis and properties of MCM-41 and SBA-15 through
mesostructure. .........................................................................................................................78
S.D. Kirik, V.A. Parfenov, I.V. Ponomarenko, S.M. Zharkov
O-1.3-07 Synthesis of hierarchical zeolite catalysts with lamellar structural features ............78
M. Tsapatsis, X. Zhang, M. Khaleel, D. Xu
O-1.3-08 On the formation mechanism of nanostructured MFI zeolite: towards molecular
understanding of zeolite synthesis by templating agents .........................................................78
M. Goesten, X. Zhu, N. Kosinov, R. Rohling, B.M. Szyja, L. Wu, J. Gascon, F. Kapteijn, E.J.M.
Hensen
O-1.3-09 Bi-functional catalyst based on transition-metal oxides in zeolites with hierarchical
pore system..............................................................................................................................79
Carolina Neudeck, Sandra Kestermann, Wolfgang Schmidt and Ferdi Schüth
O-1.3-10 Progress on synthesis of hierarchical zeolite single crystal materials using a carbon
templating method...................................................................................................................79
J. O. Abildstroem, J. J. Mielby, M. Kegnæs, S. Kegnæs
O-1.3-11 Synthesis and performance of hierarchical zeolite FeZSM-5 ...................................79
K. A. Sashkina, E. V. Parkhomchuk, V. N. Parmon
O-1.3-12 Preparation of Ti-MFI with Hierarchical Structures by Alkali Treatment .............80
Masahiko Matsukata, K. Nagashima,
O-1.3-13 The function of unstable-site in mesopore formation of zeolite Y framework and its
catalytic cracking performance ...............................................................................................80
Baojian Shen, Dongdong Guo, Yuchen Qin, Chengyu Guo, Hao Li, Qiaoxia Guo
O-1.3-14 Permeable ceramometal monolith composites with incorporated mesoporous
Al-SBA-15................................................................................................................................80
S.F.Tikhov, V.E.Ramanenkau, Ya.Ya.Piatsiushyk, T.Ye.Yeutukhova, E.A.Mel’gunova1,
M.A.Mel’gunov S.V.Cherepanova, A.N.Shmakov, K.R.Valeev
O-1.3-15 New routes to nanozeolite crystals with very few framework defects.......................81
Laurence Burel, Alain Tuel
O-1.3-16 Multimodal zeolites with hierarchically micro-meso-macroporous structure..........81
L.H. Chen, X.Y. Li, X.Y. Yang, B.L.Su
O-1.3-17 Narrowing the mesopore size distribution in hierarchical TS-1 zeolite by surfactantassisted reorganization ............................................................................................................81
D. P. Serrano, R. Sanz, P. Pizarro, I. Moreno, S. Shami
O-1.3-18 Silicone Oil Surfactants Templating for Micro-and Nano-materials........................82
Ji Feng, Bo Sun, Caiyun Guo, Yuan Yao and Shunai Che
O-1.3-19 Functionalized mesoporous sorbents and membranes obtained by hydrolytic
polycondensation reaction of alkoxysilanes.............................................................................82
I.V. Melnyk, О.А. Dudarko, G.I. Nazarchuk, N.V. Stolyarchuk, V.V. Tomina, V.М. Kochkodan,
Yu.L. Zub, A.Kozak, A.Lobnik
SECTION 1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc).........83
O-1.4-01 Optimization of Lipase Immobilization in Mesoporous Organosilicas for Continuous
Flow Biocatalysis .....................................................................................................................83
Zhou Zhou, Frank Piepenbreier, Karl Karbacher, Martin Hartmann
11
O-1.4-02 Catalysis with AuI onto a Coordination Polymer: A Solid Porous Ligand with Free
Phosphine Sites ........................................................................................................................83
M. Ranocchiari, J. Václavík, M. Servalli, C. Lothschütz, J. Szlachetko, and J. A. van Bokhoven
O-1.4-03 Highly Ordered Mesoporous Fullerene Framework ................................................83
K. Hou; N.K. Minar; M. Döblinger; F. Hanusch; T. Bein
O-1.4-04 Preparation of Zeolite/Chitosan Hybrid Composites and Binderless Zeolite
Microspheres and Their Applications .....................................................................................84
Liang Yu, Jie Gong, Changfeng Zeng, Lixiong Zhang
O-1.4-05 From the crystallization to the large scale synthesis of porous Metal Organic
Frameworks of interest............................................................................................................84
Florence Ragon, Patricia Horcajada, Hubert Chevreau, Stuart Miller, Florent Bridoux, Thomas
Devic, Nathalie Steunoux, U.-Hwang Lee, Young Kyu Hwang, Jong San Chang, Christian Serre
O-1.4-06 Assessing the 3D internal structure of MOF-based mixed matrix membranes for
natural gas and biogas upgrading ...........................................................................................85
T. Rodenas, M. van Dalen, P. Serra-Crespo, F. Kapteijn and J. Gascon
O-1.4-07 In Situ NMR, XRD and SEM Study of the Hydrothermal Crystallization of
Nanoporous Aluminum Trimesates MIL-96, MIL-100, and MIL-110....................................85
M. Haouas, C. Volkringer, T. Loiseau , G. Férey, F. Taulelle
O-1.4-08 New porous M4+ (Zr, Ti) based MOFs: from poly-carboxylate to naturally occurring
-carboxyphenolate ligands.......................................................................................................86
Florence Ragon, Lucy Cooper, Laura Pardo, Ana Lago, Nathalie Guillou, Charlotte Martineau,
Thomas Devic, Christian Serre, Guillaume Clet, Alexandre Vimont and Marco Daturi
O-1.4-09 Hierarchical Polyoxometalate-based Metal-organic Frameworks ...........................86
L.H. Wee, C. Wiktor, S. Turner, W. Vanderlinden, G. Van Tendeloo, S. De Feyter, C.E.A.
Kirschhock, J. A. Martens
O-1.4-10 Microporous and mesoporous phenylenecarboxylate metal-organic frameworks as
host matrices for Pd nanoparticles stabilization......................................................................87
E.V. Afonina, V.I. Isaeva, E.E. Said-Galiev, V.V. Chernyshev, L.M. Kozlova, O.P. Tkachenko,
L.M. Kustov
O-1.4-11 Influence of octahedra connectivity and linker shape on the formation of
microporous and highly stable chain-based Al-based MOFs ..................................................87
N. Stock, H. Reinsch, F. Niekiel, M. Krüger
O-1.4-12 Controlling MIL-53 flexibility by functionalization and metal nodes – Impact on
carbon dioxide separation, optical properties and mechanical stability..................................87
P. Serra-Crespo, Freek Kapteijn, Jorge Gascon
O-1.4-13 Metal-organic framework thin films and post-synthetic modification for enhanced
selectivity in the adsorption of CO2 .........................................................................................88
Andrew D. Burrows, Dongmei Jiang, Luke L. Keenan and Karen J. Edler
O-1.4-14 Highly mesoporous and enantioselective metal-organic frameworks.......................88
Stefan Kaskel, Irena Senkovska, Frank Glorius, Elias Klemm, Eike Brunner
O-1.4-15 Reversed Crystal Growth in Selected Zeolites and MOFs........................................88
W. Z. Zhou, H. F. Greer, C. M. Zheng, Y. H. Liu, R. E. Morris
SECTION 1.5. Zeolite and MOF membranes and films .............................................................89
O-1.5-01 Purification of MFI-Nanosheets by Density Gradient Centrifugation and Their
Application as Ultrathin Zeolite Membranes ..........................................................................89
Michael Tsapatsis, K.V. Agrawal, B. Topuz, L.F. Francis
O-1.5-02 Incorporation of bifunctional Pd/ZSM-5 within microreactors for MIBK synthesis
.................................................................................................................................................89
L.A. Truter, V.V. Ordomsky, T.A. Nijhuis, J.C. Schouten
12
O-1.5-03 3D Architecture Formation with Zeolite Crystals on Solid Substrates with
Lithographic Approaches ........................................................................................................90
S.K. Kirdeciler, B. Akata
O-1.5-04 Synthesis of up-scaled tubular high-silica CHA-type zeolite membranes for an
industrial application to 2-propanol dehydration under high temperatures and pressures ...90
K. Sato, T. Kyotani, T. Kikuchi
O-1.5-05 Synthesis of Ordered Mesoporous TiO2 Membranes as Functional Materials ........90
R. Passalacqua, C. Ampelli, S. Perathoner, G. Centi
O-1.5-06 Programmed Functions with Surface Mounted Metal Organic Framework Thin
Films (SURMOFs) ...................................................................................................................91
Roland A. Fischer, Min Tu, Bo Liu
O-1.5-07 Interfacial Effects Control Mass Transport in Mixed Matrix Membranes..............91
Anna Santaniello, Maria Giovanna Buonomenna, Giovanni Golemme
SECTION 2. Advances in fundamental understanding of structure and properties ..................93
SECTION 2.1. Theory and modeling ..........................................................................................94
O-2.1-01 Quantum Chemical Studies of Zeolite-Catalyzed Reactions ....................................94
A. T. Bell, P. Zimmermann, J. Gomes, Sh. M. Sharada, M. Head-Gordon
O-2.1-02 Monte Carlo Simulation of Zeolite Crystal Growth .................................................94
M.W. Anderson, J.T. Gebbie
O-2.1-03 Spectacular diffusion behavior of aromatics in MOF type materials : A combination
of Molecular Dynamics simulations and Quasi-Elastic Neutron Scattering experiments .......94
S. Rives, H. Jobic, N. Ramsahye, Y. Ke, D.I. Kolokolov, A.G. Stepanov, T. Devic, C. Serre and G.
Maurin
O-2.1-04 Anisotropic Elastic Properties of Flexible Metal-Organic Frameworks...................95
Aurélie Ortiz, Anne Boutin, Alain H. Fuchs, François-Xavier Coudert
O-2.1-05 Structure, stability and reactivity of extraframework iron-containing sites in
Fe/ZSM-5 zeolite......................................................................................................................95
E.A. Pidko, G. Li, I. Filot, E.J.M. Hensen
O-2.1-06 Probing bridging hydroxyls under controlled conditions: a surface science approach
to study zeolites........................................................................................................................95
J.A. Boscoboinik, X. Yu, E. Emmez, B. Yang, F.D. Fischer, R. Wlodarczyk, M. Sierka, S.
Shaikhutdinov, J. Sauer, H.-J. Freund
O-2.1-07 DFT studies of T-atom distribution and mobility in zeolites and zeotypes...............96
S. Svelle, T. Fjermestad, S. Malola, M. Zokaie, K. P. Lillerud, O. Swang
O-2.1-08 Inter-conversion of EFAL species and influence of alkaly cations in dealuminated
zeolites .....................................................................................................................................96
Andrei A. Rybakov, Alexander V. Larin, Georgy M. Zhidomirov
SECTION 2.2. Advanced characterization techniques ...............................................................97
O-2.2-01 Redistribution of iron among various sites in micro- and mesoporous ferrisilicates
upon redox cycling...................................................................................................................97
K. Lázár
O-2.2-02 Critical evaluation of the catalytic potential of zeolites with controlled Al
distribution in the framework .................................................................................................97
Zdenek Sobalik, Petr Sazama, Jiri Dedecek and Blanka Wichterlova
O-2.2-03 Competitive Diffusion of Gases in a Zeolite Using A Slice Selection Procedure.......97
S. Leclerc, M. Petryk, D. Canet, J. Fraissard
13
O-2.2-04 Normal and Single-File Diffusion in One-Dimensional Nanochannels: New Insights
from Advanced NMR ..............................................................................................................98
Sergey Vasenkov, M. Dvoyashkin, A. Katihar, A. Wang, J. Zang, G.I. Yucelen, S. Nair, D.S. Sholl,
C.R. Bowers
O-2.2-05 MAS-PFG and HP-129Xe NMR spectroscopy to reveal the dynamics of
encapsulated ibuprofen............................................................................................................98
Antoine Gédéon, F. Guenneau, A. Nossov, M.-A. Springuel-Huet, T. Azais, F. Babonneau
O-2.2-06 Development of fully-automatic ammonia IRMS-TPD analyzer..............................98
Kazuyuki Nakai, Yoshikazu Senga, Tatsuya Torikai, Naonobu Katada, Miki Niwa
O-2.2-07 How to quantify the nickel and copper species in zeolites? IR studies of CO and NO
adsorption................................................................................................................................99
K. Góra-Marek, J. Datka
O-2.2-08 New TEM techniques for solving unknown zeolites, metal-organic frameworks and
other porous materials.............................................................................................................99
Xiaodong Zou
O-2.2-09 The Morphology of Pt/Zeolite Y Hydrocracking Catalysts: 3D Imaging and
Quantification at Nanoscale.....................................................................................................99
J. Zečević, H. Friedrich, P.E. de Jongh and K.P. de Jong
O-2.2-10 The top surface observation of nano porous materials using ultra low voltage SEM
...............................................................................................................................................100
S. Asahina, Y. Sakuda, M. Kudo, N. Kikuchi, R. Ryoo, O. Terasaki
SECTION 2.3. Mechanistic studies; impact of in-situ and operando techniques ......................101
O-2.3-01 Key Molecular Mechanisms for Zeolite Formation................................................101
M. Castro, W. Park, M. Houas, G. Brabants, E. Breynaert, I. Lim, C. Kirschhock, F. Taulelle, R.
Ryoo, F. Schüth, W. Schmidt
O-2.3-02 At-line analysis of the crystallization of Zeolite LTA by Raman spectroscopy ......101
T.F. Chaves, F.L.F. Soares, R.L. Carneiro, D. Cardoso
O-2.3-03 Multi-Faceted Spectroscopy Reveals H-ZSM-5 Phosphatation Pathways .............102
Hendrik E. van der Bij, Luis R. Aramburo, Bjørnar Arstad, Bert M. Weckhuysen
O-2.3-04 Reactive intermediates in methane to methanol conversion over Cu containing
zeolites ...................................................................................................................................102
P. Vanelderen, J. Vancauwenbergh, P. J. Smeets, R. G. Hadt, J. S. Woertink, R. A. Schoonheydt, E.
I. Solomon and B. F. Sels
O-2.3-05 Methane activation and transformation on Ag/H-ZSM-5 zeolite studied by solidstate NMR in situ ...................................................................................................................102
A.G. Stepanov, A.A. Gabrienko, S.S. Arzumanov, A.V. Toktarev
O-2.3-06 Evidence of transition-state shape selectivity in the reaction of methanol to olefins
on nanoSAPO-34 ...................................................................................................................103
Zhibin Li, Joaquín Martínez-Triguero, Jihong Yu, Avelino Corma
O-2.3-07 Activation energies and pre-exponential factors of C3 to C8 alkane conversion over
various zeolites and non-zeolitic solid acids...........................................................................103
N. Katada, S. Sota, K. Okumura, M. Niwa
O-2.3-08 Regeneration of an organophilic ZSM-5 after sulfamethoxazole antibiotic
adsorption: an in situ high-temperature synchrotron powder diffraction study...................103
L. Leardini, A. Martucci, I. Braschi, S. Blasioli, R. Arletti, S. Quartieri
SECTION 3. Industrial and emerging applications ..................................................................105
SECTION 3.1. Oil refinery and petrochemistry .......................................................................106
14
O-3.1-01 Versatility of MFI catalytic applications in refining and base chemicals: Total
experience ..............................................................................................................................106
N. Nesterenko, D. Minoux, J-P Dath
O-3.1-02 Hydrocarbon Transformations Catalyzed by UZM-35, a Material Containing Both
10MR and 12MR Pores .........................................................................................................106
Christopher P. Nicholas, Jaime G. Moscoso, Deng-Yang Jan
O-3.1-03 Acidic and diffusional properties of hierarchical H-ZSM5 and the application in
toluene methylation ...............................................................................................................106
J.H. Ahn, R. Kolvenbach, S.S. Al-Khattaf, A. Jentys, J.A. Lercher
O-3.1-04 Peculiarities of benzene alkylation by ethene on binder-free zeolites.....................107
I.M. Gerzeliev, L.M. Kustov, M.L. Pavlov, Yu.A. Lapshina, R.A. Basimova, O.P. Tkachenko, S.
N. Khadzhiev
O-3.1-05 Catalytic Cracking of n-Octane over Medium-Pore Zeolites: Influence of Pore
Architecture, Aluminum Content and Crystallite Morphology on Activity and Selectivity .107
F. Bager, S. Ernst
O-3.1-06 Hydrogen transfer in transformations of olefins and thiophene compounds on
zeolite-containing catalysts ....................................................................................................107
Oleg V. Potapenko, V.P. Doronin, T.P. Sorokina, V.P. Talsi, O.V. Krol, V.A. Likholobov
O-3.1-07 Replacing rare earth in FCC catalyst by alkaline earth.........................................108
R. Bergstraesser, S. Wellach, S. Sirotin, A. Vimont,V. Valtchev, J.-P. Gilson and A. Travert
O-3.1-08 Commercial experience of operating FCC unit with decrease in the catalyst/feed
mass ratio...............................................................................................................................108
M.I. Levinbuk, I.S. Maksimov, S.E. Kuznetsov
O-3.1-09 Mesostructured Y Zeolites: First Refinery Results of a Hierarchical FCC Catalyst
...............................................................................................................................................108
M. Rico, A. Grau, Kunhao Li, J. Garcia-Martinez
O-3.1-10 Synthesis and application of zeolite W in the catalyst for FCC gasoline hydroupgrading ..............................................................................................................................109
Huan Niu, Aijun Duan, Zhen Zhao, Guiyuan Jiang, Jian Liu, Yuechang Wei, Huifang Pan
SECTION 3.2. Non-oil fossil feedstocks into end products .......................................................110
O-3.2-01 Non-oxidative aromatization of methane: assessment of zeolite framework effects by
catalyst descriptors from microkinetic modeling. .................................................................110
C. Martínez, M.T. Portilla, K.S. Wong, J.W. Thybaut, E. Tangstad, M. Stöcker, G.B. Marin
O-3.2-02 Photocatalytic Conversion of Small Organic Molecules in Zeolitic Materials........110
Lu Li, Guo-Dong Li, Yi-Yu Cai, Kai-Xue Wang, Jie-Sheng Chen
O-3.2-03 Distillate-range products from non-oil based sources by catalytic cascade reactions
...............................................................................................................................................110
V. Hulea, A. Lacarriere, J. Robin, D. Swierczynski, A. Finiels, F. Fajula, F. Luck
O-3.2-04 Morphology Induced Shape Selectivity in Zeolite Catalysis...................................111
Shewangizaw Teketel, Lars F. Lundegaard, Unni Olsbye, Karl Petter Lillerud, Stian Svelle, Pablo
Beato
O-3.2-05 Regeneration for Promotion to Catalytic Activity of H-ZSM-5 for DME Conversion
to Olefin.................................................................................................................................111
A. Muramatsu, M. Nakaya, K. Omata, M. Yamada, Y. Yamazaki
O-3.2-06 Insights into the selective and catalytic oxidation of methane to methanol with Cupromoted Fe-ZSM-5 at mild conditions ................................................................................111
C. Hammond, N. Dimitratos, H. Hagen, E. E. Stangland, D. J. Willock and G. J. Hutchings
15
O-3.2-07 Methanol synthesis over Cu/ZnO nanoaggregates encapsulated in carbon nanotubes
and mesoporous silica............................................................................................................112
D. Großmann, A. Dreier, C. Lehmann W. Grünert
SECTION 3.3. Environmental catalysis and conversion of biomass.........................................113
O-3.3-01 Mesoporous Carbon as a Superior Catalyst Support in One-pot Conversion of
Cellulose to Polyols ................................................................................................................113
Aiqin Wang, Jifeng Pang, Yanhua Zhang, Mingyuan Zheng, Tao Zhang
O-3.3-02 Decomposition of Hexose Sugars to Levulinic Acid Using Graphene Oxide Catalysts
with Brønsted Acid Sites........................................................................................................113
Pravin P. Upare, Ji-Woong Yoon, Hyo-Yoon Kang, Dong Won Hwang, Young Kyu Hwang,
Harold H. Kung, and Jong-San Chang
O-3.3-03 Zeolite water treatment in a thermochemical biofuel production process .............114
A. Bosetti, G. Franzosi, C. Perego
O-3.3-04 Application and Stability of Ru/H-USY Zeolites in Hot Liquid Water ..................114
J.A. Geboers, T. Ennaert, S. Van De Vyver, K. Houthoofd, P.A. Jacobs and B.F. Sels
O-3.3-05 The direct conversion of rapeseed oil over pilot Pd Zn/MFI/Al2O3 catalyst...........114
M. A. Gubanov, A. V. Chistyakov, M. V. Tsodikov
O-3.3-06 Metal-substituted TUD-1 for the Synthesis of Valuable Chemicals from Glycerol
and Related Compounds........................................................................................................115
Li Li, Bert F. Sels, and Paolo. P. Pescarmona
O-3.3-07 The Catalytic Conversion of Waste Glycerol to Value-Added Products ................115
G. Sanchez, L. Harvey, J. Friggieri, B. Z. Dlugogorski, E. Kennedy, M. Stockenhuber
O-3.3-08 Hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-zeolite and Ptheteropolyacid catalysts.........................................................................................................115
M.A. Alotaibi, E.F. Kozhevnikova, I.V. Kozhevnikov
O-3.3-09 Selective hydroconversion of acetic acid over indium doped Ni-zeolites ................116
Sz. Harnos, Gy. Onyestyák, Sz. Klébert, A. Kaszonyi, M. Štolcová, D. Kalló
O-3.3-10 Selective catalytic reduction (SCR) of nitrogen oxides over Fe zeolites New insights
into active sites and reaction mechanisms .............................................................................116
I. Ellmers, R. Velez, A. Brückner, U. Bentrup, H. Huang, V. Schünemann, W. Grünert
O-3.3-11 Effect of ammonia addition on copper electronic state and DeNOx reactivity of Cusubstituted ZSM-5 .................................................................................................................116
S. A. Yashnik, N.T. Vasenin, V.F. Anufrienko, Z.R. Ismagilov
O-3.3-12 Sulfur stable precious metal loaded zeolites for CH4 combustion..........................117
Arno Tißler, Frank Klose, Olga Manoylova
O-3.3-13 Catalytic activity of NixSiBEA and NixHAlBEA in conversion of 1,2-dichloroethane
...............................................................................................................................................117
A. Śrębowata1, I.I.Kamińska, D.Łomot, D. Lisovytskyi, R. Baran, T. Onfroy, S. Dzwigaj
O-3.3-14 Iron-functionalized silica nanoparticles as highly efficient catalyst for decomposition
of VOCs .................................................................................................................................117
M. Popova, A. Ristić, K. Lazar, D. Maučec, M. Vassileva N. Novak Tušar
O-3.3-15 CO2 hydrogenation into CH4 on Ni zeolite based catalysts.....................................118
I. Graça, L.V. González, C. Henriques, J.M. Lopes, M.F. Ribeiro
SECTION 3.4. Chemicals and fine chemicals ...........................................................................119
O-3.4-01 Intramolecular carbon shifts in carbohydrates are catalyzed by microporous tincontaining solid Lewis acids with borate salts in aqueous media ..........................................119
Yuriy Román-Leshkov, W.R. Gunther, Y. Wang, Y. Ji, V.K. Michaelis, R.G. Griffin
16
O-3.4-02 Simple and scalable synthesis of highly active Lewis acidic Sn-β ...........................119
C. Hammond, S. Conrad, C. Aellig, P. Wolf and I. Hermans
O-3.4-03 Promotive effects of alkylation of nitrogen atom doped in silicate framework on the
basic properties of porous silica materials.............................................................................120
M. Ogura, K. Sugino, Y. Furukawa, S. Fukunaga
O-3.4-04 Selective formation of hydroquinone in the phenol oxidation with H2O2 over TiMCM-68 zeolite catalyst ........................................................................................................120
Satoshi Inagaki, Y. Tsuboi, K. Mamiya, Y. Kubota
O-3.4-05 Cyclohexene oxidation by TAPO-5 catalysts prepared with Ti(III) source............120
Almudena Alfayate, Manuel Sánchez-Sánchez, Joaquín Pérez-Pariente
O-3.4-06 Tailoring faujasitic frameworks for the sustainable synthesis of nylon..................121
M.E. Potter, S. Newland, R. Leithall, M. Carravetta, R. Raja, A. Levy
O-3.4-07 MPVO reduction of crotonaldehyde over Zr containing molecular sieves.............121
V.L. Sushkevich, E. Taarning, S. Tolborg, I.I. Ivanova
O-3.4-08 High-selective direct amination of primary alcohols using a Pd/cryptomelane
catalyst...................................................................................................................................121
M. Ousmane, G. Perrussel, J-M. Clacens, M. Pera-Titus, F. Decampo
O-3.4-09 Mesoporous MIL-101 metal-organic frameworks as heterogeneous catalysts for
liquid-phase selective oxidation .............................................................................................122
N.V. Maksimchuk, I.D. Ivanchikova, K.A. Kovalenko, V.P. Fedin, O.A. Kholdeeva
SECTION 3.5. Adsorption and separation................................................................................123
O-3.5-01 In-depth Study of Surface Resistances in Nanoporous Materials by Microscopic
Diffusion Measurement .........................................................................................................123
Jörg Kärger
O-3.5-02 Understanding Stimuli-Induced Structural Transitions in Metal-Organic
Frameworks From the Unit Cell to the Crystal.....................................................................123
F.-X. Coudert, A. Boutin, A. V. Neimark, A. H. Fuchs
O-3.5-03 Equilibrium and kinetics of water adsorption on the pure and substituted
aluminophosphates: application for energy transformation .................................................123
I.S. Girnik, Yu.I.Aristov
O-3.5-04 Storage of oxygen and hydrogen in zeolites and their release behaviors................124
M. Fujiwara, Y. Fujio, H. Sakurai, H. Senoh, T. Kiyobayashi, I. Kumakiri
O-3.5-05 A Novel Titano-Silico-Alumophosphate for Heat Management .............................124
Silke Sauerbeck, Arno Tißler, Rolf Kurzhals
O-3.5-06 Adsorption of sulfonamide antibiotics into high silica zeolites from water: A
combined structural, spectroscopic and computational approach ........................................124
I. Braschi, S. Blasioli, M. Cossi, L. Marchese, A. Martucci, S. Quartieri
O-3.5-07 Amine-Containing Nanoporous Materials for CO2 Removal .................................125
A. Sayari
O-3.5-08 n- and cyclohexane separation on the UiO-66 Metal-Organic Framework............125
Belgin Bozbiyik, Tim Duerinck, Gino V. Baron, Dirk E. De Vos , Pieterjan Valvekens and Joeri
F.M Denayer
O-3.5-09 Effect of Room Temperature Ionic Liquids on the Gas Adsorption in Cu-BTC
Metal-Organic Framework: A Simulation Study..................................................................125
J. M. Vicent-Luna, J. J. Gutiérrez-Sevillano, J. A. Anta, and S. Calero
O-3.5-10 Synthesis of DNL-6 with high concentration of Si (4Al) species and its good
performance for CO2 separation ...........................................................................................126
Xiong Su, Peng Tian, Dong Fan, Yue Yang, Shutao Xu, & Zhongmin Liu1
17
O-3.5-11 Cation gating and selective carbon dioxide adsorption in flexible zeolite Rho.......126
M.M. Lozinska, P.A. Wright, J.P.S. Mowat, X. Hu, S. Brandani, M. Palomino, J.L. Jorda, S.
Valencia, F. Rey
O-3.5-12 Effective Separation of Hydrocarbon Mixtures by Zeolitic Imidazolate Frameworks8 (ZIF-8) Membranes ............................................................................................................126
Yichang Pan, Zhiping Lai
O-3.5-13 Adsorption and differential heats of adsorption of hexane isomers on ZIF-8 ........127
A. Ferreira, M. Mittelmeijer-Hazeleger, M.A. Granato, V.F.D. Martins, A. Rodrigues, G.
Rothenberg
O-3.5-14 Investigation of Small Pore Zeolites Via Vapor Phase Adsorption of n-Hexane....127
C.Y. Chen and S.I. Zones
O-3.5-15 Towards the Computational Screening of MOFs for Xylene Separation ...............127
M. Lennox, P.Z. Moghadam, A.D. Gellan, T. Düren
SECTION 3.6. Novel applications (health, electronics, sensors) ...............................................128
O-3.6-01 A Photoconductive Covalent Organic Framework Showing Light-Induced Charge
Transfer Towards Included Fullerene...................................................................................128
Mirjam Dogru, Matthias Handloser, Florian Auras, Thomas Kunz, Dana Medina, Achim
Hartschuh, Paul Knochel and Thomas Bein
O-3.6-02 Enhancement of catalysis by the localized surface plasmon resonance of size- and
color-controlled Ag prepared using microwave and mesostructure......................................128
Koujiro Fuku, Ryunosuke Hayashi, Takashi Kamegawa, Kohsuke Mori, Hiromi Yamashita
O-3.6-03 Ultrafast optical study on silver nanoparticles stabilized in zeolite Beta colloidal
suspensions ............................................................................................................................128
F. A. Kawtharani, V. De Waele, R. Retoux, S. Mintova, G. Buntinx
O-3.6-04 NH2-MIL-101 as adsorbent for potential application in nuclear medicine.............129
P. Serra-Crespo, H.G.M.E. van Ostaay, .A.G. Denkova, H.Th. Wolterbeek, F. Kapteijn, J. Gascon
O-3.6-05 Ordered Mesoporous Silicas for Drug Delivery in Dermatological Applications...129
B. Onida, R. Mortera, B. Camarota, D. Caldarola, G. Chieregatti, A. Gignone
O-3.6-06 Influence of the silica support morphology on the long-term corticoid release. .....129
R.A. García, V. Morales and P.E. Gonzalez
O-3.6-07 Control of dye fluorescence by encapsulation into 1D nanochannels .....................130
Virginia Martínez-Martínez, Raquel García, Luis Gómez-Hortigüela, Joaquín Pérez-Pariente, Íñigo
López-Arbeloa
O-3.6-08 Maya Blue analogs prepared with various zeolite matrices....................................130
S. Kowalak, A. Zywert, M. Szyld
O-3.6-09 Energetic performances of channel and cage-type zeosils ......................................130
L. Tzanis, M. Trzpit, M. Soulard, T.J. Daou, J. Patarin
O-3.6-10 Effect of Hydrophobic Tail Length of Polysorbate Surfactants on Properties of
MFI-type zeolite Ultra-Low-k Films......................................................................................131
Ting-Yi Li, Chun-Hsien Yu, Hsin-Yan Lu, and Ben-Zu Wan
POSTER COMMUNICATIONS ..............................................................................................133
SECTION 1. Ordered porous materials: synthesis and modification.......................................133
SECTION 1.1. Zeolites and zeotypes.........................................................................................134
P-1.1-01 Microporosity of amorphous aluminosilicate precursors of zeolites.......................134
A. Morsli, R. Arletti, A. Bengueddach, F. Quignard, F. Di Renzo
18
P-1.1-02 Effect of SDA on FAU-CHA Interzeolite Conversion .............................................134
Naoki Yamanaka, Masaya Itakura, Yoshimichi Kiyozumi, Masahiro Sadakane, Tsuneji Sano
P-1.1-03 Hydrothermal synthesis of zeolite SSZ-16 (AFX) from optimized synthesis solutions
...............................................................................................................................................134
P. Hrabanek, A. Zikanova, J. Drahokoupil, O. Prokopova, L. Brabec, I. Jirka, V. Fila, J. Cookney,
M. Kocirik
P-1.1-04 Comparison of Properties between Zeolites Heated by Microwaves and Electric
Oven.......................................................................................................................................135
T. Ohgushi, S. Ando, M. Susaki
P-1.1-05 Fluorine-Free Synthesizing Fluoride-Caused AlPO4-34.........................................135
Jinxiong Wu, Huiru Zhao, Niu Li, Qianqian Luo, Chunqian He, Naijia Guan, Shouhe Xiang
P-1.1-06 An efficient method to synthesize IM-5 zeolite........................................................135
Junwen Chen, Chao Zhang, Yongrui Wang, Xuhong Mu
P-1.1-07 Isomorphous substitution of Nb and Ta into Y-type zeolite as a tool for creation of
new surface properties...........................................................................................................136
Anna Wojtaszek, Maciej Trejda, Frederik Tielens, Maria Ziolek
P-1.1-08 Ionothermal Synthesis of Zinc Phosphate or Phosphite framework Materials.......136
Lei Liu, Sanying Li, Jinxiang Dong
P-1.1-09 Li+ Exchange into Zeolite Na-Y from Aqueous Methanol Depends upon Water
Content .................................................................................................................................136
H. S. Kim, W. T. Lim, K. Seff
P-1.1-10 Synthesis of ZSM-22/ZSM-23 intergrowth zeolite ..................................................137
K.B. Chi, Z.J. Tian, L.J. Yan, B.C. Wang, S. Hu, M.W. Tan, Y.F. Liu, S.B. Gao
P-1.1-11 Synthesis and characterization of zeolite ZSM-5 in the presence of ammonia and
phosphate...............................................................................................................................137
Jianzhun Jiang, Jing Feng, Mingsen Zhang, Li Ke, Yuanyuan Ji
P-1.1-12 Estimation of acid site distribution in pores of H-ZSM-5 zeolite prepared with
various structure-directing agents.........................................................................................137
Hiroshi Mochizuki, Toshiyuki Yokoi, Seitaro Namba, Junko N. Kondo, Takashi Tatsumi
P-1.1-13 Ionothermal synthesis, crystal structure and magnetic properties of a new
manganese phosphite with intersecting structure .................................................................138
Miao Yang, Peng Chen, Xinjie Li, Chang Wang, Peng Tian, Meiqi Zhang, Peifang Yan, Qingshan
Liu
P-1.1-14 Synthesis of ZSM-5 from natural rectorite minerals activated by different methods
...............................................................................................................................................138
H.Y. Liu, W.W. Wang, T. Shen, X.J. Bao
P-1.1-15 Synthesis and study of the structural and adsorption properties of synthetic zeolite
ECR-18 with paulingite structure..........................................................................................138
O. Yu. Golubeva, N. Yu. Ulyanova, A. V. Yakovlev
P-1.1-16 Seed-assisted Synthesis of VET-type zeolite without the Use of Organic StructureDirecting Agents ....................................................................................................................139
Kenta Iyoki, Keiji Itabashi, Tatsuya Okubo
P-1.1-17 A study on dry gel conversion of silicas of different nature into Silicalite-1 ...........139
M. S. M. Kamil, K. Manikandan, S. P. Elangovan, K. K. Cheralathan
P-1.1-18 Aminothermal Synthesis of CHA-SAPO Molecular Sieves with High Solid Yield and
their Catalytic Performance in MTO Reaction .....................................................................139
Dong Fan, Peng Tian, Xiong Su, Dehua Wang, Yangyang Yuan, Chan Wang, Zhongmin Liu
P-1.1-19 Study on the crystallization of the hollow titanium silicalite zeolite........................140
Min Lin, Bin Zhu, Xingtian Shu, Chunfeng Shi, Guofan Li, Gang Shen, Bin Li, Hua Li
P-1.1-20 Green synthesis of zeolites from submolten salt depolymerized aluminosilicate
minerals .................................................................................................................................140
Xiaojun Bao, Ning Li, Haiyan Liu, Tiesen Li, Yuanyuan Yue
19
P-1.1-21 Synthesis of beta zeotypes by a method of microwave drying of gels......................140
Farlán Taborda
P-1.1-22 Preparation and Crystal Structure of Ga42Tl9.3-Si121Al71O384 (Zeolite Y, FAU)
Containing Ga57+, Ga+, Ga2+, Ga3+, and Tl+ ...........................................................................141
N.H. Heo, J.J. Kim, C.W. Kim, J.Y. Kim, K. Seff
P-1.1-23 Design Synthesis of Efficient Catalysts from Layered Zeolite Precursors ..............141
Hao Xu, Jingang Jiang, Boting Yang, Jianggan Wang, Haihong Wu, Yueming Liu, Peng Wu
P-1.1-24 Synthesis of a Fe-MFI zeolite with super-micropores by using potassium
hexacyanoferrate (III) as an iron source ...............................................................................141
Baoshan Li, Junqing Xu, Chunying Han
P-1.1-25 Synthesis and modification of small-crystal titanium silicalite-1: The active species in
titanium silicalite-1 ................................................................................................................142
Yi Zuo, Min Liu, Wancang Song, Haiying Jiang, Luwei Hong, Xiangsheng Wang, Xinwen Guo,
Yongsheng Chen, Pengyu Zhu, Cherno Jaye, Daniel Fischer
P-1.1-26 Synthesis of zeolite from waste materials at low temperature.................................142
Claudia Belviso, Francesco Cavalcante, Antonio Lettino, Simone Pascucci, Stefano Pignatti,
Saverio Fiore
P-1.1-27 Synthesis of MSE-type zeolite without using organic structure-directing agent and
its catalytic application ..........................................................................................................142
Y. Kubota, K. Itabashi, S. Shinoda, R. Komatsu, S. Inagaki, T. Okubo
P-1.1-28 Influences of sodium salts on crystallization of large mordenite crystals................143
Koji Nishi, Kenjiro Sadamori, Masahiro Kasukawa, Minako Mizobuchi, Kosei Makino, Natsumi
Kamiya, Yoshinobu Yokomori
P-1.1-29 Polymorphism in organic-free precursor mixtures .................................................143
H. Awala, R. Retoux, J. Toufaily, S. Mintova
P-1.1-30 Nucleation events in alumosilicate hydrogels of different density...........................143
Ana Palčić, Valentin Valtchev, Josip Bronić
P-1.1-31 On the true symmetry of pure silica ITQ-7.............................................................144
J.-L. Paillaud, B. Marler, L. Tzanis, J. Patarin, H. Gies
P-1.1-32 In-situ Calorimetric Study on Y Zeolite Synthesis ..................................................144
Jihong Zhou, Yibing Luo, Xuhong Mu, Xingtian Shu, Minjiang Gao
P-1.1-33 Morphology Control of Silicalite-1 by Adding NH4F ..............................................144
Xiaoqiang Yao, Xiangyu Xu, Zhi Lv, Jiaqing Song, Zhaofei Li, Qian Wang, Lijun Yan, Mingyuan
He P-1.1-34 A perspective in the industrial applications of beta by OSDA-free synthesis:
Improved hydrothermal stability, despite of its high aluminum content ..............................145
S. P. Elangovan, K. Itabashi, T. Hieda, M. Yamamoto, K. Momma, M. Ogura, Y.Yamazaki, T.
Okubo
P-1.1-35 Controllable intergrowth of EU-1/ZSM-48 zeolite using EU-1 seed .......................145
Yafei Zhang, Yanjun Gong, Xiaoling Liu, Tao Dou
P-1.1-36 Effect of seeds on crystallization on zeolite FER by method VPT modifying the
OSDAs and Al source ............................................................................................................145
L.M.O. Ribeiro, P.P. Modesto Neto, T.R.D. Mendonça, B.J.B. Silva, T.P.M. Costa, L.V. Sousa
Junior, A.O.S. Silva, M.M. Urbina
P-1.1-37 Synthesis of ZSM-22/-23 intergrowth zeolite and the hydroisomerization
performance of long-chain paraffins .....................................................................................146
Bingchun Wang, Huaijun Ma, Zhijian Tian, Renshun Xu, Peng Li, Wei Qu, Lin Wang, Jianqiang
Han, Zhusheng Xu, Liwu Lin
P-1.1-38 Processing line for the synthesis of zeolites from fly ash .........................................146
W. Franus, M. Wdowin, R. Panek
20
P-1.1-39 The role of lithium cations in a novel synthesis of a low silica KFI type
aluminosilicate.......................................................................................................................146
L. Van Tendeloo, K. Lauwers, Y. Lorgouilloux, J.A. Martens, C.E.A. Kirschhock
P-1.1-40 New Zeolitic Phases Obtained using 1,8-diazabiciclo[5.4.0]undec-7-eno Derivatives
as Structure Directing Agents................................................................................................147
E. M. Diaz-Canales, M. J. Diaz-Cabañas
P-1.1-41 In-situ generation of silver oxide nuclei for the size control of zeolite crystals ......147
F. Hamidi, F. Boukli-Hacène, T. Cacciaguerra, A. Bengueddach, F. Di Renzo
P-1.1-42 Synthesis of AlPO4-5 molecular sieve in the absence of water................................147
H. J. Ma, Z. J. Tian, B. C. Wang, W. Qu, R. S. Xu, P. Li, D. E. Wang, Z. D. Pan
P-1.1-43 The Zeolite adsorbent NewSieve ANT-4A with nano-structured protective layer with
a high mechanical strength, adsorption capacity and resistance to condensed moisture ......148
Sergey Fastov, Ilya Fastov
P-1.1-44 Synthesis of zeolite X-carbon from coal bottom ash ...............................................148
Nurul Widiastuti, Didik Prasetyoko, Hamzah Fansuri, Mila Zhely Nurul Hidayah
P-1.1-45 Rapid Synthesis of Sn-Beta for the Isomerization of Cellulosic Sugars .................148
C.C. Chang, W. Fan
P-1.1-46 Synthesis of FAU- and EMT-type zeolites using novel templates designed by
molecular modeling ...............................................................................................................149
T.J. Daou, J. Dhainaut, A. Chappaz, N. Bats, B. Harbuzaru, G. Lapisardi, H. Chaumeil, A. Defoin,
L. Rouleau, J. Patarin
P-1.1-47 Interzeolite conversion of MCM-49 zeolite into ZSM-35 zeolite .............................149
S.J. Xie, S.L. Liu, K.F. Liu , N.N. Gao , X.J. Li, Y. Gao, L.Y. Xu
P-1.1-48 Synthesis of SAPO-34 molecular sieve using piperazine as a template ...................149
Huiru Zhao, Yue Ding, Niu Li, Naijia Guan, Shouhe Xiang
P-1.1-49 Synthesis of porous aluminophosphates using self-assembling 1,3-diphenylguanidine
as structure-directing agent...................................................................................................150
Teresa Álvaro-Muñoz, Joaquín Pérez-Pariente, Luis Gómez Hortigüela
P-1.1-50 Effect of the alumosilicate gels pH on zeolite phase composition for the cocrystallization of BEA/MOR zeolites in Na2O-ТЕАBr-Al2O3-SiO2-H2O system...................150
Anastasia F. Gizetdinova, Svetlana A. Skornikova, Sergey S. Kolesnikov, Marina I. Tselyutina,
Irina D. Reznichenko
P-1.1-51 Influence of preparation procedure on state and distribution of Co species in
modified BEA zeolite .............................................................................................................151
R. Baran , S. Casale, T. Grzybek, S. Dzwigaj
P-1.1-52 Mild desilication synthesis of hollow zeolite microtubes .........................................151
Z.C. Liu, Y.D. Wang, H.X. Gao
P-1.1-53 Thermal stability of the pillaring structure in silylated MCM-22 zeolite................151
N. Gao , S. Xie, S. Liu, X. Li, L. Xu
P-1.1-54 Synthesis of novel layered silicates HUS-2, HUS-3 and HUS-4: their ability of the
precursor of zeolite and incorporation of aluminum.............................................................152
Nao Tsunoji, Takuji Ikeda, Yusuke Ide, Masahiro Sadakane, Tsuneji Sano
P-1.1-55 Multistep Cluster Synthesis: A Novel Zeolite Modification Method.......................152
A.B. Ponomaryov, V.E.Vakhmistrov, M.V.Shostakovsky, A.P.Kosolapova, V.N.Kalinin,
E.S.Mortikov
P-1.1-56 Alkylation of toluene with methanol over phosphorous and silica modified IM-5
zeolite.....................................................................................................................................153
Junwen Chen, Chao Zhang, Yongrui Wang, Xuhong Mu
P-1.1-57 Highly Accessible, Stable and Active Sn Catalysis in Partially Dealuminated Beta
Zeolites ..................................................................................................................................153
J. Dijkmans, D. Gabriëls, F. De Clippel, M. Dusselier, P. Van Elderen, B.F.Sels
21
P-1.1-58 Bead-Milling and Post-Milling Recrystallization: An Organic Template-Free
Methodology for the Production of Nano-Zeolite X ..............................................................153
Toru Wakihara, Koki Sato, Kaku Sato, Junichi Tatami, Katsutoshi Komeya, Takeshi Meguro
P-1.1-59 Depolymerization and Reorganization of Faujasite Y.............................................154
P. Pérez-Romo, H. Armendáriz-Herrera, J. S. Valente, M.L. Guzmán-Castillo, F. HérnándezBeltrán and J. Fripiat
P-1.1-60 Synthesis, modification, and characterization of zeolite A and some cationexchanged forms....................................................................................................................154
L.Wang, I. Spiess, H. Lührs, W.H. Baur, R.X. Fischer
P-1.1-61 Effect of ion exchange preparation variables on the reduction of Co metalloxo
clusters in zeolites. ................................................................................................................154
O.A. Kirichenko, G.I. Kapustin
P-1.1-62 Framework Sites Preferred by Aluminum in Zeolite ZSM-5. Structure of a Fully
Dehydrated, Fully Cs+-exchanged ZSM-5 Crystal (MFI, Si/Al = 24) ..................................155
Cheol Woong Kim, Hyeon Seung Lim, Nam Ho Heo, Karl Seff
P-1.1-63 Synergistic Effect of Lanthanum and Phosphorus on the Aromatization Activity of
Zn/ZSM-5 ..............................................................................................................................155
H.Y. Long, F.Y. Jin, X.S. Wang
P-1.1-64 B-, Al-, Ga- and Fe-containing extra-large pore zeolites with UTL topology:
synthesis, structure and catalytic properties .........................................................................155
O.V. Shvets, M.V. Shamzhy, M.V. Opanasenko, P.S. Yaremov, M.V. Solomakha, L.Kurfiřtova,
W.J.Roth
P-1.1-65 Framework transformation of FAU-type zeolite in high alkalinity.........................156
L. Van Tendeloo, E. Gobechiya, E. Breynaert, J.A. Martens, C.E.A. Kirschhock
P-1.1-66 Influence of the framework Li+ distribution on the thermal stability of Low silica
Zeolite X ................................................................................................................................156
M.H. Fan, S.Y. Bai, B. Ren, J.H. Sun
P-1.1-67 Cu/zeolites catalysts obtained by impregnation and milling mechanics..................156
Geovanni R. Melchor, Beatriz Zeifert, José L. Contreras-L, José Salmones
P-1.1-68 Highly Dispersed Silver Nanoparticles in Beta Suspensions ...................................157
F. A. Kawtharani, S. Thomas, R. Retoux, V. De Waele, S. Mintova
P-1.1-69 Ruthenium Nanoparticles Encapsulated Disordered Titanosilicate ETS-10...........157
Melda İşler, S. Galioglu, Burcu Akata Kurç
P-1.1-70 Incorporation of fluoride in as-made zeolites: new developments and applications157
X. Liu, A. Tuel
P-1.1-71 Using InCl Vapor to Ion Exchange Indium into Zeolite Na–X. Two Single-Crystal
Structures of Fully Dehydrated Inn+-Exchanged Zeolite X..................................................158
D. Sen, N.H. Heo, K. Seff, H.-C. Kang, M.K. Park
P-1.1-72 Single Gold nanoparticle in Single crystal hollow zeolite ........................................158
S. Li, L. Burel, A. Tuel, C. Aquino, D. Farrusseng
SECTION 1.2. Natural zeolites…………………………………………………………………….159
P-1.2- 01 Regularities of sorption pyridoxine hydrochloride on native clinoptilolite tuff .....159
Kotova D.L., Fam Thi Gam, Krysanova T.A., Vasilyeva S.U., Timchenko U.A.
P-1.2-02 CO2 adsorption on Erionite exchanged with Ca2+, Mg2+, K+, Na+ and H+...............159
M. A. Hernández, Corona, F. Rojas, R. Portillo
P-1.2-03 Cobalt-exchanged natural zeolites (Australian and Indonesian) for catalytic
oxidation of phenol solutions .................................................................................................159
Hongqi Sun, Edy Saputra, Ha Ming Ang, Moses O. Tadé, Shaobin Wang
22
P-1.2-04 Use of zeolitites from Central Italy in an integrated cycle aimed at water and
chemical fertilizers saving (ZEOLIFE - LIFE+10ENV/IT/000321) .....................................160
M.F. Brigatti, A. Laurora, D. Malferrari, E. Passaglia, G. Vezzalini
P-1.2-05 Activated Natural Zeolite Supports Human Health and Physical Performance as an
Antioxidant............................................................................................................................160
T. Oberwinkler, D. Maurer, K. Pavelić, S. Kraljević Pavelić, M. Lamprecht, I. Triebnig, N. Bachl
P-1.2-06 Removal of radionuclides by zeolite-bearing rocks.................................................161
D.A. Shushkov, O.B. Kotova, I.I. Shuktomova
P-1.2-07 Elimination of Fluoride using Natural Zeolites from Ethiopia ...............................161
Luis Gómez-Hortigüela, Joaquín Pérez-Pariente, Yonas Chebude and Isabel Díaz
P-1.2-08 About Possibility of Using Modified Natural Zeolite in Catalytic Cleaning of Exhaust
Gases from NO and CO.........................................................................................................162
L. Akhalbedashvili, G. Maisuradze, A. Mskhiladze, Sh. Sidamonidze
P-1.2-09 Investigation and mathematical modeling of Sr+ ion-exchange kinetics from surface
drinking water on natural clinoptilolite ................................................................................162
V.A. Nikashina, М.G.Tokmachev, I.B.Serova, T.G.Kuzmina, I.A.Roschina, .A.Tikhonov
P-1.2-10 The characterization of geomorphic molecular sieve particles using Zero Length
Column chromatography ......................................................................................................163
S.A. Hosseinzadeh Hejazi, J. Sawada, G. Dechaine, S. Kuznicki
P-1.2-11 Natural iron exchanged Mordenite: FTIR study and Catalytic Activity in NO
Reduction...............................................................................................................................163
I. Rodríguez Iznaga, D. Tito Ferro, V. Petranovskii, F. Castillon Barraza, A. Simakov, B.
Concepción Rosabal, F. Chávez Rivas, I. E. Tellez León, G. Berlier
P-1.2-12 Adsorption of urea onto Iranian natural phillipsite and stilbite zeolites.................163
C. F. Linares, L. Uray, F. Ocanto, X. Cardozo, S. Yazdani
P-1.2-13 Mechanical activation of zeolite powders for improving efficiency of sorption of oil
spills on water surface ...........................................................................................................164
L. Y. Atyutskaya, A. G. Bebia
P-1.2-14 Zeolitized tuff as raw material for alkali activated binders ....................................164
B.Liguori, C. Ferone, I. Capasso, R. Cioffi, C. Colella
P-1.2-15 The choice of optimal conditions for fixing α-tocopherol on acid activated
clinoptilolite tuff ....................................................................................................................164
Vasilyeva S.Y., Kotova D.L., Krysanova T.A.
P-1.2-16 Application of Natural Zeolites for creation of polymer composite materials ........165
I.N. Meshkova , T.M. Ushakova, V.G. Grinev, V.A.Nikashina, T.A.Ladygina, L.A. Novokshonova
P-1.2-17 Zeolite-bearing rocks of the Komi Republic (Russian Federation) ........................165
D.A. Shushkov, O.B. Kotova
P-1.2-18 EPR study of some modified clinoptilolites from deposit of Georgia......................165
L. Akhalbedashvili, N. Kekelidze, R. Mirianashvili
P-1.2-19 Investigation of Sulphur Dioxide (SO2) Adsorption Properties of Natural and Acid
Modified Clinoptilolites from Turkey ...................................................................................166
Burcu Erdoğan Alver, Meryem Sakızcı
P-1.2-20 Low-temperature behavior of the cancrinite-group minerals ................................166
G.D. Gatta, P. Lotti, V. Kahlenberg
SECTION 1.3. Mesoporous materials and hierarchical porous structures...............................167
P-1.3-01 Micro-mesoporous materials prepared using zeolite nanoparticles as catalysts for
N2O decomposition and reduction.........................................................................................167
M. Rutkowska, L. Chmielarz, D. Macina, Z. Piwowarska, B. Dudek, W. Roth, L. Obalová, C.J.
Van Oers, P. Cool
23
P-1.3-02 Improved catalytic performance of mesoporous zeolite ZSM-5 synthesized by
desilication with surfactants ..................................................................................................167
F. Schmidt, M. R. Lohe, B. Büchner, F. Giordanino, F. Bonino, S. Kaskel
P-1.3-03 Anchored Pt(II) complex on mesoporous silica materials: correlation between
photoluminescence emission and visible-light driven photocatalytic activity .......................167
Kohsuke Mori, Kentaro Watanabe, Hiromi Yamashita
P-1.3-04 Meso and microporous materials for confined space synthesis of noble metal
catalysts to address their sintering problems .......................................................................168
R. Nandini Devi, Atul Prashar, Anupam Samanta, Sumona Ghosh
P-1.3-05 Silylation and hydrothermal stability of composite materials based on MCM-41 .168
E.O. Korabelnikova, S.I.Karpov, N.A. Belanova, V.F. Selemenev, F. Roessner, A. Inayat
P-1.3-06 Synthesis of mesoporous graphic C3N4 using cross-linked bimodal mesoporous
SBA-15 as hard-template.......................................................................................................168
H.-M. Zhao, Y. Chun, L. Ji, Q.-H. Xu
P-1.3-07 Hierarchical Mesoporous MFI Zeolites by Steam-Assisted Crystallization and
Applications in Catalysis .......................................................................................................169
J. Zhou, Z. C. Liu, H. X. Gao, Y. D. Wang, Z. K. Xie, Y. Tang
P-1.3-08 Organosilanes affecting the structure and formation of mesostructured cellular
foams......................................................................................................................................169
K. Stawicka, I. Sobczak, M. Trejda, B. Sulikowski, M. Ziolek
P-1.3-09 As-synthesized CTA-MCM-41 modified with methacrylate polymers:
characterization and catalytic evaluation .............................................................................169
J. A. Araújo, D. Cardoso
P-1.3-10 Desilication of MFI Zeolites under Hydrothermal Condition.................................170
Guang Zeng, Congbiao Chen, Debao Li, Bo Hou, Yuhan Sun
P-1.3-11 Structural and Diffusion Characterizations of Mesostructured Composite Zeolites
BFZ........................................................................................................................................170
Jiajun Zheng, Meng Pan, Qiu Zhang, Yan Wang, and Ruifeng Li
P-1.3-12 Synthesis of Novel Micro-mesoporous Beta-MCM-48 and Catalytic Performance in
FCC gasoline Hydro-upgrading Process ...............................................................................170
Aijun Duan, Huadong Wu, Zhen Zhao, Guiyuan Jiang, Jian Liu, Yuechang Wei
P-1.3-13 Mesoporous HZn-ZSM-5 for methanol to aromatics..............................................171
M.H. Qiu, Z.Y. Liu, L. Xia, X. Liu, L. Wu, H.J. Zhu, Y.H. Sun
P-1.3-14 Incorporation of Catalytic and Luminescent Activity in Mesoporous Silica Via SolGel Coordination Chemistry .................................................................................................171
N. Linares, M. Rico, A. Sepulveda, E. Serrano, E. Lalinde, J. Berenguer, J. Garcia-Martinez
P-1.3-15 Facile Large-Scale Synthesis of Monodisperse Mesoporous Silica Nanospheres with
Tunable Pore Structure ........................................................................................................171
Kun Zhang, Lang-Lang Xu, Hai-Hong Wu, Bélen Albela, Laurent Bonneviot, Peng Wu
P-1.3-16 Study on synthesis and cracking properties of hydrothermally disordered
mesoporous silica-alumina material ......................................................................................172
J. Y. Zheng, Y. B. Luo, X. H. Mu, X. T. Shu
P-1.3-17 Synthesis of mesoporous basic zeolites for upgrading biofuels ...............................172
V. Callejo, J.M. Gómez, M.D. Romero
P-1.3-18 Switchable Wettability in a Bulk Material: Synthesis and Function of an Azobenzene
Grafted Silica Material..........................................................................................................172
L. Gräfenstein, M. Ried, I. Köhl, R. Herges and W. Bensch
P-1.3-19 Desilicated mesoporous zeolites for methane dehydroaromatization......................173
Selene Hernández Morejudo, Christian Kjølseth and Stian Svelle
P-1.3-20 One-pot synthesis of mesoporous MCM-22 for benzene alkylation ........................173
C.H.L. Tempelman, N.G.R. de Caluwé, B. Mezari, E.J.M. Hensen
24
P-1.3-21 Synthesis of micromesoporous materials by assembling of sol-precursors ZSM-5 in
the structure of the mesoporous molecular sieve...................................................................173
R.Yu. Barakov, N.D. Scherban, P.S. Yaremov, V.M. Solomakha, V.G. Ilyin
P-1.3-22 Improved SSZ-13 zeolite catalysts for the methanol-to-olefins reaction .................174
X. Zhu, L. Wu, E.J.M. Hensen
P-1.3-23 Surfactant silica vesicles used as templates to obtain macro-mesoporous silicas or
biphasic mesoporous carbons ................................................................................................174
C.F. Santa, S. Casale, M. Jaber, J.L.Guth, L. Sierra
P-1.3-24 Facile synthesis of nano-crystallite orientated self-assembled ZSM-5 catalyst and its
LDPE cracking properties.....................................................................................................174
Hongbin Zhang, Yahong Zhang and Yi Tang
P-1.3-25 Template assistant synthesis of mesoporous ZrO2 for application in catalysis .......175
E.V. Golubina, N.E. Kavalerskaya, E.S.Lokteva
P-1.3-26 Comparative study of the porous structure of the products of the direct synthesis
miсromesoporous materials ZSM-11/MCM-41 and their mixtures ......................................175
P.S. Yaremov, V.L. Struzhko, V.G. Ilyin
P-1.3-27 Supported mesoporous and hierarchical porous Pd-TiO2 coatings with concomitant
control of particle size and pore structure.............................................................................175
E. Ortel, S. Sokolov, C. Zielke, I. Lauermann, S. Selve, K. Weh, B. Paul, J. Polte, R. Kraehnert
P-1.3-28 Stabilizing Self-Assembled Alumina Mesophases ...................................................176
L. López Pérez, S. Perdriau, G. ten Brink, B.J. Kooi, H.J. Heeres, I. Melián-Cabrera
P-1.3-29 Catalytic Oxidation of N-heterocycles over Mesoporous TS-1................................176
Jacob Oskar Abildstroem, Jerrik Mielby, Soeren Kegnaes
P-1.3-30 The influence of preparation conditions on the formation micromesoporous
materials on the basis of MCM-41 and zeolite MEL.............................................................176
V. L. Struzhko, P. S. Yaremov, E. V. Senchylo, V. M. Solomakha, V. G. Ilyin
P-1.3-31 Ion exchange as a technique of mesopore formation in low-silica zeolite X ............177
A.B. Ayupov, A.A. Leonova, V.B. Fenelonov, M.S. Melgunov
P-1.3-32 Direct synthesis of hierarchical porous SAPO-34-H nano-rod through the doubletemplate approach.................................................................................................................177
Shang Jiang, Runwei Wang, Zongtao Zhang, Shilun Qiu, Hongri Suo
P-1.3-33 Synthesis of hollow mesoporous silica spheres by treatment of core-shell structured
mesoporous spheres with alkaline solutions ..........................................................................177
M. Okamoto, H. Tsukada, S. Fukasawa
P-1.3-34 Synthesis and Catalysis of Core-Shell Structured Microporous Titanosilicate and
Mesoporous Materials ...........................................................................................................178
Le Xu, Hong-gen Peng, Haihong Wu, Kun Zhang, Peng Wu
P-1.3-35 Controlled mesoporosity in ZSM-5 by desilication: Effect of surfactant and
quaternary amine additives...................................................................................................178
Yun-Jo Lee, Ki-Won Jun, Kyoung-Su Ha, Geun Jae Kwak, Hae-Gu Park
P-1.3-36 Nanoporous magnetic silicate matrixes ...................................................................178
Pshenko О. А., Antropova Т. V.
P-1.3-37 Structural and dynamics properties of confined water in MCM-41 samples (Ø =
40Å; 25Å and 19Å) ...............................................................................................................179
J.P. Coulomb, N. Floquet, G. André
P-1.3-38 Generation of mesopores in ZSM-5 and its effect on catalytic properties...............179
Quanyi Wang, Yingxu Wei, Jinzhe Li, Shutao Xu, Jingrun Chen, Yue Qi, Shuanghe Meng,
Fuxiang Chang, Baolian Su, Zhongmin Liu
P-1.3-39 Amine Templating Synthesis of Mesoporous Mo-M (M = Ce or Zr) Mixed Oxides179
Nabil Al-Yassir, Abdouelilah Hachimi, Mohammed Al-Yami, Mohammed Al-Rasheedi
25
P-1.3-40 Hierarchically Porous Single Crystal-like Mesoporous Silica and Zeolite by
Mesomorphous Polyelectrolyte-Surfactant Complexes as Dynamic Template .....................180
Chengxiang Shi, Hui Zhao, Jinyu Liu, Na Li, Jingui Wang, Tiehong Chen
P-1.3-41 Properties of MCM-41 and SBA-15 mesoporous silicas modified by ionic liquid...180
M. I. Onishchenko, I. A. Tyablikov, A. V. Yatsenko, E. E. Knyazeva, B. V. Romanovsky
P-1.3-42 Synthesis of IM-5 Zeolite Hollow Spheres...............................................................180
Weiya Yang, Fengxiang Ling, Lei Wang, Zhiqi Shen, Shaojun Wang
P-1.3-43 Mesoporous mordenites of different textures prepared by desilication and
recrystallization: a comparative characterization by N2 adsorption and electron tomography
techniques ..............................................................................................................................181
C. Bertrand-Drira, G. Melinte, O. Ersen, D. Minoux, A. Finiels, F. Fajula, C. Gerardin
P-1.3-44 Highly ordered TiO2 nanotube arrays: factors affecting their morphology............181
А.N. Morozov, A.I. Mikhaylichenko
P-1.3-45 Synthesis of hierarchically porous MFI zeolites via controlled steam crystallization
in the mesoporogen-free system and minimum presence of zeolite structure-directing agent
...............................................................................................................................................181
R. R. Mukti, M. Rilyanti, M. Ogura, H. Nur, Ismunandar
P-1.3-46 Synthesis of regular hexagonal nut-like SBA-15 without additives.........................182
Juan Wang, Huali Zhao, Huijing Zhou, Yuping Liu
P-1.3-47 Hierarchical TS-1 zeolite for the oxidation of bulky molecules...............................182
A. Silvestre-Albero, A. Grau-Atienza, E. Serrano-Torregrosa, J. García-Martínez, J. SilvestreAlbero
P-1.3-48 Calorimetric study on acidic properties of hierarchical MFI zeolites obtained from
protozeolitic units ..................................................................................................................182
Claudia Mónica López-León, Héctor Armendáriz-Herrera, Ma. De Lourdes Guzmán-Castillo, José
J. Fripiat, María-Guadalupe Cárdenas-Galindo, Brent E. Handy
P-1.3-49 Synthesis of Zeolitic and non-Zeolitic Support of Random and Ordered
Mesoporosity for Nanosized Mo-M (M = Ce or Zr) Mixed Oxides .......................................183
Nabil Al-Yassir, Mohammed Al-Yami, Mohammed Al-Rasheedi
P-1.3-50 Synthesis of Mesoporous Zeolite ZSM-58 ...............................................................183
T. Biemelt, C. Selzer, F. Schmidt, S. Kaskel
P-1.3-51 Design of hierarchical porous aluminas by using one-pot synthesis and different
calcination temperatures ......................................................................................................183
A. R. Passos, L. Martins, S. H. Pulcinelli, C. V. Santilli
P-1.3-52 Hierarchic zeolites: the accessibility of acid sites followed by quantitative IR studies
of pivalonitrile adsorption .....................................................................................................184
K. Góra-Marek, K. Sadowska, J. Datka
P-1.3-53 Synthesis of hierarchical SAPO-31 molecular sieves...............................................184
Rui Zhang, Wei Wu, O.V. Kikhtyanin, Linfei Xiao, Aijuan Zhao, Huimin Wu, A.V. Toktarev,
G.V. Echevsky
P-1.3-54 Synthesis of cubic Ia3d mesoporous silica AMS-6 with the aid of acetate...............184
S.X. Deng, W.C. He, X.L. Zhang, J.G. Wang, H.J. Zhou, T.H. Chen
P-1.3-55 Influence of temperature on the synthesis of SBA-3 nanostructured catalytic
material..................................................................................................................................185
M. V. Ponte, M. L. Martínez, J. Cussa, O.A Anunziata, A. R. Beltramone
P-1.3-56 Synthesis of mesoporous ZSM-12 using a soft-template - Acid activity in the
cyclohexane cracking.............................................................................................................185
Kele T. G. Carvalho, Ernesto A. Urquieta-Gonzalez
P-1.3-57 Remarkable enhancement of catalytic performance in the benzylation of aromatics
with benzyl alcohol over hierarchical mordenite...................................................................185
K. Leng, Y. Wang, Y. Sun
26
P-1.3-58 CoZr/Mesoporous Zeolite Hβ Hybrid Catalyst for Efficient Synthesis of C5-18
Paraffins from Syngas ..........................................................................................................186
Xing Huang, Bo Hou, Jungang Wang, Debao Li, Litao Jia, Yuhan Sun
P-1.3-59 Hierarchical SAPO-11: synthesis, characterization and catalytic behavior in long
chain n-alkane hydroisomerization .....................................................................................186
R. Bértolo, A. Fernandes, M. F. Ribeiro, J. M. Silva, A. Martins
SECTION 1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc).......187
P-1.4-01 Flexibility of ZIF-8 structure studied by 129Xe NMR .............................................187
Marie-Anne Springuel-Huet, Andrei Nossov, Flavien Guenneau, Antoine Gédéon
P-1.4-02 Synthesis and characterization of Zeolite/Fe3O4 nanocomposite material and
investigation catalytic reaction of it .......................................................................................187
Mojgan Zendehdel, Safura Molla Mohammad Zamani
P-1.4-03 The Secret of the Maya Blue. A Story of Microporous Solid .................................187
E. Lima, A. Guzmán, M. Vera, J.-L. Rivera, J. Fraissard
P-1.4-04 Fluorinated Hydrotalcites: A New Family of Layered Double Hydroxides ............188
Enrique Lima, María de Jesús Martínez-Ortiz, Jorge L. Flores-Moreno
P-1.4-05 In Situ Generated Metal Nanoparticles on Porous Copper Chlorophosphate
Frameworks for Catalytic Aerobic Oxidations ....................................................................188
C. S. Hinde, R. Leithall, T.S.A. Hor, R. Raja
P-1.4-06 Layered lanthanide 1,3,5-benzenetriphosphonates pillared with organic cationic
species ....................................................................................................................................188
Takahiro Araki, Atsushi Kondo, Kazuyuki Maeda
P-1.4-07 Synthesis of Metal-Free Highly Nitrogen-Doped Carbon Porous Materials for
Oxygen Reduction Reaction in DMFC..................................................................................189
Chin-Te Hung, Ningya Yu, Yu-Siang Kao, Tuan-Chi Liu, Shang-Bin Liu
P-1.4-08 Selective olefin’s formation from butanol-2 on mesopores iron-phosphates LISICON
and NASICON catalysts ........................................................................................................189
A.I. Pylinina, I.I. Mikhalenko
P-1.4-09 Impact of group VI metals on Ni/MgO for catalytic growth of CNTs by ethylene
chemical vapor deposition .....................................................................................................189
A. E. Awadallah
P-1.4-10 COK-16: a tunable MOF with cation exchange properties.....................................190
Sneha R. Bajpe, Eric Breynaert, Ana Martin-Calvo, Danilo Mustafa, Sofia Calero, Christine E. A.
Kirschhock, Johan A. Martens
P-1.4-11 Preparation of magnetic ZIF-based core-shell structure and its potential application
in a microreactor ...................................................................................................................190
Tong Zhang, Xinjuan Yan, Haiou Liu, Xiongfu Zhang
P-1.4-12 Enhanced luminescent performance of hybrid mesoporous silicas via grafting by 1,8naphthalic anhydride and then modification with Europium...............................................190
F. Wang, J.P. Wang, S.Y. Bai, J.H. Sun
P-1.4-13 Versatile and Scalable Cooperative Template-Directed Coating Method to Construct
Uniform Microporous Carbon Shell for Multifunctional Core-shell Nanocomposites .........191
Buyuan Guan, Xue Wang, Yu Xiao, Yunling Liu, Qisheng Huo
P-1.4-14 Construction of Two 3D Copper-Based Coordination Polymers With
Multifunctional Ligand, PmBC.............................................................................................191
Jiahuan Luo, Jing Wang, Peng Tian, YunlingLiu, Lirong Zhang
P-1.4-15 Construction of Two 3D Metal-Organic Frameworks Based on 1,2,3-Triazole-4,5dicarboxylate Ligand.............................................................................................................191
Tingting Zhao, Dongmei Wang, Huoqi Sheng, Yunling Liu
27
P-1.4-16 Synthesis and Applications of Nitrogen-containing Ordered Mesoporous Carbons
...............................................................................................................................................192
Jinming Xu, Xiaochen Zhao, Aiqin Wang and Tao Zhang
P-1.4-17 Growing a porous γ-AlO(OH) layer of tunable thickness on MIL-53(Al) particles 192
I. Bezverkhyy, G. Ortiz, G. Chaplais, C. Marichal-Westrich, J.-P. Bellat
P-1.4-18 Metal-organic frameworks as strong basic catalysts via post-synthetic deprotonation
of hydroxyl groups.................................................................................................................192
P. Valvekens, D. Jonckheere, D. De Vos
P-1.4-19 Fast Synthesis of MOFs Using Nanosized Zeolite Crystal Seeds.............................193
Suyan Liu, Ying Zhang, Yan Meng, Fei Gao
P-1.4-20 Cu Schiffbase Functionalized Periodic Mesoporous Organosilica: A Highly Stable
Heterogeneous Catalyst .........................................................................................................193
X.F. Shi, X.H. Hu, B.B. Fan, W.B. Fan, R.F. Li
P-1.4-21 Highly porous neutral, acid and basic micro- and mesoporous carbon materials:
synthesis and properties .......................................................................................................193
N.D. Scherban, P.S. Yaremov, V.G. Ilyin, S.M. Filonenko
P-1.4-22 Determining the indomethacin loading efficiency in isostructural MIL-101
frameworks with the solid-state NMR...................................................................................194
Tomaž Čendak, Emanuela Žunkovič, Tina Ukmar, Venčeslav Kaučič, Gregor Mali
P-1.4-23 Synthesis and crystal structures of two new microporous copper rubidium
diphosphates .........................................................................................................................194
L.V. Shvanskaya, O.V. Yakubovich, V.S. Urusov
P-1.4-24 Anomalous paraffin selectivity of ZIF-7 in the separation of light olefin/paraffin
mixtures.................................................................................................................................194
Canan Gücüyener, Johan van den Bergh, Jorge Gascon, Freek Kapteijn
P-1.4-25 Synthesis of porous materials based on a Si-N network in Ionic Liquids................195
Ana Isabel Saugar, Joaquín Pérez-Pariente
P-1.4-26 Materials Center – Materials for every Challenge ..................................................195
Ronny Grünker, Martin R. Lohe, Stefan Kaskel
P-1.4-27 Kinetic Water Stability of an Isostructural Family of Zinc-based Pillared MetalOrganic Frameworks ............................................................................................................195
Himanshu Jasuja, Nicholas C. Burtch, You-gui Huang, Yang Cai, Krista. S. Walton
P-1.4-28 Zr and Hf based Metal-Organic Frameworks.........................................................196
Volodymyr Bon, Irena Senkovska, Volodymyr Senkovskyy, Stefan Kaskel
P-1.4-29 Mesoporous carbon functionalized with Ni nanoparticles for hydrogen storage....196
D. Fernand, P.L. Llewellyn, V. Hornebecq
P-1.4-30 Synthesis and properties of photochromic quartz-like glasses ...............................196
M.A. Girsova, I.N. Anfimova, T.V. Antropova, O.A. Pshenko
P-1.4-31 N-containing heterocyclic carboxylate−CaFe layered double hydroxide
nanocomposites − synthesis, characterisation and some catalytic reactions..........................197
M. Sipiczki, Á. Kukovecz, Z. Kónya, P. Sipos, I. Pálinkó
P-1.4-32 Synthesis and characterization of Zn-tartarate MOF.............................................197
Ana Palčić, Matjaž Mazaj, Emanuela Žunkovič, Josip Bronić
P-1.4-33 Synthesis, Characterization, and CO2 Adsorption Properties of Chromium-based
MOF-Graphene Oxide Composite.........................................................................................197
Zhou Xin, Xia Qibin, Li Zhong
P-1.4-34 Enhancement of the mechanical resistance of Metal Organic Frameworks by
functionalization: A subtle combination of X-ray diffraction and molecular simulations ....198
P.G. Yot, Y. Ke, F. Salles, P. Horcajada, T. Devic, C. Serre, G. Férey, G. Maurin
28
P-1.4-35 Controlled defect introduction during synthesis as a novel tool to improve the
catalytic activity of Zr-MOF UiO-66.....................................................................................198
Frederik Vermoortele, Bart Bueken, Ben Van de Voorde, Alexandre Vimont, Dirk De Vos
P-1.4-36 Crystal Structures, Sorption Properties and Photochemistry of a Versatile Series of
Aluminium MOFs..................................................................................................................198
H. Reinsch, M. A. van der Veen, F. Hinterholzinger, T. Bein, D. De Vos, N. Stock
P-1.4-37 Synthesis and characterization of Mixed ligand Zr-MOFs. ...................................199
Sachin Chavan; Stian Svelle, Silvia Bordiga, Karl Petter Lillerud
P-1.4-38 EPR study of the mobility of nitroxide radicals confined in MIL-53(Al) nanochannel
system ....................................................................................................................................199
Alena Nishchenko, Matvey Fedin, Alexander Stepanov, Daniil Kolokolov, Anton Gabrienko,
Sergey Gromilov, Inna Shundrina, Elena Bagryanskaya
P-1.4-39 Mg- and Ca-based metal-organic frameworks: from design to application............199
M. Mazaj, T. Birsa Čelič, M. Rangus, G. Mali, N. Zabukovec Logar, V. Kaučič
P-1.4-40 A combined computational and experimental FTIR study of CH4 and CO2
adsorption on Porous Aromatic Framework (PAF) materials ..............................................200
G . Gatti, M . Errahali, L. Canti, L. Tei, M . Cossi, L. Marchese
P-1.4-41 Chemical and thermal switch in copper-based MOF materials .............................200
B. Gil, B. Marszalek, R.E. Morriss
P-1.4-42 Controlling hydrothermal stability of Zn-MOF materials......................................200
T. Birsa Čelič, M. Mazaj, M. Rangus, T. Čendak, G. Mali, N. Zabukovec Logar
P-1.4-43 Alternate Layered Nanostructures using Click Reaction of Organic-modified Metal
Oxides ....................................................................................................................................201
Dai Mochizuki, Kozue Kumagai, Funinao Kishimoto, Masato Maitani, Yuji Wada
P-1.4-44 Dual Template-Directed Synthesis of Hierarchically Zeolitic Imidazolate
Framework-8 (ZIF-8) in an Aqueous System with Enhanced Porosity.................................201
Y.N. Wu, B.Z. Wu, F.T. Li
P-1.4-45 Stability of CPO-27 materials upon activation and rehydration.............................201
Mojca Rangus, Benjamin Barth, Martin Hartmann
P-1.4-46 A novel (3,3,6)-connected luminescent metal-organic framework for sensing of
nitroaromatic explosives........................................................................................................202
Libo Sun, Xiaowei Song, Zhiqiang Liang, Jihong Yu, Ruren Xu
P-1.4-47 Pillar-Layer Assembly of Four Novel Cd-based Metal-Organic Frameworks with
Structural Varieties Derived from the Replacement of Organic Linkers .............................202
Fang Wang, Xuemin Jing, Bing Zheng, Guanghua Li, Guang Zeng, Qisheng Huo, Yunling Liu
P-1.4-48 Evaluation of CTA-MCM-41 modified with polyacrylates for use in catalytic
transesterification..................................................................................................................202
F. T. Cruz, D. Cardoso
P-1.4-49 Nanocrystalline M-MOF-74 (M= Mg, Mn, Co, Ni, Zn) prepared at room
temperature ..........................................................................................................................203
Manuel Díaz-García, Manuel Sánchez-Sánchez, Álvaro Mayoral, Isabel Díaz
P-1.4-50 Effect of Solvent Reduction on the Synthesis of the Highly Robust Zr-BDC (UiO-66)
MOF .....................................................................................................................................203
Himanshu Jasuja, Deonte Fletcher, Krista S. Walton
P-1.4-51 Non-classic Crystal Growth of Some Selected MOFs..............................................203
H. F. Greer, C. M. Zheng, Y. H. Liu, R. E. Morris, W. Z. Zhou
P-1.4-52 Phase transformations in the system of two iron carboxylates................................204
T. Birsa Čelič, M. Rangus, V. Kaučič, N. Zabukovec Logar
P-1.4-53 The study of I2 guest molecule binding ability in different organic solution of PAF-1
and JUC-Z2 ...........................................................................................................................204
Cuiying Pei, Teng Ben, Shilun Qiu
29
SECTION 1.5. Zeolite and MOF membranes and films ...........................................................205
P-1.5-01 Synthesis and characterization of nanocomposite Ge-MFI alumina membranes for
CO2/N2 separation from wet flue gases..................................................................................205
C-H. Nicolas, M. Pera-Titus,
P-1.5-02 Oriented Zeolite Membranes: Preparation, Characterization and Special Wettability
...............................................................................................................................................205
Jiancheng Di, Xiaofang Wang, Kangjian Tang, Yangdong Wang, and Weimin Yang
P-1.5-03 Oriented Heterostructured Surface Mounted Metal-Organic Frameworks:
[Cu3btc2]@[Cu2(ndc)2(dabco)] ..............................................................................................205
Min Tu, Roland A. Fischer
P-1.5-04 Improved performance of supported zeolite and MOF membranes by chemical
support modification for seeding-free syntheses....................................................................206
J. Caro, A. Huang
P-1.5-05 Synthesis and surface modification of silicalite membranes ...................................206
N.A. Kosinov, E.J.M. Hensen
P-1.5-06 Zeolite hybrid films for space decontamination ......................................................206
N. Lauridant, T.J. Daou, G. Arnold, H. Nouali, J. Patarin, D. Faye
P-1.5-07 Synthesis of ion-exchanged SAPO-34 zeolite membrane.........................................207
Yanfeng Zhang, Meng Li, Dongyan Zheng, Yuhan Sun
P-1.5-08 Sulfur stabilized sodalite for membrane applications .............................................207
Christiane Günther, Hannes Richter, Ingolf Voigt
P-1.5-09 Zeolite membranes on full zeolite bodies.................................................................207
Hannes Richter, Gundula Fischer, Ingolf Voigt
P-1.5-10 Sod-ZMOF/Matrimid Mixed Matrix Membranes for CO2/CH4 Separation...........208
A. Kılıç, Ç. Atalay-Oral, A. Sirkecioğlu, Ş.B. Tantekin-Ersolmaz, M.G. Ahunbay
P-1.5-11 ZIF-8 mixed matrix membranes for natural gas and exhaust gas purification.......208
L. M. Diestel, X. Liu, F. Steinbach, Y. Li, W. Yang, J. Caro
P-1.5-12 Zeolite MFI membranes on inexpensive supports for pervaporation .....................208
Zhengbao Wang, Yong Peng, Zhiying Zhan, Yushan Yan
P-1.5-13 Hexane isomers separation through tubular silicalite-1 membrane........................209
M. Matsukata, T. Kaneko, M. Sakai
P-1.5-14 Effect of Na+ Cation on the Water/Acetic acid Separation through Mordenite
Membrane .............................................................................................................................209
M. Matsukata, Y. Imanishi, M. Narashima
P-1.5-15 SBS/Aminated SBA-15 Mixed Matrix Membranes For Gas Separation ................209
Maria Giovanna Buonomenna, Giovanni Golemme, Cristina Maria Tone, Maria Penelope De
Santo, Federica Ciuchi, Enrico Perrotta
P-1.5-16 Elucidating the kinetics of pentene cracking on H-ZSM-5 by combining theory with
experiment .............................................................................................................................210
J. Van der Mynsbrugge, S. Schallmoser, M. Waroquier, J.A. Lercher, V. Van Speybroeck
P-1.5-17 Zeolite Films: A New Synthetic Approach ..............................................................210
Davinder S. Bhachu, Andrew J. Smith, Ivan P. Parkin, Andrew J. Dent, Gopinathan Sankar
P-1.5-18 Self-templated Synthesis of Porous Coordination Polymer thin Films based on Metal
Oxides ....................................................................................................................................210
K. Khaletskaya, H. Parala, R. A. Fischer
P-1.5-19 Cascade pervaporation through polymer and zeolite membranes for biobutanol
recovery .................................................................................................................................211
D.A. Fedosov, A.V. Smirnov, E.E. Knyazeva, I.L. Borisov, V.V. Volkov, I.I. Ivanova
P-1.5-20 Ionothermal Synthesis of Aluminophosphate Molecular Sieve Membranes through
Substrate Surface Conversion ...............................................................................................211
Xiaolei Li , Keda Li , Zhijian Tian, Renshun Xu, Huaijun Ma, Bingchun Wang
30
P-1.5-21 The preparation of the integrated metal-organic framework membranes on ceramic
support under mild conditions ..............................................................................................211
V.I. Isaeva, M.I. Barkova, M.M. Ermilova, E.A. Mironova, A.V. Kucherov, L.M. Kustov
P-1.5-22 Electrospinning technology applied in the synthesis of Zeolite and MOF membranes
...............................................................................................................................................212
L. Fan, Z. Kang, M. Xue, S. Qiu
P-1.5-23 Pure silica LTA zeolite membranes on porous alumina supports...........................212
M. Palomino, H. Ono, S. Valencia, A. Corma
P-1.5-24 Electrochemical Synthesis of cobalt containing Metal-Organic frameworks..........212
S. K. Vankova, M. Cataldo Hernandez, M. Thalluri, N. Russo, G. Saracco
P-1.5-25 Preparation of b-oriented HZSM-5 multilayer on stainless steel tube with
remarkably enhanced catalytic performances.......................................................................213
Meiling Ji, Guozhu Liu, Li Wang, Xiangwen Zhang
P-1.5-26 Separation of CH4/CO2 binary mixtures using micro- and nano-sized ZIF-8
membranes ............................................................................................................................213
J. Cookney, K. Lecoanet, P. Hrabanek, V. Fila
P-1.5-27 Size and Drying Effects on Preparation of Nafion/ZSM-5 Composite Membranes
for DMFC Application ..........................................................................................................213
Wei-Jen Chou, Soofin Cheng
P-1.5-28 Amine-Functionalized MIL-53 Metal-Organic Framework and Aminosilanes
Grafted FAU/EMT zeolite In Polyimide Mixed Matrix Membranes for CO2/CH4 Separation
...............................................................................................................................................214
Xiao Yuan Chen, Vinh-Thang Hoang, Omid Ghaffari Nik, Denis Rodrigue, Serge Kaliaguine
P-1.5-29 Fabrication of new mixed matrix membranes based on poly-etherimide and metal
organic frameworks...............................................................................................................214
M. Galizia, N. Gargiulo, D. Caputo, P. Musto, G. Mensitieri
SECTION 2. Advances in fundamental understanding of structure and properties ................215
SECTION 2.1. Theory and modeling ........................................................................................216
P-2.1-01 Methane, hydrogen and carbon dioxide adsorption in porous aromatic frameworks
(PAFs): a computational study..............................................................................................216
M. Cossi, G. Gatti , L. Canti, M. Errahali , L. Tei, L. Marchese
P-2.1-02 A theoretical study of hydrocarbon pool mechanism for methanol-to-olefins
conversion in HSAPO-34: Cluster model ..............................................................................216
Chuan-Ming Wang, Yang-Dong Wang, Zai-Ku Xie
P-2.1-03 Enumeration and interpretation of ABC-6 zeolites via intuitive framework encoding
Yi Li, Jihong Yu, Ruren Xu .....................................................................................................216
P-2.1-04 Methanol carbonylation and oxidative carbonylation over alkaline earth and
transition metal zeolites .........................................................................................................217
Andrei A. Rybakov, Alexander V. Larin, Georgy M. Zhidomirov, Daniel P. Vercauteren
P-2.1-05 Impact of framework topology on CO2/N2 separation properties of zeolite
frameworks: A building-block based approach ....................................................................217
Michael Fischer, Robert G. Bell
P-2.1-06 Modeling of structure, sorption, and transport in zeolite-impregnated membranes
for gas separation ..................................................................................................................217
A.J. Petsi, V.N. Burganos
P-2.1-07 Distribution of Al and Adsorption of NH3 and Pyridine in ZSM-12: A
Computational Study ............................................................................................................218
G. Feng, Y.-Y. Lian, X. Qi, D. Yang, J. Liu, D. Kong
31
P-2.1-08 Understanding adsorption and diffusion of highly polar vapors on mesoporous
MOFs through a combined experimental and molecular simulation approach...................218
M. F. De Lange, J. J. Gutierrez-Sevillano, S. Hamad, J. Gascon, T.J.H. Vlugt, S. Calero, F.
Kapteijn
P-2.1-09 Electronic propensity of Cu(II) / Cu(I) sites in zeolites to activate NO: spin- and
orbital-resolved Cu–NO electron transfer.............................................................................218
E. Broclawik, P. Kozyra, M. Radon, A. Stępniewski, J. Datka
P-2.1-10 Atomic structure of Fe- and Ti- substituted thin films of silica on Ru(0001) .........219
F.D. Fischer, R. Wlodarczyk, J. Sauer, X. YuJ.A. Boscoboinik, E. Emmez, B. Yang, S.
Shaikhutdinov, H.-J. Freund
P-2.1-11 Theoretical Study of Effects of Exchangeable Cations on Electronic, Structural
Properties of ETS-10 .............................................................................................................219
M. Koç, D. Toffoli, H.Toffoli, B.A. Kurç
P-2.1-12 Computational Approach of the Inverse Sigma Transformation of Zeolites ..........219
Elke Verheyen, Lennart Joos, K.Van Havenbergh, E. Breynaert, N. Kasian, E.Gobechiya, K.
Houthoofd, C. Martineau, M. Hinterstein, F. Taulelle, Veronique Van Speybroeck, Michel
Waroquier, S.Bals, G.Van Tendeloo, Christine E.A. Kirschhock, Johan A. Martens
P-2.1-13 Enhancing diffusion selectivities in FER-type structures by molecular traffic control
...............................................................................................................................................220
C. Chmelik, F. Hibbe, A. Lauerer, J. Kärger, J.M. van Baten, R. Krishna, V.R.R. Marthala, J.
Weitkamp
P-2.1-14 A DFT study on the acidity of SAPO-34 molecular sieves with different Si contents
...............................................................................................................................................220
Yanyan Chen, Zhihong Wei, Junfen Li, Mei Dong, Zhangfeng Qin, Weibin Fan, Jianguo Wang
P-2.1-15 Effect of Electrostatic Properties on VOCs Binding in IRMOFs: Density Functional
Theory Study .........................................................................................................................220
Wu Ying, Wu Yongbiao, Liu Defei, Xia Qibin, Li Zhong, Xi Hongxia
P-2.1-16 Water adsorption in a flexible metal-organic framework (IM19): adsorption-induced
structural transition and hydrothermal stability ..................................................................221
V. Haigis, D. Bousquet, F.-X. Coudert, A.H. Fuchs, R. Vuilleumier, A. Boutin
P-2.1-17 Computational design of a highly gas selective acidic substituted porous Zr
terepthalate toward the synthesis & adsorption characterization.........................................221
Qingyuan Yang, Dong Wu, Sébastien Vaesen, Ana Lago, Florence Ragon, Thomas Devic,
Christian Serre, Guy De Weireld, Philip Llewellyn, Chongli Zhong, Guillaume Maurin
P-2.1-18 Evaluation of site occupancy factors in refinements of zeolite-type crystal structures
...............................................................................................................................................221
R.X. Fischer, W.H. Baur
P-2.1-19 A theoretical study of Cu2O and Cux clusters hosting in MOR dealuminated zeolite
...............................................................................................................................................222
D. Homero Galván, Joel Antúnez-García, Vitalii Petranovsky
P-2.1-20 Application of DFT calculations to study the active site on the MCM-41 with Tatoms substituted...................................................................................................................222
E.O. Castrejón-González, J.C. Fierro-González, G. Herrera-Pérez
P-2.1-21 Lithium as a Trojan Horse for Aluminum Incorporation in Zeolites .....................222
Lennart Joos, Leen Van Tendeloo, K. Lauwers, Y. Lorgouilloux, Veronique Van Speybroeck,
Christine E. A. Kirschhock, Johan A. Martens
P-2.1-22 Molecular Simulation of Zn+, Cu2+, NH4+ Ion-Exchange on Clinoptilolites ............223
B. Demir, R. Ekhteiari Salmas, A. Sirkecioglu, M. Yurtsever, M.G. Ahunbay
P-2.1-23 Molecular simulation by KMC of early stages of zeolites nucleation and study of
synthesis parameters..............................................................................................................223
M. Ciantar, C. Nieto-Draghi, C. Mellot-Draznieks, P. Sautet, Thuat T. Trinh
32
SECTION 2.2. Advanced characterization techniques .............................................................224
P-2.2-01 Synthesis of gold catalysts supported on Ce-modified mesoporous zirconia: Effect of
Ce/Zr molar ratio on the dispersion of gold particles............................................................224
H. Azzi, L.Aouali-Chérif, S. Siffert, S.Royer, A.Aissat, R. Coussin,S. Spronier,A. Bengueddach.
P-2.2-02 Dehydration dynamics of levyne: evidence for a new zeolite topology...................224
Rossella Arletti, Simona Quartieri, Giovanna Vezzalini, Fernando Cámara
P-2.2-03 Estimation of the real temperature of samples in IR cell using OH frequency of silica
...............................................................................................................................................224
H. Yamazaki, H. Shima, E. Yoda, T. Yokoi, T. Tatsumi, J.N. Kondo
P-2.2-04 Structural characterization of fluorenone dye in zeolite L......................................225
L. Gigli, G. Agostini, R. Arletti, E. Fois, C. Lamberti, G. Tabacchi, S. Quartieri, G. Vezzalini
P-2.2-05 New phospho-silicate and niobo-phospho-silicate MCF materials modified with
MPTMS – structure, surface and catalytic properties ..........................................................225
K. Stawicka, M. Trejda, M. Ziolek
P-2.2-06 Direct hydrothermal synthesis of monodisperse nickel oxide in SBA-15, and its
enhanced catalytic selectivity.................................................................................................226
Baowang Lu, Katsuya Kawamoto
P-2.2-07 Synthesis of Silica-alumina with Tunable Acidity Investigated by MAS NMR
Spectroscopy..........................................................................................................................226
Jun Huang, Yijiao Jiang, Alfons Baiker, Michael Huang
P-2.2-08 Powder Diffraction Analysis of Porous Structures Using the Derivative Difference
Method...................................................................................................................................227
L.A. Solovyov, A.G. Anshits, S.N. Vereshchagin, G.V. Echevsky, A.V. Toktarev
P-2.2-09 Evaluation of the behavior of nitrogen and sulphur compounds whith adsorbents in
fixed bed to be used in pre treatment of diesel in hydrotreatments units..............................227
L.S. Silva, M.A.G. Figueiredo
P-2.2-10 Exploring diffusion and reaction in nanoporous catalysts by IR micro-imaging....227
Tobias Titze, Christian Chmelik, Dirk Enke, Roger Gläser, Jens Kullmann, Jörg Kärger, Lutz
Prager, Jens Weitkamp
P-2.2-11 Characterizing the Hydrothermal Stability of Zeolites for Thermal Energy Storage
Applications...........................................................................................................................228
F. Fischer, A. Hauer, E. Lävemann
P-2.2-12 Investigation of distribution and chemical state of Ti species in deactive Hollow TS-1
zeolite from industrial ammoxidation processing..................................................................228
Changjiu Xia, Yanjuan Xiang, Bin Zhu, Aiguo Zheng, Min Lin, Xu Guangtong, Xingtian Shu
P-2.2-13 Investigation of the templates in microporous SAPO STA-7 and MgAPO STA-15
using polarised synchrotron IR radiation..............................................................................229
E. C. Eschenroeder, A. Turrina, L. Picone, G. Cinque, P. Cox, R. Howe, P. A. Wright
P-2.2-14 Local order in zeolites from 14N NMR ...................................................................229
Eddy Dib, Bruno Alonso
P-2.2-15 Nonlinear optical spectroscopy reveals the external surface and phase transitions of
metal-organic frameworks.....................................................................................................230
Monique A. van der Veen, Helge Reinsch, Karen Markey, Ivo Stassen, Thierry Verbiest, Mischa
Bonn, Norbert Stock, Ellen H.G. Backus, Dirk E. De Vos
P-2.2-16 Characterization of Zeolites via Isomerization and Disproportionation of 1,3Dimethylbenzene, 1,3-Diethylbenzene and 1,3-Diisopropylbenzene as Catalytic Test Reactions
...............................................................................................................................................230
C.Y. Chen, R. Bermejo-Deval, S.I. Zones, S.A. Elomari, D. Xie
33
P-2.2-17 A Synergic Exploration of the Rotational Dynamics of MOFs upon Drug
Encapsulation by Combining Dielectric Relaxation Spectroscopy & Molecular Simulations
...............................................................................................................................................230
S. Devautour-Vinot, G. Maurin, D. Cunha, P. Horcajada, C. Serre
P-2.2-18 Influence of the nitric acid treatment on framework composition and acidity of BEA
zeolite: MQ MAS NMR and FTIR studies ............................................................................231
R. Baran , Y. Millot, T. Onfroy, J.-M. Krafft, T. Grzybek, S. Dzwigaj
P-2.2-19 Preparation of Highly Dispersed Pt on Beta by the Assistance of Cr......................231
Yoshiyuki Izutsu, Yusuke Hidaka, Yoshiki Nakajima, Jun Fukuroi, Kaname Yoshida, Yukichi
Sasaki, Masahiko Matsukata
P-2.2-20 Structure determination of a new interrupted zeolite PKU-14 by combining powder
X-ray diffraction, rotation electron diffraction, NMR and IR spectroscopy.........................231
Jie Su, Jie Liang, Yingxia Wang, A. Ken Inge, Junliang Sun, Xiaodong Zou, Jianhua Lin
P-2.2-21 Luminescence activity of irradiated SiO2-clathrate Melanophlogite ......................232
G. Buscarino, L. Vaccaro, M. Cannas, F.M. Gelardi, R. Boscaino
P-2.2-22 Titanium Site Dispersion and Catalytic Epoxidation Activity Control in Mesoporous
Silica Capped using a Dipodal Organosiloxane.....................................................................232
L. Fang B. Albela, B. Yang, Y. Zheng, P. Wu, M.-Y. He, L. Bonneviot
P-2.2-23 9,10-Anthraquinone Paramagnetic Complexes on Surfaces of Zeolites and Their
Thermal Transformations .....................................................................................................233
A.V. Fionov, I.Yu. Shchapin, A.I. Nekhaev, A.L. Maximov, V.V. Lunin
P-2.2-24 3D electron diffraction, a new solution for structural studies of micro-sized porous
crystalline solids.....................................................................................................................233
D.L. Zhang, S.L. Qiu
P-2.2-25 The structure of two new disordered zeolites ITQ-38 and ITQ-39 solved by electron
crystallography......................................................................................................................233
T. Willhammar, J.L. Sun, W. Wan, P. Oleynikov, D.L. Zhang, X.D. Zou, M. Moliner, J. Gonzalez,
C. Martínez, F. Rey, A. Corma
P-2.2-26 NMR and powder diffraction crystallography of a layered aluminophosphate :
determination of the average structure, description of non-periodic sub-networks and water
cycle .......................................................................................................................................234
B. Bouchevreau, C. Martineau, C. Mellot-Draznieks, A. Tuel, F. Taulelle
P-2.2-27 Evaluation of texture of micro/mesoporous materials from standard nitrogen
adsorption data. A new practical approach...........................................................................234
Pavol Hudec
P-2.2-28 Application of in situ and ex situ X-ray techniques for the study of metal ions
substituted microporous materials ........................................................................................234
G. Sankar, M. Martis, K. Simmance, A.J. Smith
P-2.2-29 Speciation of OH groups of steamed zeolites by H-D exchange and inversion of time
resolved FTIR spectra ...........................................................................................................235
S. Sirotin, A. Travert, A. Vimont, V. Valtchev, J.-P. Gilson, R. Bergstraesser, S. Wellach
P-2.2-30 Crystallographic Verification that Copper(II) Coordinates to Four of the Oxygen
Atoms of Zeolite 6-Rings in Two Single-crystal Structures of Fully Dehydrated, Largely Cu2+exchanged Zeolite Y (FAU, Si/Al = 1.56) ..............................................................................235
S. M. Seo, W. T. Lim, K. Seff
P-2.2-31 How Acid Characteristics of Deactive Industrial Hollow TS-1 Zeolite Influences Its
Catalytic Oxidation Performance? .......................................................................................235
Changjiu Xia, Bin Zhu, Min Lin, Xingtian Shu
P-2.2-32 Formation peculiarities of hollow copper particles supported on ZSM-5...............236
S. A. Yashnik, V.I.Zaikovskii, Z.R. Ismagilov
34
P-2.2-33 MZ-35, a new layered pentasil borosilicate synthesized in the presence of large alkali
cations....................................................................................................................................236
Rossella Arletti, Enrico Mugnaioli, Ute Kolb, Francesco Di Renzo
P-2.2-34 The influence of bimodal porosity on ZSM-5 deactivation during methanol
conversion studied by operando AGIR spectroscopy............................................................236
Louwanda Lakiss, Zhengxing Qin, Philippe Bazin, Karine Thomas, Valentin Valtchev and
Christian Fernandez
P-2.2-35 3-D Location and Orientation of ZSM-5 Crystals within the Matrix of a Fluid
Catalytic Cracking Particle ...................................................................................................237
C. Sprung, A. M. Beale, B. M. Weckhuysen
P-2.2-36 Determination of the acidic properties of non-Brønsted acidic zeolites by using
solvatochromic probe molecule .............................................................................................237
M. Hureau, A. Moissette, K. Smirnov, H. Jobic
P-2.2-37 Solid-state NMR Characterization of Metal Center Environment in Metal-organic
Frameworks at Ultrahigh Magnetic Field .............................................................................237
J. Xu, P. He, A. Sutrisno, V. V. Terskikh, Y. Huang
SECTION 2.3. Mechanistic studies; impact of in-situ and operando techniques ......................238
P-2.3-01 Mobility of tert-Butyl Alcohol in MFI Framework Type Studied by Deuterium NMR
...............................................................................................................................................238
Alena M. Nishchenko, Daniil I. Kolokolov, Anton A. Gabrienko, Alexander G. Stepanov
P-2.3-02 Structure-directing effect of piperazine revealed by reverse temporal evolution
processes ................................................................................................................................238
W.F. Yan, X.Q. Tong, J. Xu, J.H. Yu, F. Deng, R.R. Xu
P-2.3-03 In situ MAS NMR for Investigation of Acidity, Porosity and Reaction Mechanism of
Silicoaluminate and Silicoaluminophosphate Catalysts ........................................................239
S.T. Xu, Y.X. Wei, L.H. Chen, P. Tian, J.Z. Li, J.R. Chen, X. Su, Q.Y. Wang, Y. Zhou, J.B. Wang,
M.Z. Zhang, B.L. Su, Z.M. Liu
P-2.3-04 Deactivation of HTS catalyst for ammoximation of Acetone ..................................239
Yi Wang, Shengjian Zhang, Yingxian Zhao
P-2.3-05 Studies on the crystallization process of SAPO-35..................................................240
P. Tian, B. Li, D. Wang, L. Zhang, S. Xu, X. Su, D. Fan, Y. Qi, Z. Liu
P-2.3-06 Differences in acid-base properties of Nb species located in the framework of zeolites
and mesoporous molecular sieves estimated by in-situ NO adsorption.................................240
I. Sobczak, A. Wojtaszek, M. Ziolek
P-2.3-07 Direct identification of carbenium cations and their role during MTO conversion
over SAPO molecular sieves ..................................................................................................241
J.Z. Li, Y.X. Wei, J.R. Chen, S.T. Xu, P. Tian, B. Li, Xiong Su, Y. Zhou, Q.Y. Wang, G.Y. Liu,
Z.M. Liu
P-2.3-08 The investigation of interaction between modified ZSM-5 zeolites and dimethyl ether
by means of in situ high-temperature diffusive reflectance FTIR spectroscopy ...................241
A.S. Rodionov, G.N. Bondarenko, N.V. Kolesnichenko, G.N. Shirobokova, E.N. Khivrich
P-2.3-09 Elementary steps of light olefin cracking on MFI type zeolites...............................241
S. Schallmoser, A.C. van Veen, J.A. Lercher
P-2.3-10 Molecular and dissociative adsorption of H2O on Zn/ZSM-5 zeolite .....................242
A.N. Subbotin, G.M. Zhidomirov, I.R. Subbotina, V.B. Kazansky
35
P-2.3-11 Acidic properties of Ag- and Cu-exchanged Y zeolites prepared by solid state ion
exchange ................................................................................................................................242
F. Benaliouche, Y. Boucheffa, F. Thibault-Starzyk
P-2.3-12 The study of the transformation of dimethyl ether in the presence of p-xylene on
zeolite ZSM-5 catalysts by means of in situ high-temperature diffuse reflectance FTIRspectroscopy...........................................................................................................................242
Y.V. Pavluk, G.N. Bondarenko, N.V. Kolesnichenko
P-2.3-13 NH3-SCR of NOx over Cu-zeolites for Diesel engine applications: reactivity and
spectroscopy study under real catalytic conditions ...............................................................243
F. Giordanino, S. Bordiga, C. Lamberti, F. Bonino, P. Beato
P-2.3-14 A study on Zn- and Ga- containing ZSM-5 catalysts for MTA reaction by in situ
XAFS and DFT calculation....................................................................................................243
Xianjun Niu, Qing Miao, Mei Dong, Guofu Wang, Weibin Fan, Zhangfeng Qin, Jianguo Wang
P-2.3-15 Photoinduced electron transfers in zeolites: Impact of the aluminum content on the
activation energies .................................................................................................................243
M. Hureau, A. Moissette
P-2.3-16 In situ spectral kinetic study of ethanol conversion over zeolite hzsm-5 catalyst....244
V.F. Tretyakov, K.V. Tretyakov, O.N. Silchenkova, V.A. Matyshak
P-2.3-17 Role of radical “coke” in ethanol transformation into hydrocarbons over HZSM-5
zeolite.....................................................................................................................................244
S. Hamieh, L. Pinard, K. Ben Tayeb, H. Vezin, C. Canaff, S. Maury, O. Delpoux, Y. Pouilloux
P-2.3-18 Mechanism and kinetics of Metal-Organic Framework Crystallization investigated
by Time-Resolved X-ray Scattering.......................................................................................244
M.G. Goesten, J. Juan-Alcañiz, C. Gucuyener, E. Stavitski, A. Petukhov, E. Pidko, E.J.M. Hensen,
F. Kapteijn, J. Gascon
P-2.3-19 The high thermal stability of the zeolite K-L: dehydration mechanism by in-situ SRXRPD experiments ................................................................................................................245
Lara Gigli, Rossella Arletti, Simona Quartieri, Francesco Di Renzo, Giovanna Vezzalini
P-2.3-20 Crystal Growth and Materials Discovery of Metal Organic Frameworks Revealed by
Atomic Force Microscopy......................................................................................................245
P. Cubillas, M. W. Anderson, M. P. Attfield
SECTION 3. Industrial and emerging applications ..................................................................247
SECTION 3.1. Oil refinery and petrochemistry .......................................................................248
P-3.1-01 Preparation of Mesoporous Ce-Ni2P/SBA-15 Catalysts and Their Catalytic
Performance for Hydrodesulfurization of Dibenzothiophene ...............................................248
Qingyuan Li, Pingyi Wu, Ling Lan , Shengfu Ji, Hui Liu
P-3.1-02 The influence of desilication and dealumination on the activity of mordenite
catalysts in alkylation of aromatics with 1-alkenes................................................................248
M. Horňáček, M. Horňáčková, P. Lovás, P. Veis, P. Hudec, A. Smiešková, K. Velebná
P-3.1-03 Reactivities of C6-8 hydrocarbons and effect of coexisting hydrocarbon for cracking
on H-ZSM-5 catalyst at high temperatures ...........................................................................248
Takashi Takahashi, Kohei Kubo, Hajime Iida, Seitaro Namba, Akira Igarashi
P-3.1-04 The Research and Commercial Applications of the Catalysts for Ethylbenzene
Production via Benzene Ethylation in Gas Phase..................................................................249
Zhen-hao Shen, Hong-min Sun, Wei-min Yang
P-3.1-05 Catalytic cracking of n-Hexane to Produce Propylene on Organic structure directing
agent (OSDA) Free Beta Catalysts ........................................................................................249
Yong Wang, Toshiyuki Yokoi, Seitaro Namba, Junko N. Kondo, Takashi Tatsumi
36
P-3.1-06 Isomerization of n-Decane on Mesoporous Support Based Catalysts – Design of
Experiments in Combination with Kinetic Modeling ...........................................................249
A. Rüfer, A. Werner, W. Reschetilowski
P-3.1-07 Catalytic Dehydrogenation of Hydrocarbons over Iron-Silicate ZSM-5.................250
Jang Ho Yun, Raul F. Lobo
P-3.1-08 Preparation of MCM-48 supported Mo catalyst via carbide and sulfided with
elemental sulfur for hydrodesulfurization.............................................................................250
F. E. Imbert, L. Contreras, J. Brito, P. Rodriguez, M. Villarreal
P-3.1-09 The shape selective effect of BETA zeolite in FCC process.....................................250
Beiyan Chen, Ying Ouyang, Yuxia Zhu, Yibin Luo
P-3.1-10 Obtaining synthetic oils on the basis esters of dicarboxylic acids ...........................251
R.R. Shiriyazdanov, A.R. Davletshin, M.F. Kuzmenko, A.R. Karimova, U.I. Kazakbaev
P-3.1-11 Realumination of MCM-22 and its use in alkylation of benzene with LPG............251
Kefeng Liu, Huijuan Wei, Sujuan Xie, Shenglin Liu, Longya Xu
P-3.1-12 Joint conversion of n-butane and methanol over modified hzsm-5 zeolites ............251
D. B. Tagiyev, S. B. Agayeva, S. I. Abasov, R. V. Starikov, A. A. Imanova, N. S. Asadov, F.M.
Nasirova
P-3.1-13 Oxidative dehydrogenation of ethane over iron modified SBA-3............................252
E. Janiszewska, J. Kowalska-Kus, K. Nowinska, S. Kowalak
P-3.1-14 Propene and Butenes from Selective Ethene Conversion Over Acidic 10Membered Ring Zeolites......................................................................................................252
S. Follmann, S. Ernst
P-3.1-15 Synthesis of zeolite-type sorbents for sorption of petroleum hydrocarbons............252
W. Franus, M. Wdowin, M. Franus, L. Bandura
P-3.1-16 Synthesis of SAPO-41 using different templates and their catalytic performance in
n-decane hydroisomerization.................................................................................................253
Aijuan Zhao , Wei Wu, Rui Zhang, Min Liu, Huimin Wu, Linfei Xiao
P-3.1-17 Effect of Impurities in Benzene on Benzene Ethylation over MCM-22...................253
Shih-Yuan Chen, Tsung-Han Lin, Soofin Cheng, Chyi-Woei Young
P-3.1-18 Hydroisomerization of Long-Chain Paraffins over Nano-Sized Zeolite Pt/H-Beta.253
K. Ficht, F. Bauer, T. Kuchling, R. Gläser
P-3.1-19 Catalytic properties of zeolite-containing cracking catalysts with controlled content
of rare earth elements............................................................................................................254
T.P. Sorokina, V.P. Doronin, P.V.Lipin, O.V. Potapenko, V.I.Gordenko
P-3.1-20 Hydrogenation of tetralin over Ir-TiO2/SBA-16......................................................254
B. Ledesma, V. Valles, M. Martínez, O. Anunziata, A. Beltramone
P-3.1-21 Mixed Naphtha-Methanol as Feedstock in the Catalytic Cracking Process............254
Y.Y Ji, M.S. Zhang, J.Z. Jiang
P-3.1-22 Dehydrogenation of 4-vinylcyclohexene and ethyl benzene using carbon dioxide and
molecular oxygen on platinum-gallium pentasils modified with REE oxides........................255
Alimardanov Kh.M., Jalilova A.A., Abasov S.I., Suleymanova E.T.
P-3.1-23 Synthesis of nanoscale sulfide catalysts based on tungsten and nickel for
hydrodearomatization processes ...........................................................................................255
I.A. Sizova, A.S. Vilesov, D.V. Borisov, S.I. Serdyukov, A.L. Maximov, E.A. Karahanov
P-3.1-24 Synthesis and examination of catalytic properties of modified ZSM-5 type
aluminosilicates......................................................................................................................255
A.I. Terentyev, A.V. Vosmerikov, N.A. Yurkin, Ya.E. Barbashin, A.L. Khlytin, E.G. Poduryan
P-3.1-25 Effect of the channel system, aluminum content and acidity of H-zeolites in the
activity and light olefins yield during the cyclohexane cracking ...........................................256
Alexandre A. S. Gonçalves, Ernesto A. Urquieta-Gonzalez
37
P-3.1-26 Mesoporous Aluminosilicates-Supported Noble Metal Catalysts for Aromatics
Hydrogenation.......................................................................................................................256
S.I. Shirokopoyas, S.V. Lysenko, S.V. Baranova, A.L. Maximov, S.V. Kardashev, A.B. Kulikov,
N.F. Kovaleva, V.A. Ostroumova, E.A. Karakhanov
P-3.1-27 The effect of incorporation Zn species on the acidity and catalytic performance of
the nano-ZSM-5 zeolite in aromatization of 1-hexene...........................................................257
Gaoliang Wang, Wei Wu, Wang Zan, Wenjing Wang, Xin Qi
P-3.1-28 Synthesis of aluminum modified 3D mesoporous TUD-1 materials and catalytic
hydrotreating of FCC diesel ..................................................................................................257
Y. C. Deng, A. J. Duan, Z.G. Wang, Z. Zhao, J. Liu, G. Y. Jiang, Y. C. Wei
P-3.1-29 Non-noble metal hydrcarbon hydroisomerization catalyt supported on SAPO-11 of
small-size and enhanced acidity.............................................................................................258
Lin Guo, Yu Fan, Gang Shi, Xiaojun Bao
P-3.1-30 Selective ring opening of tetralin on Pt/Beta catalysts.............................................258
K.B. Chi, Z.J. Tian, L.J. Yan, H.J. Ma, T.F. Zhang, S. Hu, C. Luo, R.S. Xu
P-3.1-31 Enhance catalytic properties of the MFI/MCM-41 composite materials ................259
F. E. Imbert, E. Sosa, F. Aguirre, L. Belandría, P. Rodríguez, A. Uzcátegui, A. E. Mora, G.
González and J. Fernandez
P-3.1-32 Oligomerization of dicyclopentadiene on some zeolites and mesoporous catalysts.259
Pugacheva A.A., Kulikov A.B., Maximov A.L.
SECTION 3.2. Non-oil fossil feedstocks into end products .......................................................260
P-3.2-01 Fine tuning of MCM-22 acidity for improving its catalytic properties in MTO
reaction..................................................................................................................................260
P.F. Wang, L.Z. Huang, M. Dong, J.F. Li, W.F. Fan, J.G. Wang
P-3.2-02 Synthesis of size-controlled FeMFI zeolites and their catalytic activities................260
H. Kobayashi, M. Nakaya, K. Kanie, A. Muramatsu
P-3.2-03 Methane conversion into aromatics over Fe-Mo/ZSM-5 catalysts ..........................260
L.L. Korobitsyna, N.V. Arbuzova, V.I. Zaikovskii, V.V. Kozlov, Vosmerikov A.V.
P-3.2-04 Deposition of ZSM-5 on structured supports using dip-coating for MTO..............261
Jasper Lefevere, Jasper Van Noyen, Steven Mullens, Frans Snijkers, Pegie Cool, Vera Meynen
P-3.2-05 Effect of Mo precursor on Methane dehydroaromatization over Mo-MFI with coreshell structure ........................................................................................................................261
Z. Jin, S. Liu, L. Qin, Z. Liu, Y. Wang, Z. Xie, X. Wang
P-3.2-06 The influence of zeolite nature on the behavior of the composite catalyst in FischerTropsch synthesis...................................................................................................................261
E.Yu. Khatkova, L.V. Sineva, V.Z. Mordkovich
P-3.2-07 Effect of synthesis conditions of CON-type zeolite on MTO reaction activity ........262
M. Yoshioka, T. Yokoi, T. Tatsumi
P-3.2-08 Metal-containing zeolites: their preparation, investigation of physical and chemical
properties and activity in the ethane aromatization..............................................................262
L.N.Vosmerikova, V.I.Zaikovskii, A.V.Vosmerikov
P-3.2-09 The influence of catalyst acid strength on reactions relevant to Methanol To
Hydrocarbons (MTH) catalysis .............................................................................................262
M. Westgård Erichsen, S. Svelle, U. Olsbye
P-3.2-10 Relationship between coking, intraparticle diffusion and product selectivity in DTO
...............................................................................................................................................263
Y.X. Li, J.H. Guo, M.Y. Zhang, D.Z. Wang, Y. Wang
P-3.2-11 The relationship between acid and catalytic properties of Сa,H-BEA zeolites in the
reaction of methanol to dimethyl ether dehydration .............................................................263
Yu.N. Kochkin, N.V. Vlasenko, A.V. Shvets, N.V. Kasyan
38
P-3.2-12 Effect of zeolite’s structure, acidity and crystal size on the methanol to dimethylether
(DME) reaction......................................................................................................................263
S.S. Akarmazyan, S.A. Karakoulia, K.S. Triantafyllidis, D.I. Kondarides
P-3.2-13 Heterogeneous catalysis of methanol conversion over 8-ring SAPOs: aspect of coke
formation and deactivation....................................................................................................264
Y.X. Wei, C.Y. Yuan, J.Z. Li, S.T. Xu, J.R. Chen, Q.Y. Wang, Y. Zhou, Z.M. Liu
P-3.2-14. Outstanding stability of SBA-15 for promoting the catalytic methane decomposition
towards H2 production ..........................................................................................................264
David P. Serrano, Juan A. Botas, Patricia Pizarro and Gema Gómez
P-3.2-15 Propane-butane fraction aromatization on promoted zeolites ................................264
A.G. Dedov, A.S. Loktev, D. A. Levchenko, S.D. Golikov, I.K. Poliwina, A.E. Gekhman, I.I.
Moiseev
P-3.2-16 Study of HZSM-5 and its modifications in the conversion of methanol to
hydrocarbons.........................................................................................................................265
B.B.Guliyev, R.H. Ahmadova, F.A.Babayeva, H.J.Ibrahimov, M.I.Rustamov
P-3.2-17 The combined influence of Raney cobalt and zeolite on the composition of the
products of Fischer–Tropsch synthesis..................................................................................265
E.Yu. Khatkova, L.V. Sineva, V.Z. Mordkovich
P-3.2-18 Effect of acid site distributions in the framework of Al-MWW on its catalytic
properties in methylation of ethene .......................................................................................265
L.Z. Huang, P.F. Wang, J.F. Li, M. Dong, J.G. Wang, W.B. Fan
P-3.2-19 Effect of platinum amount on the catalytic properties of beta nanozeolite for WGSR
...............................................................................................................................................266
M. C. Rangel, L.H. Silva, S.T.F. Grecco, T.F. Silva, J.M. Assaf and J.M. Grau
P-3.2-20 Toward supported co-catalysts for the direct conversion of styrene to styrene
carbonate in the presence of O2 and CO2 ..............................................................................266
C. Rocha, M. Ramin, R. Sassine, T. Onfroy, F. Launay
P-3.2-21 New catalytic systems of synthesis of gasoline hydrocarbon components from
dimethyl ether on zeolite ZSM-5............................................................................................266
E.E. Kolesnikova, E.N. Khivrich, L.E. Kitaev, Z.M. Bukina, N.V. Kolesnichenko.
P-3.2-22 DME conversion on the surface of the modified zeolite catalysts studied with hightemperature diffusive reflectance FTIR spectroscopy in situ ................................................267
G.N. Shirobokova, E.N. Khivrich, T.I. Batova, A.S. Rodionov, N.V. Kolesnichenko, G.N.
Bondarenko, A.E. Kuzmin
P-3.2-23 Methanol conversion into light olefins over silicoaluminaphosphates coated with
silica .......................................................................................................................................267
S.V. Konnov, I.L. Aranovich, E.E. Knyazeva, I.I. Ivanova
P-3.2-24 The decomposition of nitrous oxide and partial oxidation of methane over ZSM5
catalysts; the effect of cobalt or iron loading.........................................................................267
N. A. Khan, M. Scollay, A. Crowfoot, E. Kennedy, B.Z. Dlugogorski, M. Stockenhuber
P-3.2-25 Nanosized ZSM-5 Synthesized with Different Templates for MTP reaction ..........268
Lanlan Zhang, Yanjun Gong, Qing Zhang, Wenlong Li, Shaolong Zhang, Feiying Yang, Wugang
Wang, Tao Dou
P-3.2-26 Mesoporous Zeolite SBA-15 and MCM-41 as Supports of Ni Catalysts for Carbon
Dioxide Reforming of Methane .............................................................................................268
Huimin Liu, Dehua He
SECTION 3.3. Environmental catalysis and conversion of biomass.........................................269
P-3.3-01 Kinetics of N2O decomposition over combined micro-mesoporous zeolites
M.Rutkowska, L. Chmielarz, B. Gil, L. Obalová
39
P-3.3-02 Epoxidation of Biodiesel with H2O2 over Hierarchically Structured TS-1 Catalysts
Prepared by Desilication and Transformation......................................................................269
N. Wilde, S. Gebhardt, W. Suprun, R. Gläser
P-3.3-03 Development of Lanthanide-incorporated Fe-based Zeolite Catalysts for Selective
Catalytic Reduction of NO.....................................................................................................269
Sayeda Halima Begum, Xiaoxiang Han, Chin-Te Hung, Shing-Jong Huang, Shang-Bin Liu
P-3.3-04 Effect of preparation procedure on the structural and catalytic properties of FeZSM-5 as NH3-SCR catalyst..................................................................................................270
Alexander Shishkin, Per-Anders Carlsson, Hanna Härelind, Magnus Skoglundh
P-3.3-05 N2O decomposition over Cu-exchanged nanosheet ZSM-5.....................................270
Wei Zou, Pengfei Xie, Yinghong Yue, Weiming Hua, Dejin Kong, Weimin Yang , Zi Gao
P-3.3-06 Design of Ru loaded Zeolite Catalysts for Hydrogen-free Production of Conjugated
Linoleic Acids and Conjugated Oils ......................................................................................270
A. Philippaerts, J. Van Aelst, P. Jacobs, B. Sels
P-3.3-07 Zeolite catalyst for transesterification of vegetable oils by ethanol.........................271
L.K. Patrylak, K.I.Patrylak, M.V. Okhrimenko, V.V. Ivanenko, A.M. Levterov, V.P.
Marakhovskyi, D.V. Savytskyi, S.V. Konovalov, Yu.G. Voloshyna
P-3.3-08 Trimetallic (Cu-Ag-Zn)/Mordenite system obtained via microwave radiation:
characterization and catalytic activity in NO reduction........................................................271
I. Rodríguez Iznaga, F. F. Castillón Barraza, A. Simakov, V. Petranovski
P-3.3-09 Preparation of TiO2/Cr-Beta Zeolite as Photocatalyst ............................................271
Shu-Hua Chien, Bai-Lin Chen, Wen-Kai Tu
P-3.3-10 Co-conversion of vegetable oils and vacuum gas oil under catalytic cracking........272
P.V. Lipin, O.V. Potapenko, T.P. Sorokina, V.P. Doronin
P-3.3-11 Selective conversion of lignin to chemicals via catalytic fast pyrolysis over zeolites272
Zhiqiang Ma, Ekaterina Troussard, Jeroen A. van Bokhoven
P-3.3-12 A comparative study relating to active sites and mechanisms in the selective catalytic
reduction of NOx over Fe zeolites ..........................................................................................272
I. Ellmers, R. Velez, A. Brückner, U. Bentrup, H. Huang, V. Schünemann, W. Grünert
P-3.3-13 Ethanol conversion towards alkanes and aromatics over pilot Pd-Zn/Al2O3/MFI
catalyst...................................................................................................................................273
A. V. Chistyakov, M.A. Gubanov, M.V. Chudakova, V. Yu Murzin, M.V. Tsodikov
P-3.3-14 Hydrogen-rich syngas production from catalytic steam pyrolysis-gasification of
biomass on Ni/MCM-41.........................................................................................................273
Z. Wang, C. Wu, L. Wang, P. T. Williams, J. Shi, J. Huang
P-3.3-15 Dehydration of Renewable Feedstocks Using Single Site Heterogeneous Catalysts273
Danni Sun, Matthew. E. Potter, Martha I.C. Angel, Robert Raja
P-3.3-16 Valorization of crude glycerol into fuel additives over molecular sieves.................274
J. Kowalska-Kuś, A. Held, A. Kuźnicka, K. Nowińska, S. Kowalak
P-3.3-17 Lewis-Acid Catalyzed Conversion of Biomass-Derived Dimethylfuran to p-Xylene
...............................................................................................................................................274
E.M. Mahmoud, P. Do, R.F. Lobo
P-3.3-18 Preparation of Nano Metal Oxides through One-pot Synthesis Associated with
Mesoporous Silica and their Catalytic Applications..............................................................274
M.J. Suh, S.K. Ihm
P-3.3-19 Effect of CO2 on deNOx activity of Cu/zeolite catalysts for NH3/SCR.....................275
Y.J. Kim, I. Heo, S. Sung, K.M. Min, J.K. Lee, S.B. Hong, I.-S. Nam, B.K. Cho
P-3.3-20 The role and peculiar properties of α-sites in N2O decomposition over FeMFI......275
L.Pirutko, V.Chernyavsky, E.Starokon, A.Kharitonov
40
P-3.3-21 Cooperative effect of Lewis and Brønsted acid sites on Beta zeolites in dehydration
of sugars.................................................................................................................................275
R. Otomo, T. Yokoi, J. N. Kondo, T. Tatsumi
P-3.3-22 Gas phase glycerol dehydration to acrolein over catalysts derived from MWW
layered precursor: effect of molar ratio SiO2/Al2O3 ..............................................................276
A. J. S. Mascarenhas, C. S. Carriço, M. B. Santos, D. S. Oliveira, F. T. Cruz, H. M. C. Andrade, H.
O. Pastore
P-3.3-23 Suppression of the formation of N2O in selective reduction of NO with NH3 over Fezeolite-promoted commercial V2O5-WO3/TiO2 catalysts.......................................................276
M.H. Kim, S.W. Ham, C.H. Shin
P-3.3-24 Hydrotreatment of Vegetable Oil over Pt/Zeolite for Producing High Quality DieselRange Fuels ...........................................................................................................................276
Congxin Wang, Qianhe Liu, Lijun Yan, Chen Luo, Zhijian Tian
P-3.3-25 Activity and stability Cu-SAPO-34 as NH3-SCR catalyst: parameters governed for
the reactivity..........................................................................................................................277
Radka Nedyalkova, Foad Faghihinia, Mariana Trifonova
P-3.3-26 AgAlBEA and AgSiBEA zeolites as promising catalysts for selective reduction of NO
with ethanol and butanol .......................................................................................................277
N. Popovych, P. Kyriienko, S. Soloviev, S. Orlyk, S. Dzwigaj
P-3.3-27 Di-n-butyl ether synthesis using continuous reactor ...............................................277
V.O. Samoylov, A.I. Nekhaev, D.N. Ramazanov, A.L. Maximov
P-3.3-28 Delaminated zeolites as effective supports for the preparation of bioethanol steam
reforming catalysts with high activity, selectivity and stability.............................................278
J.F. Da Costa-Serra, S. Sayas, A. Chica
P-3.3-29 Enhancement of low temperature NH3-DeNOx performance of Fe-Beta by
modification with manganese ................................................................................................278
D.S. Krivoruchenko, N.S. Telegina, I.S. Mashkovsky, A.Yu. Stakheev.
P-3.3-30 Oil refinery wastewater treatment by catalytic ozonation with mesoporous zeolites
(FAU) and Al-MCM-41 .........................................................................................................278
Jullian Vittenet, Jeremy Rodriguez, Julie Mendret, Stephan Brosillon, Anne Galarneau
P-3.3-31 Efficient Sugar to Lactate conversion with Bifunctional Carbon Silica Hybrid
Catalysts ................................................................................................................................279
M. Dusselier, F. de Clippel, L. Giebeler, P.A. Jacobs, B.F. Sels
P-3.3-32 Influence of channel topology and zeolite defects on the catalytic etherification of
HMF to biofuel additives .......................................................................................................279
Paola Lanzafame, Daniel Montalto, Siglinda Perathoner, Gabriele Centi, Anastasia Macario,
Alfredo Aloise and Girolamo Giordano
P-3.3-33 Use of zeolite ZSM5 and hydrotalcite based mixed oxides in the dehydration of
glycerol ..................................................................................................................................280
Sz. Mészáros, J. Halász, I. Pálinkó, Z. Kónya
P-3.3-34 Conversion of Methyl Mercaptan and Methanol to Hydrocarbons over Zeolites – a
Comparative Study................................................................................................................280
V. Hulea, C. Cammarano, A. Lacarriere, B. Coq, R. Durand, E. Huguet, R. Cadours, C. Leroi
P-3.3-35 Role of isolated mononuclear iron in decomposition of N2O and SCR of NO with
ammonia on FeAlSiBEA and FeSiBEA zeolite catalysts .......................................................281
P. Boroń, L. Chmielarz, J. Gurgul, K. Łątka, T. Shishido, S. Dzwigaj
P-3.3-36 Bio-fuels production from biomass: improving ZSM-5 resistance to phenolic
compounds.............................................................................................................................281
I. Graça, A.M. Carmo, C. Sá Couto, J.M. Lopes, M.F. Ribeiro
P-3.3-37 Synthesis, Characterization and Catalytic Activity of Molecular Sieves Containig
Bismuth (SABiOs) .................................................................................................................282
A. J. S. Mascarenhas, F. T. Cruz, H. M. C. Andrade.
41
P-3.3-38 Niobium-containing mesoporous molecular sieves as catalysts for catalytic
oxidations...............................................................................................................................282
A. Feliczak-Guzik, A. Wawrzynczak, J. Goscianska, I. Nowak
P-3.3-39 Direct conversion of fatty acid triglycerides on zeolite catalysts .............................282
A.G. Dedov, A.S. Loktev, E. A. Isaeva, S.D. Golikov, E.V. Rogaleva, A.E. Gekhman, I.I. Moiseev
P-3.3-40 TCE oxidation over metal exchanged zeolite BETA ...............................................283
N.Blanch-Raga, A.E. Palomares, J. Martínez-Triguero, G. Fetter, P. Bosch.
P-3.3-41 Discrimination of Fast SCR and Standard SCR pathways in NH3-DeNOx over Fe
Beta zeolites ...........................................................................................................................283
A.I. Mytareva, G.N. Baeva, G.O. Bragina, D.A. Bokarev, A.Yu. Stakheev
P-3.3-42 Influence of iron content on the activity of Fe/SBA-15 catalysts for methylene blue
removal from aqueous effluent..............................................................................................283
M. C. Rangel, O. B. da Silva, S. T. F. Grecco, H.C. F.Santos, S. Borges, S.G. Marchetti
P-3.3-43 FTIR Spectroscopic Study of NO + O2 Coadsorption on H-SSZ-13: Formation and
Stability of NO+......................................................................................................................284
J.A. Loiland, R.F. Lobo
SECTION 3.4. Chemicals and fine chemicals ...........................................................................285
P-3.4-01 Oxidation of Phenol to Dihydroxybenzenes by N2O over MFI zeolites...................285
L.V. Pirutko, D.P. Ivanov, G.I. Panov
P-3.4-02 Disproportionation of Trimethylbenzene over Modified Beta Zeolite ....................285
Y.W. Chen, S.J. Zhu
P-3.4-03 A comparative study of glycerol dehydration catalyzed by desilicated
micro/mesoporous MFI zeolites.............................................................................................285
L.G. Possato, R.N. Diniz, T. Garetto, S.H. Pulcinelli, C.V. Santilli, L. Martins
P-3.4-04 Titanium containing Solid core Mesoporous silica shell: A novel efficient catalyst for
ammoxidation reactions.........................................................................................................286
N. Venkatathri, M. Nookaraju, A. Rajini, I.A.K. Reddy
P-3.4-05 Engineering Single-Site Lewis Base Catalysis in Mesoporous Silica for Desirable
Industrial Transformations ...................................................................................................286
S. H. Newland, D. J. Xuereb, R. Rios Torres, R. Raja
P-3.4-06 Efficient one-pot synthesis of 2, 5-disubstituted 1,3,4-oxadiazoles catalyzed by nanoZSM-5 catalyst.......................................................................................................................286
Abbas Teimouri, Alireza Najafi Chermahini
P-3.4-07 Shape-Selective Catalysis Determined by the Volume of a Zeolite Cavity: Selective
production of Propylene ........................................................................................................287
Toshihide Baba, Yasuyoshi Iwase, Akimitsu Miyaji, Ken Motokura, To-ru Koyama
P-3.4-08 Immobilized on zeolite support metallocene catalysts for olefin polymerization ....287
I. N. Meshkova, V.G.Grinev, S.A.Skornikova, N.Yu. Kovaleva, O.I. Kudinova, L. A.
Novokshonova
P-3.4-09 Selectivity comparison of 2,6-dimethylnaphthalene by methylation of naphthalene
with methanol on different zeolites........................................................................................287
Ye Zhang, Mingxian Du, Zhanjun Lv, Xuekuan Li
P-3.4-10.. Microwave-assisted Sonogashira Cross-Coupling Reaction Catalyzed by Pd-MCM41 under Solvent-free Conditions ..........................................................................................288
W. Chang , J. Shin, G.H.Chae, S. R. Jang, B. J. Ahn
P-3.4-11 Vanadium modified mesoporous and amorphous solid matrices applied for propene
epoxidation ............................................................................................................................288
A. Held, J. Kowalska-Kuś, K. Nowińska, S. Kowalak
P-3.4-12 Skillful design of new direct oxidation catalyst: Dual functional titanosilicate.......288
Chunfeng Shi, Jun Long, Min Lin, Bin Zhu
42
P-3.4-13 Mesoporous hollow silica supported Pt based bimetal catalysts: effect of promoter
and thermal treatment...........................................................................................................289
Xu Yang, Shijun Liao
P-3.4-14 EISA prepared mesostructured titanium-silicate as highly efficient catalyst for
selective oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone ................289
M. S. Mel’gunov, I. D. Ivanchikova, M. K. Kovalev, O. A. Kholdeeva
P-3.4-15 Isomerization of α-pinene oxide to campholenic aldehyde over Fe-modified microand mesoporous materials .....................................................................................................290
M. Stekrova, N. Kumar, P. Mäki-Arvela, D. Yu. Murzin
P-3.4-16 New Aibassov’s - Yuriev's reaction transformation of furan in its analogs phosphorane, arsanol, stibinol and vismutol .........................................................................290
Aibassov Erkin Zhakenovich, Baiguzhin Adil Alibekovich, Umirkulova Zhanar Sempekovna,
Serikbaeva Gulbarshyn Kuanyshkanovna
P-3.4-17 Alkylation of naphthalene with methanol in synthesis of 2,6-dimethylnaphthalene on
CoAPO-11 molecular sieve ....................................................................................................291
Min Liu, Wei Wu, Linfei Xiao, Aijuan Zhao, Xiaoran Liu
P-3.4-18 The synthesis of esters on micro- and micro-mesoporous metallsilicates................291
N.G. Grigorieva, A.M. Suleimanova, S.V. Bubennov, V.A. Veklov, B.I. Kutepov
P-3.4-19 The liquid phase oxidation of styrene with silver supported mesoporous carbons as a
catalysts .................................................................................................................................291
Joanna Goscianska, Robert Pietrzak, Izabela Nowak
P-3.4-20 Benzylation of benzene with benzyl chloride on iron-containing mesoporous
mordenite...............................................................................................................................292
Y. Sun, K. Leng
P-3.4-21 Acid modification of nature mesoporous aluminosilicate catalyst ..........................292
A.Yu. Sidorenko, G.M. Sen’kov, V.E. Agabekov
P-3.4-22 The basicity of Y zeolite containing alkylammonium cations .................................292
K.A. Almeida, D. Cardoso
P-3.4-23 Structure and selective reduction of benzonitrile to benzylamine with zeolite
catalysts .................................................................................................................................293
Ateeq Rahman, Anitha S. Deshpande, Faris Al Naomy
P-3.4-24 HZSM-5 zeolite in partial oxidation of aromatic compounds by nitrous oxide in
supercritical conditions..........................................................................................................293
A.L. Kustov, A.E. Koklin, V.I. Bogdan, L.M. Kustov
P-3.4-25 Effect of the Support on the Hydrogenation of 3-Hexyne to Cis-3-Hexene Over
Palladium Catalysts...............................................................................................................294
G. Alvez-Manoli, T.J. Pinnavaia, Z. Zhang, D.K. Lee, K. Marín-Astorga, P. Rodriguez, F. Imbert,
P. Reyes, N. Marín-Astorga
P-3.4-26 Catalytic synthesis of alkoxy norbornanes ..............................................................294
G.Z. Raskildina, A.M. Suleimanova, K.K. Gorshunova, B.I. Kutepov, S.S. Zlotsky
P-3.4-27 Synthesis of pyridine and picolines over H-beta zeolite catalyst .............................294
N.A. Filippova, N.G. Grigor’eva, I.S. Faizrakhmanov, B.I. Kutepov
P-3.4-28 Facile and Fast Laboratory Upscaling Synthesis of ZIF-8 Nanocatalyst and
Application in Monoglyceride Synthesis Process ..................................................................295
L.H. Wee, T. Lescouet, J. Ethiraj, F. Bonino, R. Vidruk, E. Garrier, D. Packet, S. Bordiga, D.
Farrusseng, M. Herskowitz, J.A. Martens
P-3.4-29 A novel zeotype palladium dodecylamino phosphate: Efficient catalyst for the
Suzuki coupling reactions......................................................................................................295
A. Rajini, M. Nookaraju, A. Ajay kumar, N. Venkatathri, I.A.K. Reddy
43
SECTION 3.5. Adsorption and separation................................................................................296
P-3.5-01 Eradication of TCA from aqueous solutions using zeolites as adsorbents ..............296
L. Ferreira, M.F. Ribeiro, A. Fernandes, C. Henriques
P-3.5-02 Selective adsorption of tobacco specific nitrosamines (TSNA) in smoke ................296
Y. Zhou, W.G. Lin, M.M. Wan, J. Yang, Y. Wang, J.H. Zhu
P-3.5-03 Properties of a novel binderless Y-type zeolite for thermal adsorption storage
applications............................................................................................................................296
J. Jänchen, T. Herzog, K. Schumann, A. Brandt, B. Unger
P-3.5-04 Сhoice of pre-activation conditions of zeolites Х by design of experiments ...........297
Ivanova E.N., Alekhina M.B, Aknazarova S.L., Konkova T.V.
P-3.5-05 Performance of Mesoporous Materials in Adsorptive Desulfurization ...............297
Y.C. Qin, X.C. Shao, X.T. Zhang, Y. Wang, Y.J. Ruan, L.H. Duan, L. Song
P-3.5-06 Synthesis and characterization of LTA/carbon hierarchical structured composite for
cobalt (II) uptake...................................................................................................................297
David A. De Haro-Del Rio, S. Holmes
P-3.5-07 Dual temperature ion-exchange separation on zeolites ...........................................298
V. A. Ivanov, R. Kh. Khamizov, O. T. Gavlina, A. A. Madani
P-3.5-08 The First Tethered Organo-AlPO as a Versatile Precursor for Tackling
Environmental Issues ............................................................................................................298
D.J. Xuereb, M.E. Potter, W. Mothersole, C. Hinde, S. Newland, R. Raja
P-3.5-09 Removal studies of UO22+ and Cu2+ ions onto synthetic NaA zeolite.......................299
D. Nibou, S. Amokrane, A. Krobba, H. Mekatel, M. Barkat
P-3.5-10 Phytase Immobilized on Hierarchical Heteroatomic Fe-ZSM-5 Zeolite as Composite
Feed Additive for Enhanced Phytate-Phosphorus Bioavailability ........................................299
Wenzhong Zhang, Fang Xu, Deju Wang
P-3.5-11 Adsorption of 2,3-DCDD on FAU and EMT-type zeolites: influence of the nature
and the content of charge compensating cations ...................................................................299
M. Mercury, N. Zouaoui, A. Simon-Masseron, Y. Zerega, C. Reynard-Carette, R. Denoyel, M.
Carette, A. Janulyte, J. Patarin
P-3.5-12 Mordenites, ZSM-5 and Beta Zeolites Modified with Cations as Adsorbents for
Control of Hydrocarbon Cold-Start Emissions .....................................................................300
V.Golubeva, A.Korableva, L.Kustov, G.Kapustin, U.S.Rohatgi, M.V.Viola
P-3.5-13 Interaction between the framework of silicalite-1 and OH group in sorbate
molecules................................................................................................................................300
N. Kamiya, T. Oshiro, S. Tan, T. Koike, K. Nishi, Y. Yokomori
P-3.5-14 Features of sorption of flavonoids on MCM-41 and composite materials based on
MCM-41 ................................................................................................................................300
S.I.Karpov, F. Roessner, N.A. Belanova, V.F. Selemenev, E.O. Korabelnikova, O.O.
Krizhanovskaya, I.V. Nedosekina
P-3.5-15 Equilibrium of adsorption of α-tocopherol and β-sitosterol onto mesoporous
composites..............................................................................................................................301
O.O. Krizhanovskaya, E.V. Borodina, S.I. Karpov, F. Roessner, V.F. Selemenev
P-3.5-16 Adsorption isotherm of pure gases at high pressures on Na-LTA zeolites of different
crystal sizes ............................................................................................................................301
R. E. Bazan, C. G. Maciel, D. C. Melo, D. Cardoso
P-3.5-17 Non-monotonic chain length dependent adsorption and diffusion of 1-alcohols in
SAPO-34 ................................................................................................................................301
J. Cousin Saint Remi, G. Baron, J. Denayer
P-3.5-18 Hydrogen adsorption by Cu(I)-Y, -SSZ-13 and –ZK-5...........................................302
B. Ipek, C.M. Brown, R.F. Lobo
44
P-3.5-19 Enhancing CCS performances of microporous materials by basic oxide coating...302
Jenny G. Vitillo, Gabriele Ricchiardi, Valentina Crocellà, Silvia Bordiga
P-3.5-20 Titanosilicate desiccants for low temperature/energy input CO2 drying ................302
S. Rezaei, B. Tanchuk, J.A. Sawada, S.M. Kuznicki
P-3.5-21 Removal of Cr(III) from aqueous solution by zeolites sintetized from exhausted
FCC catalysts. Kinetics studies and effect of Cr(III) exchange on the zeolitic structure ......303
M. R. Gonzalez, A. M. Pereyra, E. I. Basaldella
P-3.5-22 Surface concentrations of methanol/DME/C3H6/C3H8 mixtures calculated by the
Langmuir and ideal adsorbed solution theories ....................................................................303
Yasukazu Kobayashi, Yuxin Li, Yao Wang, Dezheng Wang
P-3.5-23 Pore-expanded MCM-41 for CO2 adsorption .........................................................303
E.S. Sanz Pérez, A. Arencibia, G. Calleja, R. Sanz
P-3.5-24 Adsorption of methyl tert-butyl ether on zeolites Y, Mordenite, and ZSM-5 used for
the decontamination of ground water....................................................................................304
V. Sacchetto, C. Bisio, G. Gatti, M. Cossi, L. Marchese, I. Braschi
P-3.5-25 Adsorption of hexane isomers on MFI type zeolites: Understanding the aluminium
content effect..........................................................................................................................304
A. Ferreira, M. Mittelmeijer-Hazeleger, J. Bergh, S. Aguado, J.C. Jansen, G. Rothenberg, A.E.
Rodrigues, F. Kapteijn
P-3.5-26 Purification of catalytic cracking gasoline from sulfur by the hydroadsorption
method ...................................................................................................................................305
G.S. Mukhtarova, Z.A.Qasimova, H.C. Ibrahimov, V.M.Abbasov, M.I. Rustamov
P-3.5-27 Hydrogen adsorption onto MCM-48 carbon replica modified with metals ............305
J. M. Juárez, M. B. Gómez Costa, J. Cussa, O.A. Anunziata
P-3.5-28 Adsorption of amino acids on ordered mesoporous sillicas modified with lanthanum
...............................................................................................................................................305
J. Goscianska, A. Olejnik, R. Pietrzak
P-3.5-29 Enhanced CO2 capture over CMK carbons functionalized with amino groups......306
R. Sanz, D. Serrano, P.Pizarro, A. Arencibia, A. L. López, E. Esteban, J.L. Domínguez, I. Moriña
P-3.5-30 Carbon-Silica Nanocomposites for Separation Applications ..................................306
F. de Clippel, A. Harkiolakis, A. Khan, M. Dusselier, I. Vankelecom, J. Denayer, P. Jacobs, B. Sels
P-3.5-31 Temperature Dependent Immobilization of CH4 and H2 in Narrow Pore Zeolites.306
A.Puls, F.Dreisbach, T.M. Fieback
P-3.5-32 Adsorption of Isobutane and Isobutene on H-ZSM-5 Type Zeolite and on Beta
Zeolite ....................................................................................................................................307
O.A. Sukhorebrova, O.V. Yashina, P.V. Samokhin, M.A. Kipnis
P-3.5-33 Selective Adsorption Desulfurization of Gasoline by Micro- and Mesoporous
Molecular Sieves....................................................................................................................307
L. Song, Y.C. Qin , W.G. Yu, S.W. Dong, L.H. Duan, X.T. Zhang, Y. Wang
P-3.5-34 Effect of Acidic and Basic Additives on Zr-MOF for CH4 and CO2 Adsorption ....307
Hussein Rasool Abid, Shaobin Wang
P-3.5-35 Reuse of waste of catalytic removal of contaminants in diesel ................................308
J.P.M. Miguens, Souzaw.C., M. A. G. Figueiredo, L. A. N. Mendes, F. G. Bastianelli
P-3.5-36 CO2 Sorption Mechanism in Amine-Functionalized SBA-15 Mesoporous Silica
Studied by Solid-State NMR Spectroscopy ...........................................................................308
Chin-Te Hung, Shin-Jong Huang, Jen-Shan Lin, Yu-Chi Chang, Shang-Bin Liu
P-3.5-37 Understanding Carbon Dioxide Adsorption on Alkali Metal Exchanged Zeolite
SSZ-13 ...................................................................................................................................309
Trong D. Pham, Matthew R. Hudson, Craig M. Brown, Raul F.Lobo
P-3.5-38 Adsorption studies of Propane on silicalite-1 with different morphologies.............309
Zhaofei Li, Xiaoqiang Yao, Xiangyu Xu, Jiaqing Song, Qian Wang, Qiwu Liu, Xiaohui Gao, Lijun
Yan, Xinmei Pang, Fayong Li
45
P-3.5-39 Removal of Pyrogallol from Aqueous Solution by Adsorption onto Organobentonite
and Organovermiculite..........................................................................................................310
J.I. Martinez-Costa, R. Leyva-Ramos, J. Mendoza-Barron, R.M. Guerrero-Coronado
P-3.5-40 Kinetic Separation of P/O-Xylene Isomers by SiO2/Silicalite-1 Core-Shell
Adsorbents.............................................................................................................................310
Easir A. Khan, Arvind Rajendran, Zhiping Lai
SECTION 3.6. Novel applications (health, electronics, sensors) ...............................................311
P-3.6-01 Nanocomposites “porous glass-KNO3”: structure and electric properties..............311
Pshenko О. А., Arsent’ev M. Yu., Antropova Т. V., Lapschin A. E., Anfimova I. N.
P-3.6-02 Synthesis of mesoporous TiO2-SiO2 materials for immobilization of Hemoglobin .311
L.L. Luo, S. Chu, C.C.Wang, Y. Wang , J.H. Zhu , Z. Zhou
P-3.6-03 Organophilic zeolite Y used in PRB technology: regeneration after sulfonamide
antibiotics removal from water .............................................................................................311
L. Leardini, A. Martucci, I. Braschi, S. Blasioli, R. Arletti, S. Quartieri
P-3.6-04 Formation of Nanoparticles on the External Surface of Nanopore Organic-Inorganic
Hybrid Zeolite Materials .......................................................................................................312
M. A. Hernández, F. Hernandez, F. Rojas, M. A. Salgado, Ma del Rosario Lopez
P-3.6-05 Encapsulation of dmit in zeolites, preparation of potential pigments .....................312
A. Jankowska, J. Ziółkiewicz, S. Kowalak
P-3.6-06 Characterization of the composite water sorbent CaCl2-FeKIL2 for low temperature
heat storage............................................................................................................................312
Alenka Ristić, Stefan K. Henninger, Venčeslav Kaučič
P-3.6-07 Zeolites as ion exchanger in harsh ultra-alkaline conditions - stability and selectivity
...............................................................................................................................................313
E. Breynaert, L. Van Tendeloo, E. Gobechiya, W. Wangermez, B. De Blochouse, J.A. Martens,
C.E.A. Kirschhock, A. Maes
P-3.6-08 Electrocatalytic oxygen production in alkaline media using modified electrodes with
hydrotalcite-like materials Ni/M (M=Al, Fe) ........................................................................313
M. A. Oliver-T., A. Guzmán-V., E. Lima, J. L. Flores, J. Vazquez S., G. A. Uriostegui O.
P-3.6-09 The influence of preparation conditions and doping on the physicochemical and
sensor properties of mesoporous tin oxide.............................................................................313
S.A. Sergiienko, О.L. Kukla, P.S. Yaremov, V.N. Solomakha, O.V. Shvets
P-3.6-10 Functionalized SBA-15 and PMO materials as Drug Delivery Systems..................314
J. Timm, W. Bensch
P-3.6-11 Microwave heating, a valuable tool for a straightforward synthesis of zeolite L with
tunable size and morphology.................................................................................................314
L. Gartzia-Rivero, J. Bañuelos-Prieto, I. López-Arbeloa
P-3.6-12 Photochromic Behavior of Titanosilicate ETS-10 ...................................................315
S. Galioglu, M. İşler, Z. Demircioğlu, R. Turan, B. Akata
P-3.6-13 On the use of mesoporous materials/non-wetting liquid systems in damping
application: understanding phenomena from nanoscale to macroscale................................315
M. Michelin-Jamois, L. Guillemot, E. Charlaix, G. Vigier
P-3.6-14 Nanocomposite based Zeolite for Biological Applications.......................................315
D. M. Aldhayan, T. A. Salah El-Din, A. A. Elzatahry, E. A. Elsayed, M. AM Wadaan, A. M. AlEnizi
P-3.6-15 Gas dıscharge processes ın the porous zeolıte .........................................................316
K. Koseoglu, V.I. Orbukh, N.N. Lebedeva, S. Ozturk and B.G. Salamov
P-3.6-16 Indigo pigments with MOF matrices.......................................................................316
Anna Zywert, Patryk Florczak, Małgorzata Szyld, Stanisław Kowalak
46
P-3.6-17 Application of clinoptilolite for enhancement of analytical characteristics of urease
biosensors ..............................................................................................................................316
O. Saiapina, M. Shelyakina, O. Soldatkin, V. Arkhypova, B. Akata Kurç, N. Jaffrezic-Renault, A.
Soldatkin, S. Dzyadevych
P-3.6-18 Determination of urea in blood plasma samples by using conductometric biosensor
based on urease, adsorbed on silicalite ..................................................................................317
I.S. Kucherenko, O.O. Soldatkin, B. O. Kasap, S. Öztürk, B. Akata Kurç, A.P. Soldatkin, S.V.
Dzyadevych
P-3.6-19 Rationale of the drug encapsulation and release from biocompatible porous MetalOrganic Frameworks.............................................................................................................317
P. Horcajada, D. Cunha, M. Ben Yahia, S. Hall, S.R. Miller, H. Chevreau, E. Elkaïm, G. Maurin,
C. Serre
P-3.6-20 Sustainable treatment of waters polluted with fuel-based pollutant mixtures by high
silica zeolites ..........................................................................................................................318
A. Martucci, L. Pasti, I. Braschi, L. Marchese
P-3.6-21 pH-Controlled Drug Delivery in Polymer-Coated Bimodal Mesoporous Silicas ....318
H. Zhang, Y.Y. Guo, J.H. Sun, S.Y. Bai
P-3.6-22 Silica cross-linked nanoparticles encapsulating fluorescent conjugated dyes for
energy transfer-based white light emission ...........................................................................319
Fangyuan Gai, Xiang Li, Yunling Liu, Qisheng Huo
P-3.6-23 Specific and Highly Efficient Intracellular Release with Photoactivated and
Targeted Colloidal Mesoporous Silica Nanoparticles............................................................319
A. Schmidt, S.A. Mackowiak, V. Weiss, C. Argyo, C. von Schirnding, C. Bräuchle, T. Bein
P-3.6-24 LTA containing biocidal cations as additive for waterborne coating formulations 320
A.M. Pereyra, M.R. Gonzalez, V.G. Rosato, E.I. Basaldella
P-3.6-25 Ordered mesoporous sillicas as carriers for L-phenylalanine release.....................320
J. Goscianska, A. Olejnik, R. Pietrzak
INDEX OF AUTHORS .............................................................................................................321
PLENARY LECTURES
17 IZC, 2013. PLENARY LECTURES
49
PL-01
New Directions in Zeolite Synthesis
Svetlana Mintova and Valentin Valtchev
Laboratoire Catalyse et Spectrochimie (LCS), ENSICAEN, Université de Caen, CNRS, 6 boulevard
du Maréchal Juin, 14050 Caen France; e-mail : svetlana.mintova@ensicaen.fr
The presentation will include recent developments in the field of synthesis of zeolites and zeo-type
materials. Amongst the number of interdependent factors controlling zeolite formation the most
important that will be addressed in the lecture are: (i) the gel chemistry including the ratio between
the reactants and the initial sources, the structure directing and the mineralizing agent; (ii) the
physical features of the precursor system (gel/suspension); (iii) the physical conditions
(time/temperature) of synthesis; and (iv) the heating method (conventional, microwave, sonication).
Amongst the other topics special attention will be paid to zeolite formation in conventional organictemplate-free zeolite yielding systems. A “soft” chemistry approach that allows to control zeolite
nucleation and to produce zeolite under environmentally benign conditions will be presented. The
progress in the preparation of zeolites with bimodal porosity with or without organic templates, with
special emphasis on the reduction of their size (nanosized crystallites) and one-step hydrothermal
crystallization process via introducing a rationally designed surfactants/organosilanes as
(meso)porogens will be discussed.
17 IZC, 2013. PLENARY LECTURES
50
PL-02
Methanol-to-Olefin: from fundamental to commercialization
Zhongmin Liu*, Yingxu Wei, Peng Tian, Lei Xu
National Engineering Laboratory for Methanol to Olefin, Dalian National Laboratory for Clean
Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R.
China, liuzm@dicp.ac.cn
A process technology of “Dimethylether or Methanol to Olefins (DMTO)” was recently
commercialized in the world first coal to olefin plant using SAPO molecular sieve as catalyst. Here
gives a brief review of relevant R&D progress and activities, including fundamental researchs on
reaction mechanism, molecular sieve synthesis, catalyst, process demonstration and
commercialization.
17 IZC, 2013. PLENARY LECTURES
51
PL-03
New Insights into Porous Materials from Advanced Characterization
R.F. Lobo1
Center for Catalytic Science and Technology, Dept. of Chemical and Biomolecular Engineering,
University of Delaware, Newark, DE 19716 USA, lobo@udel.edu
This plenary talk will review recent progress and discuss recent findings related to new understanding
of the properties of porous materials by the use of advanced characterization techniques. It is no
exaggeration to state that electron microscopy, optical spectroscopy, X-ray scattering and
spectroscopy, among others, have been revolutionized by new developments in radiation sources,
automation, miniaturization, data analysis and the integration of disparate techniques into
measurements that probe, with temporal and spatial resolution, properties of interest. In combination
with novel sample stage designs that allow for measurements under ‘operando’ conditions, the ability
of the scientific community to investigate complex problems has greatly increased. This is
demonstrated by a slew of new reports that use these techniques cleverly to resolve long-standing and
important problems in zeolite science and technology.
17 IZC, 2013. PLENARY LECTURES
52
PL-04
Chemistry and application of porous coordination polymers (PCPs)/metal organic
frameworks(MOFs)
Susumu Kitagawa
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Kyoto, Japan,
kitagawa@icems.kyoto-u.ac.jp
PCPs or MOFs are an emerging class of microporous solids combining the modularity of inorganic
structural building units (nodes) with organic ligands (linkers) that can be tailored through organic
synthesis.1 This particular combination of designability and the structural porosity of PCPs has led to
explosive growth in their application to gas storage/separation, catalysis, ion conductivity, chemical
sensing, and drug delivery systems. Today several hundred different MOFs are known, and over
2,000 articles on this class of materials are published annually worldwide. PCPs provide unique
properties, in particular, flexible porous frameworks which is coined soft porous crystals, dissimilar to
those of conventional porous materials because of responsive functions to chemical and/or physical
stimuli.2
1. S. Kitagawa, et.al., Angew. Chem. Int. Ed., 2004, 43, 2334.
2. S. Horike, et.al., Nature Chemistry, 2009, 1, 695.
17 IZC, 2013. PLENARY LECTURES
53
PL-05
Designing zeolites for specific applications
Avelino Corma
Instituto de Tecnología Química- UPV-CSIC
The use of different inorganic and organic structure directing agents (OSDA) such as organic
quaternary ammonium and phosphonium ions, as well as phosphazenes has allowed to synthesize
zeolites with small, medium, large and extra-large pores. In the case of small pore zeolites, we will
show their potential for gas separation and how the control of pore shape and diameter, are key
factors to optimize separation of CO2/CH4, propene/ propane or the C4 olefin fraction. We will also
show potential catalytic applications of small pore zeolites for process in where reactant diffusion
shape selective play a major role.
Emphasis will be made on the synthesis of one pot Cu-exchanged small pore zeolites for SCR of NOx
with ammonia, in where the secondary building units of the Zeolite plays a determinant role on the
hydrothermal stability of the material.
Going one step further, specific OSDASs will be presented to synthesize structures with pore
topologies in where pores (that no windows) formed by 8RX10R, 8RX12R, 10RX12R, 10RX18R,
12RX12R, 12RX14R, are obtained. The catalytic possibilities of these type of multipore system will
be presented for catalytic cracking, aromatic alkylations, alkyld aromatic transalkylation, and alcohol
carbonylation. We will also show a new reaction for the synthesis of oxazols for which this type of
zeolites give extraordinary selectivities. Finally we will describe a series of reactions in where the
combination of framework metal atoms and Broasted acid sites or metal nanoparticles allow to carry
out domino multistep reactions.
When large molecules have to be process, active site accessibility becomes an issue in the case of
zeolite catalysts. The possibilities to synthesize extralarge pore stable zeolites, single layered zeolites
prepared by post-synthesis treatment or by direct synthesis, as well as samples with large external
surfaces and their application as acid and bifunctional catalysts for transforming chemical and
biomass derived products will be presented.
In our talk, we will intend to show that each type of Zeolite can be useful, regard less of the pore
diameter and topology, provided that we find the best suited application.
54
KEYNOTE LECTURES
17 IZC, 2013. KEYNOTE LECTURES
56
KN-1.1
Simple Synthesis of Zeolites: New directions without the use of OSDAs
Tatsuya Okubo and Keiji Itabashi
Department of Chemical System Engineering, The University of Tokyo, Tokyo, Japan
okubo@chemsys.t.u-tokyo.ac.jp
Organic structure-directing agents (OSDAs) have enabled us to synthesize zeolites with novel
framework types; however, the cost of the OSDAs is a greater part in the starting materials. In
addition, for the zeolites synthesized with OSDAs, calcination (or alternative process) followed by
cleaning up of gas as well as waste water treatment including organic matter is indispensable, which
causes the increase of the production cost. The synthesis of zeolites without the use of OSDAs has
been one of the most important topics for the commercialization of zeolites. In the former part of the
lecture, our successes in broadening the framework types of zeolites are introduced based on a
working hypothesis with considering the composite building unit. In the latter part, our success in the
preparation of the hierarchical zeolite by the control of the intergrowth is introduced. The use of a
simple OSDA without the use of meso- or macroporogens results in the formation of hierarchical
structures possessing micro-, meso- and macroporosity by the sequential, 90˚ rotational intergrowth of
zeolite plates.
KN-1.2
The IZA Handbook of Natural Zeolites: a tool of knowledge of the most important family of
porous minerals
Carmine Colella
Chair of the IZA-Natural Zeolite Commission
DICMAPI (Dep. of Chemical, Materials and Industrial Production Engineering), Federico II
University, Piazzale V. Tecchio 80, 80125 Napoli, Italy, carmine.colella@unina.it
The IZA Commission on Natural Zeolites was established in 2001, at the 13th IZC of Montpellier.
The mission of this new commission was to be a reference point for the scientists working on natural
zeolites, but also to save the historical memory of zeolite minerals, which is tout court the memory of
zeolites. One of the first objectives of the Commission was to prepare updated datasheets on the
currently recognized 67 zeolite minerals, to be displayed in its website.
The handbook here presented is a collection of the above datasheets. Credit should be given to the
Commission member Prof. William S. Wise, who took on the task to compile the datasheets, which
were then carefully examined by the other members of the Commission, before approval and
publication online.
17 IZC, 2013. KEYNOTE LECTURES
57
KN-1.3
Monoliths with hierarchical porosity to enhance efficiency
and productivity of heterogeneous catalysts
Anne Galarneau
Institut Charles Gerhardt Montpellier, UMR 5253 CNRS/UM2/ENSCM/UM1, ENSCM, 8 rue de
l’Ecole Normale, 34296 Montpellier Cedex 5, France, anne.galarneau@enscm.fr
Monoliths with hierarchical porosity (macro-/mesoporous) obtained by sol-gel process and spinodal
decomposition between silica-PEO phase and water have been used as microreactors in
heterogeneous catalysis in continuous flow processes. These monoliths were functionalized by
grafting organic functions (NH2), by alumina deposition, by the in situ synthesis of MOF
nanoparticles (CuBTC) and Pd nanoparticles and by pseudomorphic transformation of the silica
skeleton into MCM-41 and zeolites (SOD, LTA). These monoliths show a tremendous improvement
in term of efficiency and long-term productivity of the catalytic reactions in comparison with more
conventional systems such as particle beds (packed-bed) and batches.
KN-1.4
Beyond the pure inorganic framework of zeolites: the Eni Carbon Silicates
Roberto Millini
eni s.p.a., refining&marketing division, San Donato Milanese Research Center, San Donato
Milanese, Italy, roberto.millini@eni.com
The incorporation of organic groups within the zeolite framework provides opportunities for
modulating its hydrophilic/hydrophobic character as well as for introducing new functionalities and
active sites useful not only in catalysis and adsorption but even for novel advanced applications. To
date, however, the possibility of incorporating even simple organic groups in the framework of known
zeolites has not unambiguously demonstrated. An answer to this problem was recently given by the
discovery of a new family of nanoporous crystalline organic-inorganic hybrid aluminosilicates called
Eni Carbon Silicate (ECS). Several different ECS phases have been synthesized so far and for some
of them the crystal structure has been determined, allowing a better understanding of the
characteristics of this promising family of materials.
17 IZC, 2013. KEYNOTE LECTURES
58
KN-1.5
Zeolite and MOF Molecular Sieve Membranes – Quo Vadis?
J. Caro
Institute of Physical Chemistry, Leibniz University Hannover, Hannover, Germany
juergen.caro@uni-hannover.de
Under laboratory conditions, zeolite and MOF membranes show much better separation performance
than organic polymer membranes (Robson plot). Examples are the use of DDR and SAPO-34
membranes in the CO2/CH4 separation. Scale up-problems, long-time stability incl. regeneration and
the relative high costs of molecular sieve membranes are the main hurdles of commercialization.
Despite much progress in the last 10 years, there is still no zeolite or metal-organic framework (MOF)
molecular sieve membrane on operation for gas separation. The question arises, if the recently
developed metal organic frameworks (MOFs) are more suitable as molecular sieve membranes
compared to zeolites.
However, during the last 12 months enormous success has been reached in mixed matrix membranes
combining MOF powders and standard membrane polymers. The production of mixed matrix
membranes with up to 50% MOF content without major modifications of the existing hollow fiber
spinning seems possible.
KN-2.1
Structure and properties of zeolite and metal organic framework nanosheets
B. Slater1
Department. of Chemistry, University College London, London, United Kingdom, b.slater@ucl.ac.uk
In recent years, there have been important developments in the field of zeolite science exploiting thin
films or nanosheets either for potential direct application or in the production of new zeolite
structures. Similarly, there is growing interest in the nature of MOF nanosheets driven in part, by the
mixed matrix composites. In this talk, I will describe how periodic density functional theory
calculations have been used to shed light on the structure of these materials. From a detailed study of
zeolite nanoslabs, it is found that Al, Ti and hydroxyl nests can occupy sites close to the surface in
thermodynamic preference over bulk, interior sites. The presence of Bronsted acid sites and/or
hydroxyl nests at surface accessible positions suggests the possibility of highly reactive regions in
nanosheet and micron-sized ZSM-5 that may have ramifications for catalytic function. I will also
focus on the nature of undercoordinated sites on and in MOF films.
17 IZC, 2013. KEYNOTE LECTURES
59
KN-2.2
Automated electron Diffraction Tomography (ADT) for solving structures of beam sensitive
nanoporous materials
U. Kolb1, E. Mugnaioli2
1Institute of applied geosciences, Technical University Darmstadt, Darmstadt, Germany,
kolb@geo.tu-darmstadt.de
2 Institute of Physical Chemistry, Johannes Gutenberg-University, Mainz, Germany
Transmission electron microscopy is an established method for structural characterization of nano
crystalline material by imaging, diffraction and elemental analysis. High resolution TEM imaging
demands high electron dose on the sample, often problematic for frameworked and hydrated
inorganic materials. By using electron diffraction a significantly lower electron dose is applied.
Traditionally, electron diffraction data is collected by orienting low index zones which delivers a
limited number of accessible reflections and enhances dynamical effects.
Automated electron Diffraction Tomography (ADT), is the first method using non-oriented
diffraction patterns. After reconstruction of the collected data in a 3D reciprocal space, cell
parameters, space group and intensity data can be taken. The strong reduction of dynamical effects in
non-oriented zones allows a standard kinematic approach usually delivering ab-initio a complete
structural model. It was possible to solve structures from a single nanocrystal down to 30 nm.
Remarkably, large cell porous minerals, zeolites and beam-sensitive metal-organic frameworks have
been solved in the last years by direct methods.
KN-2.3
Life and Death of a Fluid Catalytic Cracking Particle
B.M. Weckhuysen1
Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG
Utrecht, The Netherlands, b.m.weckhuysen@uu.nl
Fluid catalytic cracking (FCC), the major process employed in petrochemical industries for the
conversion of crude oil, makes use of catalyst particles with a diameter of ~ 70 μm. In an oil refinery
the catalyst particles are continuously circulated between reactor and regenerator. While cycling, the
structure and performance of the catalyst particles are severely affected. Here, we set out to
characterize the damage to FCC particles during cycling and regeneration and map the deactivation
pathways. Catalyst degradation was studied on a structural and a functional level with fluorescence,
IR and UV-Vis microscopies, μ-XRD, μ-XANES, iLEM and TXM. This approach allows discussing
inter- and intraparticle heterogeneities in terms of acidity, porosity and metal poison concentration.
17 IZC, 2013. KEYNOTE LECTURES
60
KN-3.1
Recent Advances and Current Challenges in Fluid Catalytic Cracking: Flexible Pilot Plant Can
Evaluate Unconventional Feedstocks and Processes
Kenneth Bryden, Gordon Weatherbee, and E. Thomas Habib, Jr.,
Grace Catalysts Technologies, W.R. Grace & Co.-Conn., Columbia, MD 21044
Tom.Habib@grace.com
The fluid catalytic cracking process has been in commercial practice for 70+ years. Feedstocks and
process designs have evolved greatly over this period. Today is a time of exciting change in the FCC
world. New feedstocks such as bio-oils (vegetable and pyrolysis), and straight run shale oils are
being investigated by refiners. New FCC designs such as High Severity Fluid Catalytic Cracking
(HS-FCC) and Deep Catalytic Cracking (DCC) have been developed. Olefins manufacturing
processes, e.g., such as the ExxonMobil PCCSM Process and the KBR Superflex™ process, and use of
FCC type processes for very light feeds (including gases and light alcohols) are being proposed.
These options represent significant change, and therefore significant risk. One way to minimize the
risk associated with these opportunities is to conduct realistic pilot plant testing prior to commercial
implementation. One pilot unit that has gained wide acceptance in mimicking commercial FCC
operation is Grace's DCR™ pilot plant. Including the two DCR pilot plants operated by W. R. Grace
& Co., a total of 26 licensed DCR pilot units have been constructed throughout the world. This paper
includes comparisons of DCR pilot plant results to commercial FCC units for petroleum derived gas
oil and resid feeds, and also describes application of the DCR pilot plant to a variety of alternative
feedstocks and process designs. Testing experiences with vegetable oil, pine-derived pyrolysis oil,
and straight run shale oil are described, highlighting the utility of the DCR unit in evaluating these
feedstocks and understanding their effects on yields and operation. Also, applications of the DCR in
studying new processes such as high temperature cracking processes designed for high light olefins
yields and processing gaseous feeds in a circulating fluidized bed are described.
17 IZC, 2013. KEYNOTE LECTURES
61
KN-3.2
Direct methane transformations into valuable products in zeolites. Is there any chance for the
methane co-conversion with higher hydrocarbons?
V. N. Parmon, A.G. Stepanov
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia, parmon@catalysis.ru
Huge deposits of fossil methane and forthcoming deficiency of other fossil hydrocarbon resources for
energetics and petrochemistry require the development of inexpensive methane conversion into more
valuable fuels and chemicals. Methane is the most inert among all alkanes with respect to their
involvement into chemical transformation. For this reason it is a challenge for chemists to involve
methane into direct chemical transformation avoiding the energy consuming formation of syn-gas.
Thermodynamic restrictions allow the direct methane transformation into higher hydrocarbons (e.g.
benzene) only at very high temperatures (above 1000 K) via direct methane insertion into heavier
hydrocarbons, whereas co-conversion of methane with higher alkanes makes the methane
transformation thermodynamically favorable even in lower temperature range.
In this presentation we discuss experimental data on the methane co-conversion with higher
hydrocarbons with respect to feasibility of this reaction. The pathways of the methane and higher
alkane activation on Zn- and Ga-modified high silica zeolites were followed with solid-state NMR
spectroscopy. The products of methane and propane co-conversion were identified. The use of 13Clabel tracing experiments (solid-state NMR and GC-MS) shows unequivocally the involvement of
methane in the reaction of propane aromatization on the Zn-(Ga-)-modified zeolites. The main
features of the mechanism of the involvement of methane into propane aromatization via direct
methane insertion into heavier hydrocarbons were established. The perspectives for the development
of the process for joint conversion of methane and higher hydrocarbons to produce aromatic
hydrocarbons on Zn- or Ga- modified zeolite ZSM-5 (BEA) are discussed.
KN-3.3
Depolymerization of wood components: role of zeolites
Dmitry Yu. Murzin
Åbo Akademi University, Turku, Finland, dmurzin@abo.fi
Due to the structure of biomass, which is different from petroleum, technologies of biomass
processing are different from those widely used in oil refining. In particular the oxygen to carbon
ratio in lignocellulosic biomass is close to unity, which is an undesirable ratio for production of
transportation fuels. As a slight amount of oxygen in the fuel is beneficial for gasoline engines,
substantial, although not total removal of oxygen from biomass is needed. On the other hand a large
number of intermediates in chemical industry contain oxygen. This implies that such substances as
methanol, acetic acid, and ethylene glycol with the carbon to oxygen ratio equal to unity do not
require a very high degree of oxygen removal. The main routes of biomass processing can be divided
into two classes. The first is based on torrefaction, combustion, gasification or pyrolysis of biomass at
rather high temperatures, while the second uses relatively mild conditions and involves hydrolysis as
the key step. Some examples of catalytic transformations of woody biomass with involvement of
zeolites performed in the laboratory of the author will be discussed in the presentation.
17 IZC, 2013. KEYNOTE LECTURES
62
KN-3.4
Clean Synthesis of Oximes and Amides over Titanosilicate Catalysts
Peng Wu
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal University, Shanghai, China, pwu@chem.ecnu.edu.cn
We will report in this presentation the preparation and structural modification of layered titanosilicate
Ti-MWW as well as its unique catalytic properties in liquid-phase oxidation reactions such as
ammoximation of ketones and epoxidation of alkenes. In continuous slurry reactor, Ti-MWW proves
to be more efficient than conventional TS-1 for the ammoximation of cyclohexanone or methyl ethyl
ketone. By coating Ti-MWW crystals with a mesoporous silica shell, the lifetime can be prolonged
effectively as a result of protection against desilication. By supporting the Rh(OH)x species onto TiMWW, a bifunctional catalyst is designed by combining together ketone ammoximation and
aldoxime rearrangement, which allows possible one–post synthesis of amides from aldehydes,
hydrogen peroxide and ammonia.
KN-3.5
Recent Advances in Adsorptive Separation Science & Technology
Joeri F.M Denayer and Gino V. Baron
Department of Chemical Engineering, Vrije Universiteit Brussel, 1050 Brussels, Belgium,
joeri.denayer@vub.ac.be
With the growing interest in cleaner production processes, sustainable and rational use of raw
materials and energy, CO2-emission reduction, a cleaner environment, better food quality, etc., it can
be foreseen that separation technologies will only gain importance. Separation processes have a major
influence on the industrial energy consumption, product costs and cost price of products. In many
cases, adsorption could be identified as an energy-efficient alternative to traditional thermal
separation processes, while in many other cases, only adsorption offers the required selectivity to
allow the desired separation or purification.
In recent years, hundreds of new adsorbent materials have been developed, including novel
adsorbents such as Metal Organic Frameworks, porous organic molecular crystals, hybrid carbonsilica materials, periodic mesoporous organosilica materials etc, but also variations of well known
zeolitic materials. Some of these materials show very interesting properties towards adsorptive
separation, many other materials suffer from stability issues.
In this contribution, selected cases where adsorption could offer a technological advantage will be
presented.
17 IZC, 2013. KEYNOTE LECTURES
63
KN-3.6
Nanoscale Manipulation of Zeolites and MOFs for Novel Bulk Scale
Applications: Tunable Photoluminescence to Nuclear Waste Remediation
T.M. Nenoff, D. F. Sava, L. E. S. Rohwer, M. A. Rodriguez, P. Crozier, J. A. Greathouse, K. W.
Chapman,* P. J. Chupas*
Authors’ affiliations: Sandia National Laboratories, PO Box 5800, Albuquerque, NM 87185, USA;
*Advanced Photon Source, Argonne National Laboratories, Argonne, IL 60439, USA
Our ability to design, synthesize and test novel Metal-organic Frameworks (MOFs) provides an
understanding of the structure-property relationship between nanoscale materials’ changes and bulk
scale applications. We present MOF research in two different applications areas: photoluminescence
and nuclear waste cleanup. For tunable photoluminescence responses, we design new MOFs by
tuning the metal centers, metal-ligand bonding, and functionalization of the ligands. The resulting
photoluminescence is tuned from broadband direct white light to intense red light. For fission gases
capture and storage, we are using a combination of modeling, mixed gas sorption and characterization
to tune MOFs for high selectivity in complex streams. This has broad applications in nuclear energy
(including reprocessing, accident cleanup, fuel supply). #Sandia is a multi-program lab operated by
Sandia Corp., wholly owned subsidiary of Lockheed Martin Co., for US DOE NNSA, contract DEAC04-94AL85000.
ORAL COMMUNICATIONS
SECTION 1:
“Ordered porous materials: synthesis and
modification”
1.1. Zeolites and zeotypes
66
O-1.1-01
Direct crystallization of CHA-type aluminosilicate zeolite without using OSDA from amorphous
aluminosilicate gel
Toshiyuki Yokoi, Hiroyuki Imai, Nozomu Hayashida, Junko N. Kondo and Takashi Tatsumi*
Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama, Japan,
ttatsumi@cat.res.titech.ac.jp
The high-silica aluminosilicate zeolite with the CHA topology, [Al]-SSZ-13, has directly been
synthesized. Unfortunately, the synthesis of [Al]-SSZ-13 requires the special and expensive organic
structure-directing-agent (OSDA), 1-trimethylammonio adamantine hydroxide, TMAdaOH. Herein,
we report a successful synthesis of CHA-type zeolites from an amorphous aluminosilicate gel by the
addition of the seed crystals with a CHA structure in the absence of OSDAs. Note that NaOH plays a
role of the crystallization of amorphous aluminosilicate gel and that KOH assists to form a CHA
phase in the synthesis of CHA-type aluminosilicate zeolite in the absence of OSDAs.
O-1.1-02
Alternate Synthesis Route for the Crystallization of CHA Zeolite:
OSDA-Containing Aluminosilicate Colloids
Ahmad Moini, Ivan Petrovic, and Subramanian Prasad
BASF Corporation, 25 Middlesex-Essex Turnpike, Iselin, NJ 08830, USA, ahmad.moini@basf.com
Aluminosilicate colloids containing organic structure directing agents (OSDA) were used for the
hydrothermal synthesis of CHA zeolites. The OSDA-containing colloids contained adamantyl
trimethylammonium cations with typical stoichiometry of [1 Al2O3 : 30 SiO2 : 1.62 R], and varying
levels of residual alkali. These colloidal particles contained all of the reactive components needed for
the crystallization of CHA zeolite. As a result, zeolite crystallization seemed to initiate within the
colloid particle rather than in solution, thus allowing for the formation of zeolite under
unconventional pH conditions and using lower OSDA contents. Such a process also allowed for
unique crystal size and agglomerate particle size of the final product.
O-1.1-03
A New aminophosphonium based Route for Synthesis of a zeolite related to STF/SFF family
R. Simancas, M. T. Navarro, A. Cantín, N. Velamazán, J. A. Vidal, J. L. Jordá, T. Blasco, F. Rey,
A. Corma.
Instituto de Tecnología Química (UPV-CSIC), Avda. De los Naranjos s/n, 46022-Valencia, Spain,
frey@itq.upv.es
SSZ-35 and SSZ-44 zeolites are the pure end-member polymorphs of the STF/SFF family. Their
structures show one-dimensional straight channels which contain pore openings that alternate
between 10MR and 18MR. The STF zeolite has shown very interesting results for toluene
disproportionation and for alkylation of toluene and p-xylene with isopropyl alcohol. It is known that
Phosphorus-modified zeolites improve their stabilities under catalytic conditions as well as during
catalyst regeneration. The main difficulty during the post-synthesis modifications of STF zeolites is
due to the one-dimensional channels structure which precludes the easy diffusion of the agents used
during the post-synthesis treatment. Here, we report a new synthesis route for preparing a Pcontaining zeolite ITQ-46 that could be structurally related to STF/SFF family. ITQ-46 was obtained
using a new aminophosphonium cation as structure directing agent that can be controllably removed
by calcination and subsequent water washing.
17 IZC, 2013. ORAL COMMUNICATIONS
67
O-1.1-04
Crystallization Mechanism of UZM-5 Zeolite in the Organic-Inorganic Mixed-SDA System
M. B. Park1, C. P. Nicholas2, G. J. Lewis2, S. B. Hong1
1Department of Chemical Engineering and School of Environmental Science and Engineering,
POTECH, Pohang 790-784, Korea, pmbum@postech.ac.kr
2UOP LLC, a Honeywell Company Des Plaines, IL 60017, USA
Here we investigate the formation pathway for UZM-5 zeolite (framework type UFI) in the
simultaneous presence of tetramethylammonium (TEA+), tetramethylammonium (TMA+), and Na+
ions as SDAs, whose synthesis mixture is same with that of UZM-9 (LTA) but crystallization
temperature is significantly different each other (150 vs 100 °C). The overall characterization results
of our work demonstrate that the nucleation of UZM-5 begins with the formation of large lta-cages
rather than smaller d4r-, rth-, or wbc-cages, like the case of UZM-9LS. Furthermore, we examined
the structure-directing role of organic and inorganic SDAs in the nucleation and crystal growth stages
of each UZM-5 and UZM-9LS zeolite synthesis according to the crystallization temperature.
O-1.1-05
New Molecular Sieves with ABC 6-Net Structures
Gregory J. Lewis, Robert W. Broach, Stuart R. Miller, Lisa M. Knight, Paulina Jakubczak, Justin
Stanczyk, and Nanette Greenlay
New Materials Group, UOP LLC, A Honeywell Company, Des Plaines, IL, USA,
gregory.lewis@uop.com
The investigation of the chemistry of two very similar SDA’s has yielded two new ABC 6-net
framework topologies with MAPO, SAPO, and MAPSO compositions. One SDA leads to AlPO-57,
which is the first ABC 6-net structure with a 5-layer repeat sequence (AABBC) and contains d6r, cha
and lev cages. The second SDA leads to AlPO-59, which is the first ABC 6-net structure with a 7layer repeat sequence (AABBCCB) and contains d6r and gme cages as well as a new 4126586 cage.
The addition of Si to high the SDA/H3PO4 syntheses that yield MAPO-57 or MAPO-59 leads to
MAPSO-64, which has the BPH topology. Lowering the SDA/H3PO4 in both systems leads to
MAPO-67 (LEV), another ABC 6-net structure with a 9-layer repeat sequence. The AlPO-59, AlPO57 and LEV topologies all exhibit 2-dimensional pore systems with access to diffusion along the caxis increasing in the order LEV < AlPO-57 < AlPO-59.
1.1. Zeolites and zeotypes
68
O-1.1-06
Synthesis of a new extra-large pore zeotype with 16-ring openings by using proton sponges as
organic structure directing agents
M. Moliner1, R. Martínez-Franco1, Y. Yun2, W. Wan2, X. Zou2, A. Corma1
1Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia, Consejo
Superior de Investigaciones Científicas, Valencia, 46022, Spain, mmoliner@itq.upv.es
2Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry,
Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm,
Sweden
The synthesis of crystalline microporous materials containing large pores are very demanded by the
industry, especially for their use as catalysts in chemical processes involving bulky molecules. The
first extra-large pore silicoaluminophosphate (SAPO) with 16-ring openings, ITQ-51, has been
synthesized by the novel use of bulky aromatic proton sponges as organic structure directing agents.
Proton sponges show exceptional properties for directing extra-large zeolites, due to their unusual
high basicity combined with large size and rigidity. This new extra-large pore material is stable after
calcination, being one of the very few examples of hydrothermally stable molecular sieves containing
extra-large pores. The structure of ITQ-51 was solved from submicrometer-sized crystals, using the
new rotation electron diffraction (RED) method. Finally, several new hypothetical zeolites related to
ITQ-51 have been proposed.
O-1.1-07
A Heteroatom-Containing Aluminophosphate with New Zeolite Structure and Tunable
Luminescent Property
Yanyan Wang1, Jiyang Li1* and Jihong Yu1
1State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, P. R. China, lijiyang@jlu.edu.cn
A new microporous magnesium-containing aluminophosphate |C5N2H13|[Mg2Al6(PO4)8(H2O)3] has
been prepared by using n-methylpiperazine as the structure-directing agent (SDA). Its anionic
framework is constructed by the alternating connection of metal-centered polyhedra (i.e. AlO4,
MgO4(H2O) or MgO4(H2O)2) and PO4 tetrahedra. After calcined at 300 ºC, the coordinated H2O
molecules can be removed, MgAPO-CJ71 transforms to a zeolitic strcuture |C5N2H13|[Mg2Al6(PO4)8]
built up absolutely from tetrahedra. It exhibits a new zeotype topology, which has two-dimensional
intersecting 8-ring channels with pore sizes of 7.2 × 3.7Å. Carbon nanoparticles are formed through
thermal decomposition of the occluded organic SDAs, meanwhile, the product shows tunable
fluorescent properties upon different calcination temperatures.
O-1.1-08
Synthesis of SUZ-4 zeolite with TEA salts
A. V. Toktarev, G. V. Echevsky
Boreskov Institute of Catalysis, Novosibirsk, Russia, atok@catalysis.ru
Crystallization of potassium aluminosilicate hydrogels in presence of tetraethylammonium salts was
studied. Phase composition of the crystallization products was analyzed by XRD technique depending
on nature of TEA salts, gel composition parameters, crystallization regimes. It is found that in
contrast to the previous practice of SUZ-4 crystallization in anion-free systems it readily goes in
presence of TEA sulfate. High quality of synthesized SUZ-4 zeolite was supported by SEM, DTA and
N2 adsorption methods. Reproducible method is found for the synthesis of the pure phase of zeolite
SUZ-4 in presence of TEAOH and K2SO4 as a complex template at crystallization temperature as low
as 144°C. Other anions like nitrate, bromide, chloride and fluoride are not suitable for SUZ-4 zeolite
formation.
17 IZC, 2013. ORAL COMMUNICATIONS
69
O-1.1-09
Synthesis of beta zeolite in the absence of alkali cations
Xiaomei Jia, Shaobing Yu, Fengmei Zhang, Xuhong Mu
State Key Laboratory of Catalytic Materials and Chemical Engineering, Research Institute of
Petroleum Processing, SINOPEC, Beijing, P. R. CHINA, muxuhong.ripp@sinopec.com
Beta zeolite was synthesized in the absence of alkali cations with low amount template (TEAOH/SiO2
=0.10) and short crystallization time (2-3 days). The physicochemical properties and catalytic
performance are similar as the conventional beta zeolite. In the alkylation of benzene with ethylene,
the ethylbenzene selectivity is 95.4% and the selectivity of ethylization is 99.4% when ethylene
conversion is 100%. The catalytic properties keep stable within 300h.
O-1.1-10
Synthesis of Zeolite ZSM-5 with novel bamboo morphology
Kun Jiao1, Zhengjia Li1, Xiaoqiang Yao1, Xiangyu Xu1, Jiaqing Song1,*, Zhaofei Li2, Qian Wang2,
Lijun Yan2, and Mingyuan He3
1State Key Lab of Chemical Resource Engineering, Beijing University of Chemical Technology,
Beijing, 100029, P. R. China
2Petrochemical Research Institute of Petrochina, Beijing, 100195, P. R. China
3Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal
University, Shanghai, 200062, P. R. China.
*Corresponding author, e-mail songjq@126.com, fax +86-10-6442-3325
The morphologies of zeolites have great influence on the adsorption and reaction of zeolites. In this
presentation, Zeolite ZSM-5 with novel bamboo morphology was successfully synthesized using
TPAOH and TPABr as SDA , water glass as silicon source and boehmite as aluminum source.
O-1.1-11
1ST Synthesis of New Frameworks by Unprecedented Top-Down Method, ADOR, from Zeolite
Precursor Monolayers
W. J. Roth1, P. Chlubna1, R. E. Morris3, P. Nachtigall2, O. Shvets4, J. Čejka1,
1J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague,
Czech Republic, wies.roth@gmail.com
2Dep. of Physical &Macromolecular Chem., Faculty of Sciences, Charles University, Prague, Czech
Republic
3EaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
4L. V. Pisarzhevskiy Inst. of Phys. Chem., Nat. Academy of Sciences of Ukraine, Kyiv, Ukraine
Mono-layers obtained from zeolite UTL are reassembled into ordered 3-D structures and upon
calcination produce two new zeolites IPC-4, assigned IZA code PCR, and IPC-2. As the 1st example
of new zeolite preparation by top-down approach the sequence is named ADOR to reflect Assembly
(of UTL)-Disassembly (into layers)-Organization-Reassembly. The corresponding zeolites comprise
homologous series with increasing number of 4-ring moieties bridging layers. There are
corresponding monotonic changes in their pores sizes and textural properties. The method may be
general, especially applicable to other zeolites with D4R supported layers.
1.1. Zeolites and zeotypes
70
O-1.1-12
Design of zeolite by inverse sigma transformation
Elke Verheyen1, Lennart Joos2, Kristof Van Havenbergh3, Eric Breynaert1, Nataliia Kasian1,4, Elena
Gobechiya1, Kristof Houthoofd1, Charlotte Martineau5, Manuel Hinterstein6, Francis Taulelle5,
Veronique Van Speybroeck2, Michel Waroquier2, Sara Bals3, Gustaaf Van Tendeloo3, Christine E. A.
Kirschhock1 & Johan A. Martens1
1Center for Surface Chemistry and Catalysis, KU Leuven, Heverlee, Belgium,
elke.verheyen@biw.kuleuven.be
2Center for Molecular Modeling, Ghent University, Zwijnaarde, Belgium
3Electron Microscopy for Materials Science, University of Antwerp, Antwerp, Belgium
4L.V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Kyiv,
Ukraine
5Tectospin, Institut Lavoisier, Universite de Versailles ST Quentin en Yvelines, Versailles Cedex,
France
6Institut fur Werkstoffwissenschaft, Technische Universitat Dresden, Dresden, Germany
A new approach for synthesizing new zeolites is described. We report the first experimentally
observed inverse sigma transformation leading to a new zeolite (COK-14). Units from existing
zeolites are harvested either from existing zeolites or during synthesis of a known structure and reassembled into new zeolite frameworks. Germanosilicate UTL zeolite served as source for its silicate
layers, which also can be obtained in crystalline form from an adapted UTL synthesis. These building
units can be used either in a direct sigma transformation into expanded structures or by inverse sigma
transformation into contracted topologies.
O-1.1-13
Interlayer expansion of RUB-36 with iron(III)chloride to obtain active alkylation catalysts
T. De Baerdemaeker1, B. Yilmaz2, M. Feyen3, U. Müller3, D. De Vos1
1Centre for Surface Chemistry and Catalysis, KU Leuven, Leuven, Belgium,
trees.debaerdemaeker@biw.kuleuven.be
2BASF Corporation, Iselin, NJ 08830, USA
3BASF SE, 67056 Ludwigshafen, Germany
The layered zeolite precursor RUB-36 can be transformed into a new zeolitic framework by interlayer
expansion using dichlorodimethylsilane as bridging agent. However, the incorporation of Al into the
precursor layer is challenging. Therefore a new approach was used to obtain an active catalyst derived
from the RUB-36 precursor. Instead of a Si-containing bridging agent, FeCl3.6H2O was used in the
interlayer expansion process. The obtained material is an active catalyst in the alkylation of toluene
with benzylchloride. The production of HCl in this reaction does not cause leaching of catalytically
active Fe species from this material.
17 IZC, 2013. ORAL COMMUNICATIONS
71
O-1.1-14
Ultrafast framework stabilization of a Ge-rich zeolite by low-temperature plasma treatment
Mohamad El-Roz, Frederic Thibault-Starzyk and Valentin Valtchev*
Laboratoire Catalyse et Spectrochimie, ENSICAEN - Université de Caen - CNRS, 6 bd du Maréchal
Juin, 14050 Caen, France. mohamad.el-roz@ensicaen.fr
Post-synthesis substitutions in zeolite frameworks are largely used in order to modify the properties
that cannot be controlled by in situ methods. These modifications are usually performed on two
stages, where first the organic template is removed and then the reaction leading to tetrahedral atoms
substitution is performed. Unfortunately, such an approach cannot be applied to materials that cannot
withstand the first step of the process. We report here a low-temperature TiCl4/SiCl4-plasma
approach, which allows a one-step template elimination and partial substitution of Ge in the
framework of Ge-silicate molecular sieves in BEC-type zeolite. The set of experimental data
unambiguously proof the successful stabilization of zeolite framework. Template extraction and
framework substitution of Ge for Si and Ti in zeolite structure is discussed as well as the
physicochemical characteristics and photoactivity of Ti-containing products.
O-1.1-15
Formation of a secondary phase during Ni2+ exchange of Faujasite: influence of conditions and
study by electron microscopies.
T. Onfroy, F. Aubrit, S. Casale, L. Gaberova, P. Massiani
Laboratoire de Réactivité de Surface, UPMC, Paris, France, pascale.massiani@upmc.fr
Cationic exchange of Ni2+ ions in solution is commonly used to prepare Ni-faujasite materials
efficient in applications such as hydrogen storage [1], biomass gasification [2] or CO hydrogenation
[3]. From available physicochemical characterizations, it is usually considered that the exchange
procedure does not affect the zeolite framework. However, we will show in this presentation that a
process of surface dissolution/recrystallization can readily take place, depending especially on the
characteristics of the parent faujasite. This leads to the presence of a secondary phase with lamellar
aspect that covers the surface of the zeolite crystallites. The influences of the Al content in the parent
faujasite (NaX and NaY) and of pH and temperature during exchange will be discussed.
O-1.1-16
Bimetallic Cu/Au-MCM-22 zeolite – surface properties and catalytic performance in total
oxidation of methanol and carbon monoxide
P. Kaminski1,3, I. Sobczak1, P. Decyk1, M. Ziolek1, W. J. Roth2, B. Campo3, M. Daturi3
1A. Mickiewicz University, Poznan, Poland, ziolek@amu.edu.pl
2J. Heyrovský Institute of Physical Chemistry, Prague 8, Czech Republic
3Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de Caen, CNRS, Caen, France
MCM-22 zeolite was used for the preparation of bimetallic (Cu-Au) catalyst for oxidation reactions.
The characterization techniques applied in this work (e.g. XRD, TEM, UV-Vis, H2-TPR, FT-IR,
ESR) allowed identification of the species formed. The presence of gold on the Cu/Au-MCM-22
surface caused much easier reduction of CuO-like species and higher mobility of oxygen promoting
total oxidation of methanol. The bimetallic catalyst was highly active in total oxidation of methanol
and CO in the temperature range 523 – 623 K. Cu/Au-MCM-22 appeared useful for the simultaneous
removal of CO and methanol (by total oxidation) from gases emitted from automotive devices and
during variety of industrial process operations.
1.1. Zeolites and zeotypes
72
O-1.1-17
Silver encapsulated in Silicalite-1
G. Pacheco-Malagon1, N.A. Sánchez-Flores1, P. Pérez-Romo2, A. García-Borquez 3, E. DiazValdes3, V. Meza-Laguna1, J.J. Fripiat1,2
1 Universidad Nacional Autónoma de México, Ciudad Universitaria, Col. Copilco, C.P. 04360,
México, D.F.
2 Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas No.152, Col. San Bartolo,
Atepehuacan, C.P. 07730, México D.F.
3 Instituto Politécnico Nacional, Juan de Dios Bátiz, Gustavo A. Madero, C.P. 07738, Ciudad
México, D.F.
Our aim is to report about the properties of silicalite -1 obtained from depolymerized crystalline
silicalite-1 with a easier access to internal surfaces and, in particular, in which silver ion has been
encapsulated. The bulky silver cation disorganizes the structure. Upon aging is squeeze out the
structure and form cubic silver crystal on the surface.
17 IZC, 2013. ORAL COMMUNICATIONS
73
O-1.2-01
Natural Zeolites from Ethiopia: Stilbite
Isabel Díaz1,2, Yonas Chebude1, Raquel García2, Luis Gómez-Hortigüela2, Joaquín Pérez-Pariente2,
Asfawossen Asrat3, Solomon Tadesse3, and Ana B. Pinar4
1Chemistry Department, Addis Ababa University, Addis Ababa, Ethiopia.
2Instituto de Catálisis y Petroleoquímica, CSIC, Madrid, Spain. idiaz@icp.csic.es
3Earth Science Department, Addis Ababa University, Addis Ababa, Ethiopia.
4Laboratory of Crystallography, Department of Materials, ETH Zurich, Switzerland.
Zeolites are a vast natural resource in Ethiopia that remains unexploited due to lack of scientific
knowledge and available manpower with a geology background. The main objective of our work is to
test the potential use of the naturally occurring zeolites of the country in fluoride extraction from
water in the Rift Valley area and assess the possibility of constructing sanitation plants based on this
zeolite technology. For this purpose, a deep knowledge and full characterisation of the zeolite
resources locally available in the country becomes essential. A first set of 10 samples were
characterized by powder X-ray diffraction to identify the crystalline phases, and by Elemental
Analyses (ICP-OES) to quantify the chemical composition. Due to its high purity, deeper studies by
Scanning Electron Microscopy, Thermogravimetry and Rietveld refinement of powder diffraction
data are conducted for sample ET1. XRD pattern of the sample showed that it is a stilbite-type (STI)
mineral.
O-1.2-02
Single and Binary Adsorption of Cadmium(II) and Copper(II) from Aqueous Solution onto
Mordenite
R. Leyva-Ramos, J. Mendoza-Barron, E. Padilla-Ortega and R.M. Guerrero-Coronado
Centro de Investigacion y Estudios de Posgrado, Facultad de Ciencias Quimicas, UASLP
Av. Dr. Manuel Nava No. 6, San Luis Potosi, SLP 78210, Mexico, rlr@uaslp.mx
The single and binary adsorption of Cd(II)-Cu(II) on mordenite was investigated in this work. The
experimental single and binary metal adsorption data were obtained in a batch adsorber. The single
adsorption equilibrium data was interpreted using the Langmuir and Redlich-Peterson isotherms. The
Redlich-Peterson isotherm fitted quite well the single adsorption data. The binary adsorption data was
interpreted with following multicomponent isotherms: non-modified, extended and modified
Langmuir; and non-modified and modified Redlich Peterson. The modified Langmuir
multicomponent isotherm best fitted the data of Cd(II)-Cu(II). At pH = 6 the single metal adsorption
showed that the capacity for adsorbing Cu(II) was near 3 times greater than that for Cd(II). However,
the competitive adsorption of Cd(II) and Cu(II) revealed that both metals presented similar
antagonism against the adsorption of the other metal. The single adsorption capacity of mordenite
towards Cd(II) and Cu(II) was increased by raising the solution pH, this trend was attributed to the
electrostatic interactions between the mordenite surface and the metal cations in solution.
1.2. Natural zeolites
74
O-1.2-03
Zn+2, Cu+2, Pb+2 and NH4+ Ion-Exchange on Clinoptilolites from Turkey and Romania
A. Sirkecioglu, M.G. Ahunbay, M.F. Yardim, H. Atakul
Department of Chemical Engineering, Istanbul Technical University, Istanbul, Turkey,
asirkeci@itu.edu.tr
Zn+, Cu+2, Pb+2 and NH4+ are the most abundant cations in the domestic, and small and medium-sized
enterprises wastewaters. It is very crucial to remove these cations from wastewaters before
discharging into surface water, such as rivers, streams, canals, groundwater or the sea due to the strict
environmental regulations. Clinoptilolite, which is one of the commercially available natural zeolite,
has high metal cation removal potential from wastewaters. In this study, candidate clinoptilolite
samples from three different regions -Bigadic and Gordes Regions of Turkey, and Marsid Region of
Romania- were investigated to determine their performances for Zn+, Cu+2, Pb+2 and NH4+ removal
from wastewaters. Batchwise cation exchange experiments were conducted on original and treated
clinoptilolite samples. Clinoptilolite samples were not only treated by washing in hot distilled water
but also treated by washing in acid and base solutions with varying concentrations. Preliminary
results show that all three pretreatment methods yield an increase in the cation exchange capacity
with different extend. Cation exchange capacity of the clinoptilolite samples benefited more from
washing in hot distilled water compared to acid and base pretreatments methods.
O-1.2-04
Modified, natural clinoptilolites from Slovakia and Mexico as catalysts for liquid-phase
isomerization of α-pinene
A. Dziedzicka, B. Sulikowski
Jerzy Haber Institute of Catalysis and Surface Chemistry Polish Academy of Sciences,
Niezapominajek 8, 30-239 Cracow, Poland, ncadzied@cyf-kr.edu.pl
Clinoptilolite is the world’s most abundant natural zeolite, widely used as an adsorbent, ionexchanger and molecular sieve. High crystallinity coupled with availability, low mining and
processing costs, make natural clinoptilolite a good choice for preparation of catalysts. The objective
of the work was to modify clinoptilolite in such a way as to obtain viable catalysts for reactions
proceeding in the liquid phase. Dealumination with hydrochloric acid was chosen as a method of
modification.
All the samples were characterized by XRD, FT IR and sorption of nitrogen. Multinuclear 1H, 27Al
and 29Si MAS NMR studies allowed deeper insights into the properties of the dealuminated
clinoptilolites. Initial rate constants of the process were calculated. It was shown that already the
treatment with diluted HCl resulted in a very significant increase of α-pinene conversion.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.2-05
Characteristics of Indonesian Natural Zeolites and Their Utilization for Increasing Crop
Production
Suwardi
Department of Soil Science and Land Resources, Bogor Agricultural University, Indonesia,
suwardi_bogor@yahoo.com
Indonesia is a country rich in natural resources including natural zeolites. More than 50 zeolite
deposits have been identified and some of them have been exploited. Some methods have been
developed for utilizing natural zeolites for soil amendments including direct application to soils;
mixed with calcite and compost; and as carrier of chemical and organic fertilizers. Indonesian zeolites
composed of mordenite, clinoptilolite, or mixed of them in different contents. Zeolites have relatively
high pH ranged from 6.3-9.7. The CEC of zeolites varied from 71.9-182 cmol(+)/kg depending on
zeolites contents in the samples. Zeolites improved the CEC and exchangeable K if they applied to
low CEC soils such as Red-yellow podzolic soils. Zeolites is better applied togather with other soil
amendments such as calcite and compost. Zeolies can be used as slow-release agent of humic
substances.
1.3. Mesoporous materials and hierarchical porous structures
76
O-1.3-01
Mesoporous Tungsten-Zirconium Composite Oxides - Preparation with a Wall Ion-Exchange
Method and Activity for Acidic Catalysis
Masashi Tanaka, Kohei Kabeya, Insuhk Suh, Haruro Ishitani, and Masakazu Iwamoto
Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama, Japan,
iwamoto@res.titech.ac.jp
The wall ion-exchange method was applied for composites of zirconium sulfate and surfactant
micelles (ZS) to prepare mesoporous tungsten-zirconium composite oxides (WZO). The ion
exchange of a monomeric tungsten oxyanion for the hydrogen sulfate anion in ZS well proceeded in
an aqueous solution. The surface areas and the pore diameters after removing surfactants by
extraction and/or calcination were 200-520 m2 g-1 and 0.8-2.4 nm, respectively. The catalytic activity
of WZO for Friedel-Crafts alkylation was greatly changed with the surfactant removal method and the
W/Zr ratio.
O-1.3-02
A general strategy for the synthesis of micelle-templated
mesoporous metal carbonates and metal oxides
Björn Eckhardt1, Erik Ortel1, Denis Bernsmeier1, Peter Strasser1, Ulla Vainio2, Jörg Polte1,
Franziska Emmerling3, Ralph Kraehnert1, *
1 Technical University of Berlin, Berlin, Germany
2 Deutsches Elektronen-Synchrotron DESY, Germany
3 BAM Federal Institute of Materials Research and Testing, Germany
ralph.kraehnert@tu-berlin.de
Catalysis, energy storage and light harvesting require functional materials with tailored porosity and
nanostructure. However, common synthesis methods that employ polymer micelles as structuredirecting agents fail for zinc oxide, cobalt oxide and for metal carbonates in general.
We report a new synthesis approach for metal carbonates and oxides with micelle-templated pore
structure. The synthesis relies on triblock copolymers poly(ethylene oxide)-block-poly(butadiene)block-poly(ethylene oxide) and a new type of precursor formed by chemical complexation of a metal
nitrate with citric acid. A general synthesis mechanism is deduced. Mechanistic insights allow for the
prediction of optimal processing conditions for different oxides and carbonates based on simple
thermogravimetric analysis.
Employing this synthesis, films of ZnO, Co3O4 and MgO with micelle-controlled mesoporosity
become accessible for the first time. It is the only soft-templating method reported so far that yields
also mesoporous metal carbonates. The developed synthesis is generic in nature and applicable to a
wide range of metal oxides and carbonates.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.3-03
New mesoporous silica-titania catalysts by biotemplating – towards green catalyst preparation
A. Sachse1, E. Belamie1, N. Marcotte1, K. Kostov2, V. Hulea1, B. Alonso1
1Institut Charles Gerhardt - UMR 5253 (CNRS/ENSCM/UM2/UM1), Montpellier, France,
alexander.sachse@enscm.fr
2 Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
A new class of porous silica-titania catalysts has been designed by combining the sol-gel process with
the self-assembly properties of chitin nanorods. The chitin templating technique gives as valuable
advantage the use of a waste product as structural agent (chitin recovered from shrimp fisheries) and
opens the way for efficient catalyst preparation with defined porosity upon calcination of the hybrid
materials.
By diverse elaboration techniques the Ti dispersion in our catalysts can be tuned, and by varying the
chitin fraction the textural properties of the obtained catalysts can be importantly influenced. Well
defined powders have been elaborated by coupling this process to spray-drying techniques.
The resulting functional materials where tested in the mild oxidation of sulphur containing
compounds. Catalytic properties in function of textural parameters have been studies and very high
conversions have been achieved for some of the designed catalysts. Further improvement of the
preparation process gives catalyst with even higher catalytic outputs.
O-1.3-04
A Spheric Mesoporous Sulfated Zirconia Material with High Catalytic Activity in Acetylation
Feng Yu, Min Guo, Wenbo Zhang, Yuming Yi, and Ruifeng Li*
Research Centre of Energy Chemical & Catalytic Technology, Taiyuan University of Technology,
Taiyuan 030024, China, Corresponding author: E-mail: rfli@tyut.edu.cn
A spherical meso-structured zirconia material was prepared by using SBA-15 containing carbonized
surfactant P123 in the mesopores as assisted template. The resultant ZrO2 material was characterized
by XRD, N2 adsorption-desorption, SEM, TEM and EDX. The mesoporous zirconia had high thermal
stability and larger surface area of more than 300 m2/g and pore volume of 0.25 cm3/g, even after the
calcined temperature of 1073K. The catalyst had a high ketone yields of 80 % in the acetylation of
anisole, compared to 45% of the conventional sulfated zirconia . This new spheric mesoporous
zirconia material may have a more extensive application in fine chemical, pharmaceutical industries
processes
O-1.3-05
Photocatalytic reduction of CO2 over modified Ti-TUD-1:
Forward vs. Backward reactions
Mohamed S. Hamdy1,2, Bastian Mei3, Jennifer Strunk3, Guido Mul1
1 PCS group, MESA+ Institute for Nanotechnology, University of Twente, The Netherlands.
m.h.saad@utwente.nl
2 Chemistry Department, Faculty of Science, Helwan University, Cairo, Egypt.
3 Department of Chemistry and Biochemistry, Ruhr-University Bochum, Germany.
The photocatalytic reduction of CO2 by water vapour to form light hydrocarbons (i.e. methane,
ethane, and ethane) over Ti-TUD-1 was carried out at room temperature by using a 120W Hg lamp as
a light source. The photocatalytic activity of Ti-TUD-1, which has a three-dimensional, open, foamlike structure, is higher than obtained for other mesoporous materials (e.g. Ti-SBA-15) under the
same reaction conditions. Furthermore, introducing nano-particles of ZnO or isolated Cr6+ species
into Ti-TUD-1, did not improve the photocatalytic performance, because their presence strongly
promotes the back reaction, i.e. the degradation of the formed hydrocarbons to CO2 and water.
1.3. Mesoporous materials and hierarchical porous structures
78
O-1.3-06
The view on synthesis and properties of MCM-41 and SBA-15 through mesostructure.
S.D. Kirik1,2 , V.A. Parfenov1, I.V. Ponomarenko1, S.M. Zharkov3,
1Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia,
kirik@icct.ru
2Siberian Federal University, Krasnoyarsk, Russia
3Kirenskii Institute of physics SB RAS, Krasnoyarsk, Russia,
The alterations of the MCM-41 and SBA-15 silicate mesostructure during synthesis have been
investigated in connection with variation of synthetic conditions. The parameters of the mesostructure
were estimated using the X-ray powder diffraction data processed by full profile analysis in
combination with the continuous electron density function. The X-ray data are supplemented by N2adsorption measurements and TEM. Considerations have been given to the variations of the synthesis
conditions affecting the hydrothermal stability and structural performance.
O-1.3-07
Synthesis of hierarchical zeolite catalysts with lamellar structural features
M. Tsapatsis1, X. Zhang1, M. Khaleel1, D. Xu1
1Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis,
Minnesota, USA, tsapatsis@umn.edu
The ordered micropores in zeolites (0.5-2 nm) are important for the selective catalytic conversion of
petroleum and biomass. In addition to the micropores, small structural features (smaller than 5 nm) as
well as mesoporosity are also needed to overcome the diffusion limitation and deactivation in
conventional zeolites. ZSM-5 (framework type MFI) and faujasites (zeolite X and Y, framework type
FAU) are two most important and most widely used zeolite catalysts in chemical industry. This study
focuses on the synthesis of hierarchical zeolites MFI and FAU composed of intersecting nanosheets.
In the hierarchical MFI zeolite, or self-pillared pentasil (SPP), 2 nm thin MFI nanosheets are prepared
in an intersecting "house-of-cards" architecture using a one-step hydrothermal synthesis. The
hierarchical FAU composed of mesoporous crystalline FAU nanosheets was prepared using a
alkoxysilane with a long alkyl chain, in which micropores, mesopores and macropores are all present
in one particle. The two growth processes are analyzed and compared.
O-1.3-08
On the formation mechanism of nanostructured MFI zeolite:
towards molecular understanding of zeolite synthesis by templating agents
M. Goesten,1 X. Zhu,2 N. Kosinov,2 R. Rohling,2 B.M. Szyja,2 L. Wu,2 J. Gascon,1 F. Kapteijn,1
E.J.M. Hensen2
1 Catalysis Engineering group, Delft University of Technology
2 Inorganic Materials Chemistry group, Eindhoven University of Technology
e.j.m.hensen@tue.nl
The formation mechanism of MFI zeolite nanosheets is investigated by in-situ methods and
computational modeling. It has been established that a diquaternary ammonium salt surfactant is able
to pre-organize silicate anions into a mesoporous silica structure containing already micropores and
local fragments reminiscent of the structure of the final crystalline zeolite nanosheets. The results are
consistent with a formation mechanism involving Si33 building units interacting in a specific manner
with the alkyl chains of the template.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.3-09
Bi-functional catalyst based on transition-metal oxides in zeolites with hierarchical pore system
Carolina Neudeck, Sandra Kestermann, Wolfgang Schmidt and Ferdi Schüth
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany, neudeck@kofo.mpg.de
A novel synthesis pathway to transition-metal oxide containing zeolites is introduced. In a first step
Fe2O3, @C nanoparticles are prepared following a nanocasting procedure. Secondly the obtained
nanoparticles are mixed with a regular carbon matrix and used as a template in the synthesis of
hierarchical zeolites. The inclusion of transition-metal oxide nanoparticles within the zeolite results in
a well-structured composite with unique properties. Bifunctional materials find wide applications in
catalysis and the redox-properties of the transition metal component together with the acidic
component in close proximity allow for two-step reactions on the different sites in a defined manner.
O-1.3-10
Progress on synthesis of hierarchical zeolite single crystal materials using
a carbon templating method
J. O. Abildstroem1, J. J. Mielby1, M. Kegnæs2, S. Kegnæs1
1Department of Chemistry, Technical University of Denmark, Lyngby, Denmark, skk@kemi.dtu.dk.
2Haldor Topsøe A/S, Nymøllevej 55, Lyngby, Denmark
The micropores in zeolite have dimensions close to those reactants and products found in many largescale processes making zeolite into widely used catalysts. However, the micropores can cause an
unacceptably slow diffusion of reactants and products to and from the active sites located inside the
zeolite resulting in low catalytic activity. By introducing mesopores during zeolite synthesis with the
use of an auxiliary carbon mesopore template this problem can be circumvented. Here the progress on
synthesis of hierarchical zeolite single crystal materials using in situ generation of carbon template is
presented. Further, the zeolite catalysts are applied in different selective oxidation reactions showing
a much higher activity for the mesoporous zeolites compared with conventional zeolite assigned to
the decrease in mass transfer limitations.
O-1.3-11
Synthesis and performance of hierarchical zeolite FeZSM-5
K. A. Sashkina1, E. V. Parkhomchuk1,2, V. N. Parmon1,2
1 Boreskov Institute of Catalysis SB RAS, 5 Lavrentieva st., Novosibirsk 630090, Russia,
sashkina@catalysis.ru
2 Novosibirsk State University, 2 Pirogova st., Novosibirsk 630090, Russia
Series of hierarchical zeolites ZSM-5 and FeZSM-5 were prepared by hydrothermal treatment using
polystyrene spheres template and characterized by X-ray diffraction, scanning and high-resolution
transmission electron microscopies, and N2 sorption techniques. Walls of the macroporous structure
consisted of ZSM-5 nanocrystals with a size of 20-300 nm and amorphous globules of SiO2.
Hierarchical FeZSM-5 contained iron in the form of iron oxide particles with a size of 2-3 nm.
Hierarchical zeolites had high values of surface area (437-613 m2/g), external surface area
(131-462 m2/g) and pore volume (0.36-0.76 cm3/g). Hierarchy of the zeolite porosity resulted in a
significant improvement of the catalyst performance.
1.3. Mesoporous materials and hierarchical porous structures
80
O-1.3-12
Preparation of Ti-MFI with Hierarchical Structures by Alkali Treatment
Masahiko Matsukata1,2, and Kentaro Nagashima1
1 Applied Chemistry, Waseda University, Tokyo, Japan, mmatsu@waseda.jp
2 Research Institute for Science and Engineering, Waseda University, Tokyo, Japan
As a solution to the diffusion limitation problem of Ti-containing MFI-type zeolite, high-silica MFItype zeolite was subjected to alkaline desilication treatment with various alkali (LiOH, NaOH, KOH,
CsOH, NH3, TMAOH, and TEAOH) aqueous solutions. Titanium was incorporated in the zeolite
framework by a post-CVD treatment. Catalytic performance for the oxidation of cyclohexane with
H2O2 was examined. Ti-MFI -treated with NH3 aq, TMAOH aq, and TEAOH aq clearly showed
higher activities than parent Ti-MFI. Those samples have increased mesopore volume and external
surface area with preserving micropore volume. In addition, these three types of samples possessed
abundant tetrahedrally coordinated Ti sites in the vicinity of external surface and successfully
showed higher activities for the cyclohexane oxidation with H2O2
O-1.3-13
The function of unstable-site in mesopore formation of zeolite Y framework and its catalytic
cracking performance
Baojian Shen*, Dongdong Guo, Yuchen Qin, Chengyu Guo, Hao Li, Qiaoxia Guo
State Key Laboratory of Heavy Oil Processing; the Key Laboratory of Catalysis of CNPC; and
College of Chemical Engineering, China University of Petroleum, Beijing, China,
baojian@cup.edu.cn
The unstable nature of Fe sites in Fe-NaY zeolite framework were employed as an inducement in
mesoporous USY zeolite preparation. It was proposed that the deferrization-created defects played a
crucial role in the formation of mesopores in Y zeolite framework during the steaming dealumination,
i.e. Fe site functioned as the initiate key to form mesopore in the following steaming deferrization and
dealumination precess. The resulting USY catalyst shows a much higher activity in 1, 3,5triisopropylbenzene catalytic cracking compared with conventional USY catalyst.
O-1.3-14
Permeable ceramometal monolith composites with incorporated mesoporous Al-SBA-15
S.F.Tikhov1, V.E.Ramanenkau2, Ya.Ya.Piatsiushyk2, T.Ye.Yeutukhova3,
E.A.Mel’gunova1, M.A.Mel’gunov1 S.V.Cherepanova1, A.N.Shmakov1, K.R.Valeev1
1 Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia, tikhov@catalysis.ru
2 Powder Metallurgy Institute NAS, Minsk, Belarus
3 Belarusian National Technical University, Minsk, Belarus
The porous monoliths with hierarchical porosity Al-SBA-15(20÷40%)/Al2O3/Al and Al-SBA15(1÷10%)/FeAlO/FeAl have been prepared via blending with the Al-containing powders and
topochemical solid phase oxidation rout. The textural, structural, mechanical and permeability
properties of the monoliths have been studied. The mutual influences of mesoporous Al-SBA-15 and
macroporous matrices Al2O3/Al, FeAlO/FeAl have been discussed.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.3-15
New routes to nanozeolite crystals with very few framework defects
Laurence Burel, Alain Tuel
IRCELYON, UMR 5256 CNRS-Université de Lyon 1, 2 Av. A. Einstein 69626 Villeurbanne Cedex,
France, alain.tuel@ircelyon.univ-lyon1.fr
In zeolites, the absence of defects is generally associated to large crystals, obtained following the
fluoride route. Defect-free nanosized zeolites are difficult to obtain by direct synthesis and their
preparation remains a challenge. In the present work, a two-steps strategy has been applied to
decrease the density of framework connectivity defects in nanosized silicalite-1 crystals. The
formation of hollow structures removed the most defective parts of the crystals whereas treatment of
the as-made hollow zeolites with NH4F considerably reduced the population of framework
connectivity defects. The combination of both methods led to nanocrystals (size of ca. 150 nm) with
unprecedented low amount of defects. 29Si NMR of the defect-free zeolites show highly resolved
patterns, similar to those observed on large zeolite crystals obtained in the presence of fluoride
species. This route opens new opportunities for the preparation of very small hydrophobic zeolite
crystals.
O-1.3-16
Multimodal zeolites with hierarchically micro-meso-macroporous structure
L.H. Chen1,2, X.Y. Li1, X.Y. Yang1,2, B.L.Su1,2*
1Laboratory of Inorganic Materials Chemistry (CMI), University of Namur (FUNDP), 61, rue de
Bruxelles, B-5000 Namur, Belgium. Email: bao-lian.su@fundp.ac.be
2State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan
University of Technology, Luoshi Road 122, Wuhan 430070, P.R. China.
A quasi-solid-state crystallization system was first developed to prepare a series of hierarchical
structured zeolitic materials with significant and stable micro-meso-macroporous structure. The
amorphous structure of these hierarchical meso-macroporous precursors were transformed into
crystalline zeolitic structure via this quasi-solid-state crystallization process with the effect of
corresponding zeolite structure directing agents at different aged temperature for different reaction
times. The resultant hierarchical structured zeolites, such as TS-1, ZSM-5, Beta, and Zr-S1 exhibited
superior catalytic activities compared to the conventional zeolitic catalysts.
O-1.3-17
Narrowing the mesopore size distribution in hierarchical TS-1 zeolite by surfactant-assisted
reorganization
D. P. Serrano1,2, R. Sanz1, P. Pizarro1,2, I. Moreno1, S. Shami1
1Dep. of Chemical and Energy Technology, Universidad Rey Juan Carlos, c/ Tulipán s/n, 28933
Móstoles, Madrid, Spain
2IMDEA Energy Institute, Avda. Ramón de la Sagra, 3, 28935, Móstoles, Madrid, Spain,
david.serrano@urjc.es
Hierarchical TS-1 zeolites, with a narrow mesopore size distribution, have been obtained by
combining two different approaches to generate the additional mesoporosity: i) crystallization of
silanized protozeolitic units and ii) treatment in presence of cationic surfactants in a basic solution.
The fist step leads to hierarchical TS-1 having a secondary porosity in a relatively broad range of
sizes. The second one produces a reorganization of this secondary porosity resulting in materials with
a narrower mesopore size distribution, around 40 Å. The catalytic activity of the treated TS-1 in
different oxidation reactions, using TBHP as oxidant, was higher than that of the parent sample,
denoting a positive effect of the more regular secondary porosity.
1.3. Mesoporous materials and hierarchical porous structures
82
O-1.3-18
Silicone Oil Surfactants Templating for Micro-and Nano-materials
Ji Feng,1 Bo Sun,1 Caiyun Guo,2 Yuan Yao1 and Shunai Che1, *
1 School of Chemistry and Chemical Technology, State Key Laboratory of Metal Matrix Composites,
Key Laboratory for Thin Film and Microfabrication Technology of the Ministry of Education,
Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 (P. R. China)
E-mail: chesa@sjtu.edu.cn
2 Petrochina Jilin Petrochemical Company Research Institute, 27 Zunyi East Road Longtan District,
Jilin, 132021 (P. R. China)
Block copolymers are widely used in the synthesis of micro- and nano- materials due to their
abundant self-assembly aggregates.[1, 2] Silicone surfactants are amphiphilic copolymers that contain
hydrophilic chains and hydrophobic polydimethylsiloxane (PDMS) chains with good compatibility
with the tetraethyl orthosilicate (TEOS), low surface tensions, the solubility in both aqueous and
organic solvents, and the low toxicity.[3] Otherwise, the micro-domains self-assembled by the silicone
surfactants are in the meso-scale, and the PDMS chains possess high decomposition temperature and
can be oxidized into silica. Therefore, the silicone surfactants not only acts as the templates for pore
formation, but also offers dimethyl siloxane segments for obtaining hydrophobic functionalized
surface, as well as provides silica source for thickening the walls or forms silica carbon composite by
calcination. Here, the self-assemble behavior and the structure transition mechanisms of the silicone
surfactants in the fabrication of the micro- and nano- materials are investigated. The mesoporous
silica with hydrophobic pore surface, mesoporous silica@carbon complex, hollow silica spheres and
various biomimetic mesostructures and morphologies have been easily formed by using PSEP as
template. The hydrophobicity of functionalized mesoporous silica have been investigated by
adsorption various hydrophobic molecules. In particular, in mesoporous silica@carbon complex, the
silica was positioned in the pores in uniform nano-size, which would facilitate the reduction of silica
by Li+ during the first discharge process due to their full contact, and therefore enhance the lithium
capacity of carbon frameworks.
O-1.3-19
Functionalized mesoporous sorbents and membranes obtained by hydrolytic polycondensation
reaction of alkoxysilanes
I.V. Melnyk1, О.А. Dudarko1, G.I. Nazarchuk1, N.V. Stolyarchuk1, V.V. Tomina1,
V.М. Kochkodan1, Yu.L. Zub1, A.Kozak2,3, A.Lobnik2,3
1Cuiko Institute of Surface Chemistry, NAS of Ukraine, 17 General Naumov Str., Kyiv 03164 Ukraine,
zub_yuriy@isc.gov.ua
2University of Maribor, Faculty of Mechanical Engineering, Centre of Sensor Technology, Smetanova
17, 2000 Maribor, Slovenia
3Institute for Environmental Protection and Sensors, Beloruska 7, 2000 Maribor, Slovenia
Applying different sol-gel techniques, there was synthesized and analyzed a number of polysiloxane
and polysilsesquioxane xerogels with amino, thiol, (thio)urea, carboxyl and (thio)phosphoryl groups;
xerogels with bifunctional surface layers; functionalized mesoporous silicas, spherical silica particles,
and ceramic membranes. The factors regulating their structural and sorption properties were
determined. Thus, hydrolytic polycondensation reaction of alkoxysilanes is a powerful tool for
creating functionalized organic-inorganic hybrid materials.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.4-01
Optimization of Lipase Immobilization in Mesoporous Organosilicas for Continuous Flow
Biocatalysis
Zhou Zhou, Frank Piepenbreier, Karl Karbacher, Martin Hartmann*,
Erlangen Catalysis Resource Center (ECRC), Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058
Erlangen, German, martin.hartmann@ecrc.uni-erlangen.de
Different approaches for the immobilization of lipase from Thermomyces Lanaginosus on ordered
mesoporous materials such as mesocellular foams and PMOs are evaluated with respect to their
performance as biocatalysts in the transesterification of 1-butanol with vinylpropionate. The catalysts
were first tested under batch conditions and then transferred to continuous flow fixed-bed reactors. It
is found that the formation of cross-linked enzyme aggregates (CLEAs) in the pores of suitable large
pore PMOs is the preferred route that results in highly active and comparably stable biocatalysts.
O-1.4-02
Catalysis with AuI onto a Coordination Polymer: A Solid Porous Ligand
with Free Phosphine Sites
M. Ranocchiari,*1 J. Václavík,2 M. Servalli,1 C. Lothschütz,2 J. Szlachetko,2 and J. A. van
Bokhoven*1,2
1 Laboratory of Catalysis and Sustainable Chemistry, Paul Scherrer Institute, Villigen PSI,
Switzerland marco.ranocchiari@psi.ch
2 Laboratory of Chemical and Bioengineering ETH Zurich, Zürich, Switzerland
LSK-1 is a novel porous coordination polymer that contains free phosphine sites homogeneously
distributed within the structure, and thus can be classified as a solid porous ligand (SPL) for transition
metals. Post-functionalization with AuI single-atom sites gives a material with an outstanding Au
content of 16% (w/w). The material is a rare example of AuI-impregnated solid, which was used as a
recyclable heterogeneous single-atom catalyst for reactions previously reported for homogeneous AuI
complexes.
O-1.4-03
Highly Ordered Mesoporous Fullerene Framework
K. Hou; N.K. Minar; M. Döblinger; F. Hanusch; T. Bein
Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians University of
Munich, Germany, norma.minar@cup.lmu.de
Here we report on a novel, highly ordered periodic mesoporous organosilica (PMO) that is entirely
constructed from individual silane-functionalized fullerene building blocks and whose mesoporosity
is controlled by cooperative self-assembly with a liquid-crystalline block-copolymer.
In contrast to most of the PMO precursors reported so far, the fullerene molecules can be
functionalized at many points, potentially resulting in an enormous multitude of possible fullerene
adducts with different symmetry and number of functionalities. This would lead to a complicated coselfassembly behavior between the precursor and surfactant, and likely to limited order in the final
product. To address this challenge, we surmised that a C60 hexakis-derivative with high Th symmetry
would be beneficial for the construction of a porous framework.
This new PMO material was obtained in the form of supported films by spin-coating the synthesis
solution directly on glass or silicon substrates, followed by a heat treatment. The material was fully
characterized by small angle X-ray diffraction, nitrogen sorption, transmission electron microscopy
and solid state NMR.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
84
O-1.4-04
Preparation of Zeolite/Chitosan Hybrid Composites and Binderless Zeolite Microspheres and
Their Applications
Liang Yu1, Jie Gong1, Changfeng Zeng2, Lixiong Zhang1*
1 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and
Chemical Engineering, Nanjing University of Technology, Nanjing 210009, PR China,
lixiongzhang@yahoo.com
2 College of Mechanic and Power Engineering, Nanjing University of Technology, Nanjing 210009,
PR China.
Zeolite A and X/chitosan hybrid composites with various shapes and high crushing strength were
prepared by bioorganic molecule-assisted impregnation-gelation-hydrothermal synthesis of
silica/chitosan monolith in a sodium aluminate solution. Zeolite A/chitosan hybrid composites with
high antimicrobial activity and bioactivity after different ion-exchange. Binderless zeolite A and X
microspheres with medium crashing strength and high adsorption capacities for water and CO2 were
obtained after calcination composites microspheres.
O-1.4-05
From the crystallization to the large scale synthesis of porous
Metal Organic Frameworks of interest
Florence Ragon1, Patricia Horcajada1, Hubert Chevreau1, Stuart Miller1, Florent Bridoux1, Thomas
Devic1, Nathalie Steunoux1, U.-Hwang Lee2, Young Kyu Hwang2, Jong San Chang2,
Christian Serre1,
Institut Lavoisier, UMR CNRS 8180, 45 Avenue des Etats Unis, Université de Versailles SaintQuentin, 78035 Versailles cedex, France, serre@chimie.uvsq.fr; 2
Catalytic Center for Molecular Engineering, Korea Research Institute of Chemical Technology
(KRICT), Daejeon, Korea
Porous Metal Organic frameworks (MOFs) are of interest for several applications such as separation,
gas storage, catalysis or biomedicine. Nevertheless, prior to their use, there is a strong need to develop
industrially relevant synthetic methods to obtain on a reproducible manner very large amounts of
solid together with an acceptable cost. In parallel, in order to deeply understand the mechanisms that
drive the formation of MOFs, there is a strong need to study the various synthetic parameters that
control their nucleation and growth. Thus, we propose here a combined study that considers the
crystallization study (either in- or ex-situ XRPD) of several porous MOFs of interest, i.e. metal(III or
IV) polycarboxylates that bear a high chemical stability and properties of interest (in separation,
catalysis, drug delivery…) such as UiO-66(Zr), MIL-125(Ti) and MIL-127(Fe), and their synthesis
optimization from the laboratory scale (grams) to their production and shaping at the pilot scale (kg).
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.4-06
Assessing the 3D internal structure of MOF-based mixed matrix membranes for natural gas
and biogas upgrading
T. Rodenas, M. van Dalen, P. Serra-Crespo, F. Kapteijn and J. Gascon.
Catalysis Engineering, Chemical Engineering dept., Delft University of Technology, The Netherlands,
t.rodenas-torralba@tudelft.nl
Mixed matrix membranes (MMMs) comprising a metal organic framework (MOF) filler embedded in
a polymeric matrix represent a promising alternative for CO2 removal from natural gas and biogas.
Here we report the synthesis of mixed matrix membranes based on the flexible NH2-MIL-53(Al)
MOF dispersed in polyimide. Quantitative analysis derived from tomographic Focused Ion BeamScanning Electron Microscopy (FIB-SEM), is presented as a powerful approach to assess the 3D
spatial distribution of the MOF filler in the membrane and quantify the volume of voids at the
filler/matrix boundary. Such unique insight into essential features of the internal structure of the
membranes opens new horizons towards a more rational design of these hybrid membranes.
O-1.4-07
In-Situ NMR, XRD and SEM Study of the Hydrothermal Crystallization of Nanoporous
Aluminum Trimesates MIL-96, MIL-100, and MIL-110
M. Haouas1, C. Volkringer2,3, T. Loiseau2,3, G. Férey2, F. Taulelle1
1Tectospin, ILV, Université de Versailles Saint Quentin, France, haouas@chimie.uvsq.fr
2Porous Solids, ILV, Université de Versailles Saint Quentin, Versailles, France
3Present address: Unité de Catalyse et Chimie du Solide, Université de Lille Nord de France
In an attempt to understand the relationship between the chemistry occurring in solution and the
topology of the final crystalline structures, ex situ and in situ methods were conducted to investigate
the formation mechanisms of three porous aluminum trimesates MIL-96, MIL-100, and MIL-110. In
situ speciation in solution during hydrothermal crystallization were monitored using 27Al and 1H
NMR spectroscopy. The nature and morphology of the various intermediate solid phases, at different
reaction times, were followed by means of ex situ powder XRD and SEM, in relation with the
solution speciation. This multimodal approach allowed assignment of the 27Al NMR signals of
species in solution. The three steps of aggregation of monomers and dimers, condensation into the
building blocks and network formation are very fast, allowing the formation of identical topologies
than those built from stable trimers as with Cr and Fe.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
86
O-1.4-08
New porous M4+ (Zr, Ti) based MOFs: from poly-carboxylate to naturally occurring carboxyphenolate ligands
Florence Ragon1, Lucy Cooper1, Laura Pardo1, Ana Lago1, Nathalie Guillou1, Charlotte Martineau1,
Thomas Devic1, Christian Serre1, Guillaume Clet2, Alexandre Vimont2 and Marco Daturi2
1 Institut Lavoisier, UMR CNRS 8180, 45 Av des Etats-Unis, Université de Versailles Saint-Quentin,
78035 Versailles, France, thomas.devic@uvsq.fr;
2 Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de Caen, UMR CNRS 6506, 6 Bd
Maréchal Juin, 14050 Caen, France.
MOFs based on Zr4+ and Ti4+ exhibit enhanced stabilities or interesting photophysical properties. We
will present here our new developments dealing first with new MOFs based on acid functionalized
dicarboxylate ligands such as derivatives of Zr terephthalate UiO-66 or presenting new topologies.
Nevertheless, carboxylate binding groups present limitations, such as a limited stability of the
resulting solids in neutral to basic medium, and a very poor electronic communication between the
inorganic cation and organic backbone. The use of phenolate derivatives could circumvolve these
limitations. The reactivity of Ti4+ with a mixed carboxylate / phenolate ligand was thus systematically
explored. This study led to the isolation of various phases, most of them presenting a ligand to metal
charge transfer resulting in a strong optical absorption in the visible range. Finally, we extended this
strategy to another tetravalent cation (Zr4+), and to naturally occurring ligands.
O-1.4-09
Hierarchical Polyoxometalate-based Metal-organic Frameworks
L.H. Wee1, C. Wiktor2, S. Turner2, W. Vanderlinden3, G. Van Tendeloo2, S. De Feyter3, C.E.A.
Kirschhock1, J. A. Martens1
1Centre for Surface Chemistry and Catalysis, KU Leuven, Kasteelpark Arenberg 23, B3001, Leuven,
Belgium, likhong.wee@biw.kuleuven.be
2EMAT, University of Antwerp, Groenenborgerlaan 171, B2020, Antwerp, Belgium
3Molecular and Nanomaterials, Laboratory of Photochemistry and Spectroscopy, KU Leuven,
Celestijnenlaan 200f, B3001, Leuven, Belgium
Rational room temperature synthesis of COK-15 (COK = Centrum voor Oppervlaktechemie en
Katalyse), an hierarchical variant of the microporous cubic HKUST-1 metal-organic framework
having strictly repetitive 5 nm wide mesopores separated by uniform microporous walls in a single
crystal structure was demonstrated via a dual-templating approach. Stability was enhanced by Keggin
type phosphotungstate (HPW) systematically occluded in the cavities constituting the walls between
the mesopores. This first hierarchical MOF inspired us to explore the synthesis of other mesoporous
material using POM for stabilizing the walls of wider mesopores.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.4-10
Microporous and mesoporous phenylenecarboxylate metal-organic frameworks as host
matrices for Pd nanoparticles stabilization
E.V. Afonina1, V.I. Isaeva1, E.E. Said-Galiev2, V.V. Chernyshev3, L.M. Kozlova1, O.P. Tkachenko1,
L.M. Kustov1
1N.D..Zelinskii Institute of Organic Chemistry RAS, Moscow, Russia, sharf@ioc.ac.ru
2 A.N. Nesmeyanov Institute of Elementoorganic Compounds RAS, Moscow, Russia
3 Dep. of Chemistry, Moscow State University, Moscow, Russia
MOFs are promising materials for stabilization of metal nanoparticles (NPs). Our work aimed at
elucidation of the difference between the catalytic performance of Pd NPs stabilized within the pores
of the metal-organic framework and on its outer surface. The microporous MOF-5, and mesoporous
MIL-100(Fe) and NH2MIL-101(Al) were utilized as the palladium carriers. Pd was introduced
according to 1) incipient wetness impregnation, and 2) fluid synthesis (supercritical CO2). The
hydrogenation of phenylacetylene into styrene was studied over Pd@MOF composites. The
dispersion and location of Pd NPs were examined by XRD, TEM, and XAS. Embedding the small Pd
nanoparticles (less 1-2 nm)metal nanoparticles mainly in the pores was achieved both in case of
1%Pd@MOF-5 prepared in supercritical CO2, and Pd@MIL-100(Fe)/Pd@NH2MIL-101(Al). This
type of the active site location resulted in the enhanced selectivity with respect to styrene.
O-1.4-11
Influence of octahedra connectivity and linker shape on the formation of microporous and
highly stable chain-based Al-based MOFs
N. Stock1, H. Reinsch1, F. Niekiel1, M. Krüger1
1Insitute of Inorganic Chemistry, CAU-Kiel, Germany, stock@ac.uni-kiel.de
Al-based MOFs containing carboxylate ions are of interest due to their structural variability, stability
and low toxicity. While rigid, linear dicarboxylate linker molecules lead preferably to isoreticular
MIL-53-type structures we have systematically studied the use of ditopic linear, flexible as well as
rigid V-shaped linker molecules in the synthesis of Al-based MOFs. These led to a number of new
stable, small pore MOFs and two new framework topologies were discovered. Larger changes in the
linker geometry led to new inorganic-building units or new connectivities. Subtle changes through
introduction of small functional groups within a given structure have large effects on the porosity and
chirality of the framework structures.
O-1.4-12
Controlling MIL-53 flexibility by functionalization and metal nodes – Impact on carbon dioxide
separation, optical properties and mechanical stability
P. Serra-Crespo1, Freek Kapteijn1, Jorge Gascon1
1Catalysis Engineering, Chemical Engineering Department, Delft University of Technology,
Julianalaan 136, 2628 BL Delft, The Netherlands. j.gascon@tudelft.nl
A series of NH2-MIL-53 (X) (X= Al, Ga & In) materials has been thoroughly investigated. In situ
XRD showed a two-phase transition upon adsorption of carbon dioxide accompanied by a change in
symmetry and cell expansion. In this case, flexibility does not only enhances CO2 separation
selectivity of these materials, but also tunes their optical properties and confirms members in this
series as high contrast non-linear optical switches. Furthermore, the mechanical stability of the
synthesized NH2-MIL-53s was studied showing a remarkably high stability against amorphization (>
10 GPa).
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
88
O-1.4-13
Metal-organic framework thin films and post-synthetic modification for enhanced selectivity in
the adsorption of CO2
Andrew D. Burrows, Dongmei Jiang, Luke L. Keenan and Karen J. Edler
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK,
a.d.burrows@bath.ac.uk
Two methods for producing crystalline thin films of the metal-organic framework MIL-101(Cr)
[Cr3OF(H2O)2(bdc)3, bdc = 1,4-benzenedicarboxylate) on porous alumina are described. These are an
in situ method involving seeding of nanoparticles and a dip-coating method in the presence of the
polymer polyethylenimine (PEI). Furthermore, a new method of covalent post-synthetic modification
is presented whereby the amino-functionalised MIL-101(Cr)-NH2 is converted into halo- and azo dyefunctionalised MOFs in a tandem process starting with diazotisation. The acid stability of the MIL101(Cr) system allows for new methods of post-synthetic modification such as this.
O-1.4-14
Highly mesoporous and enantioselective metal-organic frameworks
Stefan Kaskel,1 Irena Senkovska,1 Frank Glorius,2 Elias Klemm,3 Eike Brunner4
1Inorganic chemistry, Dresden University of Technology, Dresden, Germany,
Stefan.Kaskel@chemie.tu-dresden.de
2 Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Münster, Germany
3 Institute of Chemical Technology, University of Stuttgart, Stuttgart, Germany
4 Bioanalytical Chemistry, Dresden University of Technology, Dresden, Germany
A number of new metal-organic frameworks with pore diameter above 2 nm and specific surface area
above 4000 m2/g will be presented. A special focus will be devoted to the integration of chiral groups
for enantioselective catalysis and separation, integration of solvatochromic guests with specific
response towards solvents inside mesoporous MOFs and synthesis of chemically stable MOFs.
O-1.4-15
Reversed Crystal Growth in Selected Zeolites and MOFs
W. Z. Zhou1, H. F. Greer1, C. M. Zheng1,2, Y. H. Liu1, R. E. Morris1
1EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, United
Kingdom, wzhou@st-andrews.ac.uk
2Dep. of Materials Science and Engineering, School of Aerospace Science and Engineering, National
University of Defense Technology, Changsha, Hunan 410073, China
Step-by-step investigations of the products in the crystal growth of some selected zeolites and MOFs
have revealed that they follow a reversed crystal growth route. At an early stage, the precursor
molecules or small crystallites aggregate into disordered particles, which undergo surface recrystallization to form monocrystalline shells with a high symmetric polyhedral morphology. The
crystallization then extends from the surface to the core. This novel growth mechanism allows us to
better understand the microstructures of the materials, and will allow more freedom in the crystal
engineering of zeolite/MOF research.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.5-01
Purification of MFI-Nanosheets by Density Gradient Centrifugation and Their Application as
Ultrathin Zeolite Membranes
K.V. Agrawal, B. Topuz, L.F. Francis, M. Tsapatsis
Dep. of Chemical Engineering & Material Sciences, University of Minnesota, Minneapolis, USA,
varoo001@umn.edu
Sub-100 nm thick zeolite membranes are desirable for large-scale deployment of zeolite membranes,
and can be fabricated by assembly of high-aspect-ratio zeolite nanosheets on a porous support. We
recently reported synthesis of structurally and morphologically intact MFI-nanosheets (Varoon et al.,
Science 334 (2011) 72-75) by exfoliation of multilamellar MFI using melt blending with polystyrene.
The multilamellar MFI was prepared according to the report by Ryoo and co-workers (Nature 461
(2009) 246-249). Approximately 350 nm thick zeolite membranes were prepared by filtration of MFInanosheets on a porous support followed by mild hydrothermal treatment. To achieve a sub-100 nm
membrane, the nanosheets must be purified to obtain monodisperse (in thickness and lateral size)
suspensions, while removing polymer, organic contaminants and larger unexfoliated particles. This
can be achieved by processing the nanosheet suspension by density gradient centrifugation (DGC).
MFI-nanosheets were purified from polymer and organic contamination by nonlinear one-step density
gradient as confirmed by thermogravimetric analysis (TGA). Removal of larger unexfoliated particles
was achieved by multilayered nonlinear density gradients created by organic solvents. Transmission
electron microscopy (TEM) images of the purified nanosheets revealed that they were free of polymer
and larger unexfoliated particles. The yield of exfoliated nanosheets obtained by DGC purification
was 10%. The electron diffraction (ED) patterns of nanosheets reveal that they are highly crystalline.
The scanning electron microscopy (SEM) imaging of the nanosheet film shows that they cover the
entire support while orienting themselves along their b-axis. Cross-sections prepared by focused ion
beam (FIB) show that the films are 80nm thick and follow the contour of the underlying support.
Membranes prepared by secondary growth of the nanosheet films, separated p-xylene from o-xylene
with separation factors of 25-45.
O-1.5-02
Incorporation of bifunctional Pd/ZSM-5 within microreactors for MIBK synthesis
L.A. Truter1, V.V. Ordomsky1, T.A. Nijhuis1, J.C. Schouten1
1Dep. of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, The
Netherlands, lara.truter@tue.nl
A coating method has been developed whereby hydrothermal synthesis of ZSM-5 is conducted within
chip microchannel reactors. The concept of using the microchannel wall as a nutrient and nucleation
source was investigated by either the deposition of a silica precoating or, alternatively, the selective
dissolution and transformation of the glass microchannel surface to zeolite. The use of a silica
precoating allowed the coating thickness and zeolite crystal size to be independently controlled while
transformation of the glass microchannel wall eliminated lengthy pretreatment procedures.
Application of the Pd/ZSM-5 chip-microreactor for the multiphase conversion of acetone to MIBK
showed improvements in MIBK selectivity.
1.5. Zeolite and MOF membranes and films
90
O-1.5-03
3D Architecture Formation with Zeolite Crystals on Solid Substrates
with Lithographic Approaches
S.K. Kirdeciler1, B. Akata 1,2
1Micro and Nanotechnology Department, Middle East Technical University, Ankara, Turkey,
kaankirde@gmail.com
2Central Laboratory, Middle East Technical University, Ankara, Turkey
The design of selective coatings for advanced applications, such as selective adsorption, sensor
arrays, patterning of biomolecules and nanoparticles, miniaturized electronics and magnetic devices
as well as development of microfluidic channels and lab-on-a-chip systems have attracted growing
attention.
In this study, the aim is to generate different 3D architectures of varying properties on the same
substrate using zeolites without chemical linkers. This aim was investigated through the use of two
completely different zeolite types possessing totally different morphologies, pore structures, chemical
and surface properties. For that purpose, both electron beam lithography and photolithography
techniques were combined with direct attachment technique to produce a variety of different patterns
of well controlled nano to micron sizes.
O-1.5-04
Synthesis of up-scaled tubular high-silica CHA-type zeolite membranes for an industrial
application to 2-propanol dehydration under high temperatures and pressures
K. Sato1, T. Kyotani1, T. Kikuchi1
1 Separation Material Department, Mitsubishi Chemical Corporation, 8-3-1, Chuo, Ami, Inashiki
Ibaraki, JAPAN, 1619019@cc.m-kagaku.co.jp
High-silica CHA-type tubular zeolite membranes with 1m long were synthesized for application to
dehydration of hydrous iso-propanol under higher pressures and temperatures up to 0.43 MPaG and
130 ℃. The membranes exhibited higher membrane performance with 40 kgm-2hi-1 in permeation
flux for a vapor feed containing 20 wt% water. These results suggest that the high-silica CHA-type
zeolite membranes can be applicable to dehydration under water-rich feed conditions and practical
high-temperatures.
O-1.5-05
Synthesis of Ordered Mesoporous TiO2 Membranes as Functional Materials
R. Passalacqua, C. Ampelli, S. Perathoner, G. Centi
Dept. of Electronic Engineering, Industrial Chemistry and Engineering and INSTM/CASPE,
University of Messina, Messina, Italy, rpassalacqua@unime.it
In the present work, free-standing membranes of well-ordered vertically aligned TiO2 nanotubes (with
both the ends open) were fabricated. The high-quality of the membranes was obtained with facile and
reliable procedures by taking advantage of i) the different mechanical stability between thermal
treated and not treated layers, ii) the less defective nature of the layer anodized at lower temperature
and iii) a pulse detaching technique. These one-dimensional nanostructures exhibit unique properties
because of their special geometry, high surface area and aspect ratio paving the way for transferring
ions, electrons, photons, as well as gases and liquids.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-1.5-06
Programmed Functions with Surface Mounted
Metal Organic Framework Thin Films (SURMOFs)
Roland A. Fischer,1 Min Tu,1 Bo Liu1
1Chair of Inorganic Chemistry II, Ruhr-University Bochum, Germany, roland.fischer@rub.de
Multi-variant hetero-SURMOFs, [Cu2(NH2-bdc)2(dabco)](B)-on-[Cu2(bdc)2(dabco)](A) and
[Cu2(ndc)2(dabco)] (C)-on-[Cu2(NH2-bdc)2(dabco)](B)-on-[Cu2(ndc)2(dabco)](C) and related systems
were deposited through stepwise liquid phase epitaxy (LPE) and characterized by quartz crystal
microbalance techniques, surface X-ray diffraction, IRRAS and SEM. The location/position of
functional groups can be tailored via altering the thickness of each sub-block of multilayers. Thus,
stepwise LPE makes it possible to fabricate more sophisticated MOF thin film materials with
programmed functionalities. Hetero-SURMOFs grown on QCM substrates may serve as devices to
discriminate and determine the analytes from mixtures according to their different kinetic behaviors.
Such multi-variant SURMOFs are suggested to exhibit excellent potential for separation as stationary
phases for PLOT columns in capillary GC, especially for complicate mixtures or for components in
smart membranes for advanced separation tasks or for chemical sensors based on surface acoustic
wave guides.
O-1.5-07
Interfacial Effects Control Mass Transport in Mixed Matrix Membranes
Anna Santaniello1,2, Maria Giovanna Buonomenna1, Giovanni Golemme1
1Dept. of Chemical Engineering and Materials, Università della Calabria, Rende, Italy,
ggolemme@unical.it
2 Dept. of Physics, Università della Calabria, Rende, Italy
The gas permeability of glassy, amorphous perfluoropolymer mixed matrix membranes (MMMs)
containing permeable/impermeable silicalite-1 (MFI) crystals was measured and carefully modeled
with the standard or modified Maxwell or Cussler macroscopic models. The comparison demonstrates
that, besides the permeability in the polymer bulk, in the filler and the alteration of the polymeric free
volume next to the filler surface, also the barrier to transport on the outer surface of the porous filler
particles controls the mass transport in MMMs.
This work has been funded by the PON 01_01840 project “Microperla - Programma di Energie
Rinnovabili e Micro-Cogenerazione per l’Agroindustria”.
ORAL COMMUNICATIONS
SECTION 2:
“Advances in fundamental understanding of
structure and properties”
2.1. Theory and modeling
94
O-2.1-01
Quantum Chemical Studies of Zeolite-Catalyzed Reactions
Alexis T. Bell, Paul Zimmermann, Joseph Gomes, Shaama M. Sharada, Martin Head-Gordon
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA
94720-1462, USA, bell@cchem.berkeley.edu
Theoretical predictions of reactions occurring in zeolites are challenging because large
representations of the zeolite framework are required to capture the long-range effects of coulombic
and van der Waals interactions. These challenges can be overcome using quantum
mechanics/molecular mechanics (QM/MM. The QM/MM approach can also be used to compute
quasi-classical trajectories (QCT) initiated at transition states, from which the distribution of reaction
products formed can be determined. Here we report several illustrations of QM/MM and QCT for
describing the kinetics of reactions occurring in zeolites. Examples include the cracking and
dehydrogenation of light alkanes (propane to hexane), and methylation of alkenes by methanol
occurring in H-MFI. Calculations of heats of adsorption and activation barriers determined from
QM/MM are in close agreement with experiment for a variety of chemical reactions. QCT
calculations reveal that the pathways from transition states to products are significantly more complex
than those deduced from an analysis of minimum energy pathways and provide an accurate method
for predicting product distributions.
O-2.1-02
Monte Carlo Simulation of Zeolite Crystal Growth
M.W. Anderson1, J.T. Gebbie1
1Centre for Nanoporous Materials, School of Chemistry, The University of Manchester, Oxford Road,
Manchester M13 9PL, UK, m.anderson@manchester.ac.uk
Nanoporous materials are an important class of materials having a wide range of industrial and
commercial applications. Gaining an understanding and therefore control over the growth of these
crystals remains a very important milestone in being able to tailor materials to their respective
applications. In this study the crystal growth of nanoporous materials is investigated using a coarse
grain Monte Carlo approach based on the stability of closed cages, this approach could find wide use
for chemists that are interested in template design that stabilise specific cage types and shows the
expected effect on crystal morphology from using specific templates.
O-2.1-03
Spectacular diffusion behavior of aromatics in MOF type materials : A combination of
Molecular Dynamics simulations and Quasi-Elastic Neutron Scattering experiments
S. Rives1, 2, H. Jobic2, N. Ramsahye1, Y. Ke1, D.I. Kolokolov3, A.G. Stepanov3, T. Devic4, C. Serre4
and G. Maurin1
1ICGM, Université Montpellier 2,France, guillaume.maurins@um2.fr;
2IRCE Lyon, France;
3Boreskov Institute of Catalysis, Novosibirsk, Russia; 4 Université de Versailles-CNRS, France.
By combining experimental techniques operating at different time scales with molecular simulations,
we were able to fully characterize an unprecedented corkscrew dynamics for the benzene confined in
a series of MOFs including the MIL-47(V) containing. This spectacular diffusion behavior is also
valid for xylene molecules but in addition, we evidenced a unusual temperature dependent diffusion
regime characterized by two distinct activation energies and microscopic mechanisms.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-2.1-04
Anisotropic Elastic Properties of Flexible Metal-Organic Frameworks
Aurélie Ortiz 1, Anne Boutin 2, Alain H. Fuchs 1, François-Xavier Coudert 1
1 CNRS & Chimie ParisTech, 11 Rue Curie, Paris, France, aurelie-ortiz@etu.chimie-paristech.fr
2 École normale supérieure, Département de Chimie, 24 rue Lhomond, Paris, France
Much attention has recently been focused on Soft Porous Crystals. These flexible MOFs feature
dynamic crystalline frameworks displaying reversible structural transformations in response of
external physical constraints. Previous studies have shown that the stress induced on the framework
by mechanical pressure or guest adsorption plays a central role in structural transitions. We
characterized the mechanical properties of five different flexible MOFs by ab initio calculations of
their elastic constants. We highlighted the highly anisotropic nature of their elastic properties and
shed light onto the microscopic origin of stimuli-induced structural transitions in flexible MOFs.
O-2.1-05
Structure, stability and reactivity of extraframework iron-containing sites in Fe/ZSM-5 zeolite
E.A. Pidko, G. Li, I. Filot, E.J.M. Hensen
Inorganic Materials Chemistry group, Eindhoven University of Technology, P.O. Box 513,
NL-5600 MB, Eindhoven, The Netherlands. E-mail: e.a.pidko@tue.nl
A comprehensive DFT study of the structure, stability and reactivity of different Fe complexes
confined in ZSM-5 zeolite complemented by an ab initio thermodynamic analysis and microkinetic
modeling allowed us to develop a resolved molecular-level picture underlying the unique catalytic
properties of Fe/ZSM-5 catalysts. It is demonstrated that only a limited number of potential Fe
complexes can be present in the catalytic material. Their relative population is determined by the
synthesis and catalyst activation conditions. The high reactivity of Fe/ZSM-5 in the direct benzene
oxidation and catalytic N2O decomposition reactions is due to the presence of two distinct types of
extraframework active species. Whereas the former process is promoted by isolated Fe2+ cations, the
latter reaction takes place over more complex oxygenated binuclear iron centers. These computational
results point to the routes for further development of Fe/ZSM-5-based catalysts.
O-2.1-06
Probing bridging hydroxyls under controlled conditions:
a surface science approach to study zeolites
J.A. Boscoboinik1, X. Yu1, E. Emmez1, B. Yang1, F.D. Fischer2, R. Wlodarczyk2, M. Sierka3, S.
Shaikhutdinov1, J. Sauer2, H.-J. Freund1
1Fritz-Haber-Institut der Max-Planck-Gesellschaft, Chem. Phys. Dept., Berlin, Germany, bosco@fhiberlin.mpg.de .
2Humboldt-Universität zu Berlin, Dept. of Chemistry, Berlin, Germany.
3Friedrich-Schiller-Universität Jena, Inst. of Mater. Sci. and Tech., Jena, Germany.
An aluminosilicate ultra-thin film with bridging hydroxyls similar to the ones found within the pores
of zeolites was synthesized on a Ru(0001) support. The film consists of a planar arrangement of
polygonal prisms. This structure allows well-defined studies of the interaction of molecules with
bridging hydroxyls using the analytical tools provided by surface science. The interaction with a
series of probe molecules, including weak and strong bases commonly used to probe zeolites, was
analyzed.
2.1. Theory and modeling
96
O-2.1-07
DFT studies of T-atom distribution and mobility in zeolites and zeotypes
S. Svelle, T. Fjermestad, S. Malola, M. Zokaie, K. P. Lillerud, O. Swang
inGAP center of research based innovation, Department of Chemistry, University of Oslo P.O. Box
1033 Blindern, N-0315 Oslo, Norway, stian.svelle@kjemi.uio.no
It is well known that zeolites may be partially hydrolyzed by steaming at elevated temperature. This
will decrease their crystallinity, but in some cases improve their efficiency as catalysts as both pore
structure and acidity are modified. Also, for SAPO materials, it is well documented that Si may
agglomerate into so called silicon islands during continuous reaction/regeneration cycles. By
employing both molecular mechanics and periodic density functional theory, unprecedented insights
on the distribution and mobility of framework T-atoms in zeolites and zeotypes has been obtained.
O-2.1-08
Inter-conversion of EFAL species and influence of alkali cations in dealuminated zeolites
Andrei A. Rybakov1, Alexander V. Larin1*, Georgy M. Zhidomirov1,2
1Chemistry Department, Lomonosov MSU, Moscow, Russia; nasgo@yandex.ru; 2Boreskov Institute of
Catalysis, Novosibirsk, Russia
The step of water dissociation under the adsorption on dealuminated mordenites and Y zeolites can be
indeed controlled by the Na+ influence but both increase (8R cluster) and decrease (6R+4R) of
activation energy was obtained in our model study. Despite a slight variation between relative
stabilities of hydrated AlOH2+ and Al(OH)2+ species at the isolated cluster level and using periodic
boundary conditions, activation energies remain similar being around 0.3-0.7 eV. This shows
relatively easy transformations between the AlOH2+ and Al(OH)2+ species which can vary their AlOX
coordination between X = 4 and 5. The inclusion of the inter-conversion between EFAL species can
be important for final NMR assignment.
17 IZC, 2013. ORAL COMMUNICATIONS
97
O-2.2-01
Redistribution of iron among various sites in micro- and mesoporous ferrisilicates
upon redox cycling
K. Lázár
Centre for Energy Research, Institute of Isotopes, Budapest Hungary, karoly.lazar@energia.mta.hu
Coordination and oxidation states of iron in micro- and mesoporous ferrisilicates can be changed
during their exposure to redox treatments, which can conveniently be traced by in situ 57Fe Mössbauer
spectroscopy. Application of the method is demonstrated by comparing the cases of microporous FeMCM-22 and mesoporous Fe-MCM-41. Framework to extra-framework relocation is dominant for
MCM-22, whereas facilitated Fe3+ to Fe2+ reduction and changes in the coordination are revealed for
Fe2+ located in the pore walls of MCM-41.
O-2.2-02
Critical evaluation of the catalytic potential of zeolites with controlled Al distribution in the
framework
Zdenek Sobalik, Petr Sazama, Jiri Dedecek and Blanka Wichterlova
J. Heyrovsky Institute of Physical Chemistry, AV CR, Prague 8, Czech Republic
zdenek.sobalik@jh-inst.cas.cz
Novel approach to zeolite synthesis providing for determination of the critical role of Al distribution
in optimization of the performance of metallo-zeolites for redox processes will be summarized in the
presentation. Ferrierite zeolites with Si/Al 8-10 and ZSM-5 and beta zeolites with Si/Al 12 -15 with
targeted Al distribution were synthesized using variation of sources of aluminum and silica, templates
and precursors. Reaction of N2O decomposition over Fe-FER, NO decomposition over Cu-ZSM-5,
C10H22-SCR-NOx over Cu-ZSM-5, NH3-SCR-NOx over Cu-ZSM-5 or Fe-ZSM-5, and of C3H8-SCRNOx over Co-beta were chosen for evaluation of the role of variation of the Al distribution for
performance of the metallo-zeolites.
These result open possibility for critical evaluation of the catalytic potential of the zeolites with
tailored distribution of Al in the framework and open possibility to use the traditional and well known
high silica zeolites as tailored catalysts with optimized properties.
O-2.2-03
Competitive Diffusion of Gases in a Zeolite Using A Slice Selection Procedure
S. Leclerc1, M. Petryk2, D. Canet1, J. Fraissard3
1Méthodologie RMN, Univ. H. Poincaré, 54506 Vandoeuvre-les-Nancy cedex, France
2Modélisation du Transfert de Masse, University Ivan Pul’uy, Ternopil, 46001 Ukraine
3LPEM - ESPCI and UPMC, 10 Rue Vauquelin, 75005 Paris cedex, France
E-mail: jacques.fraissard@upmc.fr
A new NMR imaging technique is used for following the co-diffusion and co-adsorption of benzene
and hexane in a ZSM5 zeolite bed used as examples. Contrary to the classical 1H NMR imaging, the
“Slice Selection Procedure” gives a signal characteristic of each adsorbed gas. It can therefore
provide directly, at every moment and at every level of the bed, the distribution of several gases
competing in diffusion and adsorption. From these data we can calculate, for each gas, the diffusion
coefficient profiles against time, at each position of the bed, and then the corresponding concentration
distributions in the inter and intra crystallite spaces.
2.2. Advanced characterization techniques
98
O-2.2-04
Normal and Single-File Diffusion in One-Dimensional Nanochannels: New Insights from
Advanced NMR
M. Dvoyashkin1,2, A. Katihar2, A. Wang2, J. Zang3, G.I. Yucelen4, S. Nair3, D.S. Sholl3, C.R.
Bowers1, S. Vasenkov2
1Dep. of Chemistry, University of Florida, Gainesville, USA
2Dep. of Chem. Engineering, University of Florida, Gainesville, USA, svasenkov@che.ufl.edu
3School of Chem. & Biomol. Engineering, Georgia Tech, Atlanta, USA
4School of Materials Sci. and Engineering, Georgia Tech, Atlanta, USA
Fundamental understanding of transport of guest molecules in nanotube materials is an important
prerequisite for an optimization of transport properties of these materials. Here we report results of
studies of diffusion of light gases in aluminosilicate nanotubes as well as in some other model
nanotube materials. Diffusion studies were performed by pulsed field gradient NMR in combination
with hyperpolarized 129Xe NMR as well as by MD simulations. Depending on the relationship
between the nanotube diameter and sorbate size, different types of dynamics corresponding to normal
and single-file diffusion were observed.
O-2.2-05
MAS-PFG and HP-129Xe NMR spectroscopy to reveal the dynamics of encapsulated ibuprofen
F. Guenneau, A. Nossov, M.-A. Springuel-Huet, T. Azais, F. Babonneau and A. Gédéon*
UPMC Univ Paris 06, LCMCP, F-75005, Paris, France, antoine.gedeon@upmc.fr
HP-129Xe NMR has been used to follow the distribution of ibuprofen molecules in MCM-41 materials
and to point out their motional behaviour. Whereas N2 measurements indicate that the whole
mesoporous network of loaded ibu-35 solid is full of ibuprofen, 129Xe NMR demonstrates the
capability for xenon to diffuse through the organic molecules and to probe local occluded void space.
This suggests a high mobility of ibuprofen molecules allowing xenon atoms to flow through the
organic phase. The magic-angle spinning (MAS) and pulsed-field gradient nuclear magnetic
resonance (PFG NMR) techniques have been combined for the investigation of mobility of ibuprofen
in MCM-41 materials. Diffusion coefficients of 1.7.10-11 and 6.8.10-13 m2/s have been obtained.
O-2.2-06
Development of fully-automatic ammonia IRMS-TPD analyzer
Kazuyuki Nakai 1*, Yoshikazu Senga1, Tatsuya Torikai 1, Naonobu Katada2, Miki Niwa2
1BEL Japan, Inc.
2Department of Chemistry and Biotechnology, Tottori University
kazu@nippon-bel.jp
Acidic property of a solid catalyst is one of the important factor for acid-catalyzed reactions. For
evaluate acidic property, pioneering works have been carried out to develop a method of ammonia
IRMS (infrared/mass spectroscopy)-TPD by Niwa et al. for measurements of the numbers and
strength distributions of Brønsted and Lewis acid sites, and furthermore, the number and Brønsted
acid strength of each type of acidic OH group.
However, these works were done with home-made equipments, causing not only difficulty in
operation but also such problems as low accuracy due to a large dead volume of the cell and low
reproducibility of the position of sample.
We have developed a fully-automatic analyzer applicable to the ammonia IRMS-TPD measurements.
The functions, performance of analyzer and some examples of the obtained results are presented in
this talk.
17 IZC, 2013. ORAL COMMUNICATIONS
99
O-2.2-07
How to quantify the nickel and copper species in zeolites?
IR studies of CO and NO adsorption.
K. Góra-Marek, J. Datka
Jagiellonian University, Faculty of Chemistry, Krakow, Poland, gorak@chemia.uj.edu.pl
Quantitative IR experiments were realized to determine the concentration of copper and nickel
species in Cu- and Ni-zeolites. The experimental conditions in which known amount of CO and NO
interact with each type of copper (Cu2+, Cu+ex, Cu+ox, Cuo) and nickel sites (Ni2+ex, Ni+ox, Ni+ex) were
established. The condition of stoichiometric reaction between CO (NO) and sorption site was
fulfilled. Consequently, the values of the extinction coefficients of the bands of CO or NO bonded to
copper and nickel species were determined. Total concentration of all copper and nickel forms
obtained in IR studies is the same as the concentration of Cu and Ni from chemical analysis. It
validates the accuracy of our experimental procedure. The independence the extinction coefficient
values on the type of zeolite has been also stated, therefore, these values, determined for CuZSM-5,
can be applied for the determination of the concentration of copper sites in other types of zeolites.
O-2.2-08
New TEM techniques for solving unknown zeolites, metal-organic frameworks and other
porous materials
Xiaodong Zou
Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental
Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden. xzou@mmk.su.se
Here I will introduce two new transmission electron microscopy (TEM) methods: 3D Rotation
Electron Diffraction (RED) and through-focus structure projection reconstruction that are powerful
for solving unknown structures including disordered crystals. The data collection using RED is
automatic and can be used by non-TEM experts. I will present structures of several new zeolites,
metal-organic frameworks and covalent frameworks solved from the RED data. I will also
demonstrate the structure solution of an aluminosilicate zeolite family ITQ-39 solved by electron
crystallography. ITQ-39 is an intergrowth of three different polymorphs, built from the same layer but
with different stacking sequences. It has a three-dimensional intersecting pair-wise 12-ring and 10ring pore system and is a promising catalyst for converting naphtha into diesel fuel.
O-2.2-09
The Morphology of Pt/Zeolite Y Hydrocracking Catalysts: 3D Imaging and Quantification at
Nanoscale
J. Zečević1, H. Friedrich2, P.E. de Jongh1 and K.P. de Jong1*
1Inorganic Chemistry and Catalysis, Utrecht University, Utrecht, The Netherlands j.zecevic@uu.nl
2Materials and Interface Chemistry, Eindhoven University of Technology, Eindhoven, The
Netherlands
We have studied in great detail the morphological properties of the industrially relevant Pt/zeolite Y
catalyst using electron tomography and image analysis. This combination enabled us to image
thousands of Pt particles as small as 1 nm inside the zeolite Y microporous regions, and quantitatively
assess properties, such as particle-particle distances and Pt loading of individual crystals, that are
inaccessible to other techniques. This study points to the great importance of nanoscale analysis of
complex morphological systems, as nanoscale features, such as large variation in Pt loading between
crystals, can dictate catalyst behavior on a macroscale.
2.2. Advanced characterization techniques
100
O-2.2-10
The top surface observation of nano porous materials using
ultra low voltage SEM
S. Asahina1, Y. Sakuda1, M. Kudo1, N. Kikuchi1, R. Ryoo2, O. Terasaki3,4,
1 JEOL Ltd., SM Business Unit, 1-2 Musashino 3-Chome, Akisima, Tokyo 196-8558, Japan,
sasahina@jeol.co.jp
2 Department of Chemistry, and Graduate School of Nanoscience and Technology (WCU), KAIST,
Daejeon 305-701, Republic of Korea
3 Graduate School of EEWS (WCU), KAIST, Daejeon 305-701, Republic of Korea
4 Structural Chemistry, Arrhenius Laboratory, Stockholm University, 10691 Stockholm, Sweden
Nanostructured materials such as zeolites, MOFs, mesoporous silica crystals and hierarchical-porous
composites have attracted a lot of attention. To understand surface fine structures and their
compositions is essential for controlling the growth of these materials and for the future material
design and the utilization of their functions. Technical developments in low acceleration voltage high
resolution scanning electron microscopy (LVHRSEM) have made it possible to acquire invaluable
information about them even though the materials are electrical insulating and electron beam
sensitive. In this report, we focused on observations with electrons at ultra-low impact energy such as
below 500 eV in order to acquire information from top surface of material.
17 IZC, 2013. ORAL COMMUNICATIONS
101
O-2.3-01
Key Molecular Mechanisms for Zeolite Formation
M. Castro1, W. Park2, M. Houas3, G. Brabants4, E. Breynaert4, I. Lim1, C. Kirschhock4, F. Taulelle3,
R. Ryoo5, F. Schüth1, W. Schmidt1
1Max-Plank-Institut für Kohlenforschung, Mülheim a.d. Ruhr, Germany, castro@kofo.mpg.de
2Department of Chemistry, KAIST, Daejeon 305-701, Korea
3Tectospin, University of Versailles Saint Quentin en Yvelines, France
4Center for Surface Science and Catalysis, K. U. Leuven, Belgium
5Center for Nanomaterials and Chemical Reactions, Institute for Basic Science, Daejeon 305-701,
Korea
Zeolites are highly valuable materials for industrial applications, especially for catalytic processes and
as adsorbents. Nevertheless, the molecular mechanisms involved in their formation remain poorly
understood and therefore, the synthesis of zeolites continues on an empirical stage. Our research aims
to identify the key mechanisms on a molecular scale with the goal of understanding the factors that
drive the formation of zeolites. Here, we report the first study of the molecular mechanisms involved
in the formation of microporous and mesostructured zeolite beta from liquid phase using electrospray
ionization mass spectrometry (ESI-MS), 29Si and 27Al liquid-NMR spectrometry, DOSY NMR
(diffusion experiments) and small angle X-ray scattering (SAXS).
O-2.3-02
At-line analysis of the crystallization of Zeolite LTA by Raman spectroscopy
T.F. Chaves1, F.L.F. Soares2, R.L. Carneiro2*, D. Cardoso1
1Dep. of Chemical Engineering, Federal University of São Carlos, São Carlos, Brazil.
2Dep. of Chemistry, Federal University of São Carlos, São Carlos, Brazil.
*renato.lajarim@ufscar.br
Several studies have been directed to comprehend the mechanism involved in the production of
zeolites. The use of Raman spectroscopy has been shown to be an important technique for the
understanding of its catalytic mechanisms and syntheses. In this work the synthesis of zeolite LTA
was monitored by Raman spectroscopy, using a reaction mixture with high alkalinity. The synthesis
was carried out at 25 ºC and Raman spectra were collected at different reaction times, from the liquid
and solid phases during 80h of reaction. During the reaction, some spectra of the liquid phase had
shown bands centered at 618 cm-1 and 1066 cm-1, which are attributed to the soluble hydrated
aluminosilicate species and CO32- species formed in the gel due to the capture of atmospheric CO2 by
the highly alkaline mixture. After 56 h it was possible to observe a better definition of the band at 500
cm-1, which is related to the presence of the characteristic four-membered rings (4R) of this zeolite.
The LTA zeolite was successfully synthesized after 72 h of reaction. DRX analyses of solid products
at 24, 48, 72 and 80h of reaction time confirmed that there were not crystalline forms until 48h of
reaction, what confirms the data obtained by at-line Raman analysis.
2.3. Mechanistic studies; impact of in-situ and operando techniques
102
O-2.3-03
Multi-Faceted Spectroscopy Reveals H-ZSM-5 Phosphatation Pathways
Hendrik E. van der Bij1, Luis R. Aramburo,1 Bjørnar Arstad,2 Bert M. Weckhuysen1
1Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterial Science, Utrecht University,
Utrecht, The Netherlands, h.e.vanderbij@uu.nl
2Department of Process Chemistry, SINTEF, Oslo, Norway
Two preparation routes for the phosphatation of zeolite H-ZSM-5 have been explored with a series of
spectroscopic methods, leading to new insights in the physicochemical processes taking place during
phosphatation. The first pathway is a phosphatation of H-ZSM-5 and leads to a small decrease in SiO-Al bonds and strong decrease in Brønsted acid site density. Phosphorous is present mainly on the
zeolite external surface. Strong Al-O-P interactions have not been found. The hydrothermal stability
of non-distorted TFAl sites was comparable to that of non-modified H-ZSM-5. The second pathway
follows the phosphatation of a pre-dealuminated H-ZSM-5 sample. The result is a mesopororous HZSM-5 material comprising an inter-crystalline AlPO4 phase. TFAl groups in this sample have high
thermal stability.
O-2.3-04
Reactive intermediates in methane to methanol conversion over Cu containing zeolites
P. Vanelderen1, J. Vancauwenbergh1, P. J. Smeets1,2, R. G. Hadt2, J. S. Woertink2, R. A.
Schoonheydt1 E. I. Solomon2 and B. F. Sels1
1 Center for Surface Chemistry Catalysis, KU Leuven, Leuven, Belgium,
Pieter.Vanelderen@biw.kuleuven.be
² Department of Chemistry, Stanford University, Stanford, California 94305, USA
The presentation addresses new steps forward in the understanding of the methanol producing Cucore in Cu-ZSM-5, an important issue in the activation of inert methane. This is achieved by a
combined UV-vis and resonance Raman study. The complete understanding of this active copper site
will have a major contribution to different scientific disciplines. Cu-ZSM-5 could serve as a model for
the design of active sites, as well as a tool to better understand the working mechanism of enzymes.
O-2.3-05
Methane activation and transformation on Ag/H-ZSM-5 zeolite studied by solid-state NMR
in-situ
A.G. Stepanov, A.A. Gabrienko, S.S. Arzumanov, A.V. Toktarev
Boreskov Institute of Catalysis, SBRAS, Novosibirsk, Russia, stepanov@catalysis.ru
1H and 13C MAS NMR was used to follow the subsequent steps of methane activation and
transformation into aromatics on Ag/H-ZSM-5 zeolite at 423-823 K. Both Ag+ cations and Brønsted
acid sites has been shown to be involved in activation of C-H bonds of methane on Ag/H-ZSM-5
zeolite. The intermediate species at methane transformation to aromatics have been identified, they
are methoxy species, ethane and ethene (π-complex of ethene with Ag+ cation). In the presence of
ethene a conversion of methane into aromatics increases. This is rationalized by alkylation of ethene
with methane and further transformation of intermediate propene into aromatics (benzene). Thus, we
conclude that methane can be involved in aromatization reaction with ethene on Ag/H-ZSM-5
zeolite.
17 IZC, 2013. ORAL COMMUNICATIONS
103
O-2.3-06
Evidence of transition-state shape selectivity in the reaction of
methanol to olefins on nanoSAPO-34
Zhibin Li 1,2, Joaquín Martínez-Triguero1, Jihong Yu2, Avelino Corma1
1Instituto de Tecnología Química, UPV-CSIC, Valencia, 46022 (Spain), jomarti@itq.upv.es
2 State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun, 130012 (China).
NanoSAPO-34 synthesized in microwave environment showed higher lifetime than SAPO-34
prepared by conventional hydrothermal method in the reaction of methanol to olefins. When
nanoSAPO-34 after calcination was aged in contact with room moisture, silicon at the border of the
silicon islands was affected by hydrolysis resulting in much higher lifetime and lower C2/C3 ratio.
This change in activity and selectivity is better explained in terms of different acid strength than on
preferential diffusion of ethene through the 8MR pores and agrees with transition-state shape
selectivity. In addition, equilibrium of olefins and deactivation by coke were isolated, showing that
after full formation of hydrocarbon pool selectivity is independent of coke content.
O-2.3-07
Activation energies and pre-exponential factors of C3 to C8 alkane conversion over various
zeolites and non-zeolitic solid acids
N. Katada1, S. Sota1, K. Okumura1, M. Niwa2
1Dep. of Chemistry and Biotechnology, Tottori University, Tottori, Japan, katada@chem.tottoriu.ac.jp
2Dep. of Research, Nagoya Industrial Science Research Institute, Nagoya, Japan
Rates of reactions (cracking, dehydrogenation and skeletal isomerization) of linear or monomethylbranched and small alkanes, i.e., propane, butane, pentane, 2-methylbutane, hexane and octane,
around 773 K in low pressures of alkanes and low conversions under first-order kinetics were
analyzed. The following two relationships were observed with a few exceptions over various zeolites,
amorphous silica-alumina and sulfated zirconia. [1] The stronger the acid site, the lower the activation
energy. [2] The lower the activation energy, the lower the pre-exponential factor in Arrhenius
equation when the factor was normalized by the number of Brønsted acid sites. The latter relationship
was common for C4 to C8 alkanes, but different for propane.
O-2.3-08
Regeneration of an organophilic ZSM-5 after sulfamethoxazole antibiotic adsorption: an in situ
high-temperature synchrotron powder diffraction study
L. Leardini1, A. Martucci2, I. Braschi3, S. Blasioli3, R. Arletti4, S. Quartieri1
1Dep. of Physics and Earth Sciences, University of Messina, Messina, Italy, lleardini@unime.it
2Dep. of Physics and Earth Sciences, University of Ferrara, Ferrara, Italy
3Dep. of Agro-Environmental Science and Technology, University of Bologna, Bologna, Italy
4Dep. of Mineralogical and Petrological Sciences, University of Torino, Torino, Italy
The thermal regeneration of a high-silica ZSM-5 after sulfamethoxazole (SMX) adsorption was
investigated by in situ high temperature synchrotron XRPD to monitor the structural modifications
induced by heating. The sample is stable towards thermal regeneration necessary to induce complete
degradation of SMX (at 575 °C). After this, the ZSM-5 framework is very similar to that of the assynthesized material.
ORAL COMMUNICATIONS
SECTION 3:
“Industrial and emerging applications”
3.1. Oil refinery and petrochemistry
106
O-3.1-01
Versatility of MFI catalytic applications in refining and base chemicals: total experience
N. Nesterenko1, D. Minoux1, J-P Dath1
Total Refining and Chemicals, Total Research & Technology Feluy, Seneffe, Belgium, jeanpierre.dath@total.com
The properties of the MFI typology offer a lot of interesting research approaches for a vast range of
on-purpose modifications that can improve the catalyst performances. It is in part a tribute to the
versatility of the structure that a lot of refining & base chemicals products have passed through the
MFI.
Total Research and Technology Feluy developed several processes based on this topology. The most
known examples have been the Olefin Cracking Process (OCP) and the Akzo-Fina Cold Flow
Improvement process (CFI). In the communication, the approach used by Total Research and
Technology Feluy (among others, role of synthesis parameters, post-synthesis treatments) will be
discussed.
O-3.1-02
Hydrocarbon Transformations Catalyzed by UZM-35, a Material Containing Both 10MR and
12MR Pores
Christopher P. Nicholas, Jaime G. Moscoso, Deng-Yang Jan
New Materials, UOP LLC, a Honeywell Company, Des Plaines, IL USA,
Christopher.Nicholas@honeywell.com
Zeolitic materials containing both 10MR and 12MR pores are of interest as catalysts with good
conversion and shape selectivity. Several frameworks possess both 10MR and 12MR channels in the
same material. One of these is the MSE framework which contains a 12MR straight channel and two
zig-zag 10MR channels. The known material of the MSE framework is MCM-68. Recently, we have
discovered the UZM-35 family of materials via charge density mismatch approach to synthesis which
are also of the MSE zeotype.
UZM-35 is active in various catalytic transformations including catalytic cracking and benzene
alkylation. In these reactions, UZM-35 shows behavior reminiscent of either 10MR or 12MR
channels. Data from catalytic cracking and alkylation of benzene with ethylene or propylene will be
used to attempt to explain the reasons behind the varied behavior of materials containing both 10MR
and 12MR channels.
O-3.1-03
Acidic and diffusional properties of hierarchical H-ZSM5 and the application in toluene
methylation
J.H. Ahn1, R. Kolvenbach1, S.S. Al-Khattaf2, A. Jentys1, J.A. Lercher1
1Technische Universität München, Catalysis Research Center, 85747 Garching, Germany,
jentys@tum.de
2Center of Research Excellence in Petroleum Refining and Petrochemicals, King Fahd University of
Petroleum & Minerals, Dhahran, 31261, Saudi Arabia
In this contribution describe the activity and selectivity of H-ZSM5 modified by desilication and
subsequent dealumination for the alkylation of toluene with methanol. The surface modification with
TEOS increased the p-xylene selectivity and decreased the concentration of Brønsted acid sites
located in the pore mouth region. The increase in the toluene conversion rate can be attributed to the
faster diffusivity of bulky aromatic product molecules (e.g., o-xylene). In the presentation we will
discuss that the p-xylene selectivity was not determined by the Brønsted acid sites on the pore mouth
region (or they play only a minor role), but mainly by the transport properties of the xylenes.
17 IZC, 2013. ORAL COMMUNICATIONS
107
O-3.1-04
Peculiarities of benzene alkylation by ethene on binder-free zeolites
I.M. Gerzeliev1, L.M. Kustov2, M.L. Pavlov3, Yu.A. Lapshina1, R.A. Basimova3, O.P. Tkachenko2,
S. N. Khadzhiev1
1 A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, gerzeliev@ips.ac.ru
2 N.D.Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
3 “STC Salavatnefteorgsintez” Ltd., Salavat, Russia
In this work we studied zeolite Y catalysts synthesized without a binder in benzene alkylation by
ethene. It was found that deep sodium substitution effects the features of samples under study, especially
their acidity. The total concentration of acidic sites that was derived by thermo-programmed ammonia
desorption varies from 644 to 1073 mmol NH3/g. Results of diffuse reflectance infrared spectroscopy
demonstrate band at 3605 сm-1 is characteristic of the strongest bridged acid OH groups. The
observed experimental data on benzene alkylation by ethene can be described of the mechanism,
where the first stage is the formation of a carbonium ion with penta- (tetra) coordinated carbon atom.
Plausible reaction routes for superacid catalysis mechanism are discussed in the paper.
O-3.1-05
Catalytic Cracking of n-Octane over Medium-Pore Zeolites: Influence of Pore Architecture,
Aluminum Content and Crystallite Morphology on Activity and Selectivity
F. Bager1, S. Ernst1
1Department of Chemistry, Chemical Technology, University of Kaiserslautern (TU), Kaiserslautern,
Germany, ernst@chemie.uni-kl.de
The world-wide consumption of light olefins as a major feedstock for the chemical industry is
steadily increasing. Today, the major part of these olefins is produced via steam cracking and, to a
certain extent (in the case of propene), via fluid catalytic cracking (FCC). FCC is primarily used to
crack high-boiling cuts from crude oil, like vacuum gas oil (VGO) to light alkenes, high-octane
gasoline and to middle distillates. The standard catalyst for FCC is an ultrastable form of zeolite Y
(USY). The 10-membered ring zeolite ZSM-5 is admixed as an additive to the FCC catalyst in order
to improve the yield of light olefins, especially propene. The aim of our study is to investigate the
potential of more recent zeolites for increasing the propene yield from FCC. The present contribution
will give an overview over the catalytic cracking of n-octane as model hydrocarbon over mediumpore zeolites with particular emphasis on the influence of the pore architecture, the aluminum content
and the crystallite size on propene yield.
O-3.1-06
Hydrogen transfer in transformations of olefins and thiophene compounds
on zeolite-containing catalysts
O.V. Potapenko, V.P. Doronin, T.P. Sorokina, V.P. Talsi, O.V. Krol, V.A. Likholobov
Institute of Hydrocarbons Processing of Siberian Branch Russian Academy of Sciences, Omsk,
Russia, potap@ihcp.ru
Hydrogen transfer reactions are important for the catalytic cracking process. In the process two
competing reactions take place: 1) hydrogen transfer and 2) cracking of hydrocarbons. At low
temperatures the first type reactions prevail, at temperatures above 500 °C cracking reactions are
more intensive. Olefins with a chain length of 8 or more carbon atoms referring to the high reactivity
mainly involved in cracking and cyclization reactions. For pentenes and hexenes the main method of
converting are hydrogen transfer reaction. To increase the contribution of these reactions is proposed
to introduce in the feed hydrocarbons – hydrogen donors. Using the isotopic labels method
(deuterated compounds) allowed to assume main directions of hydrocarbons and thiophene
compounds transformations and main stages of the mechanism of hydrogen transfer reactions.
3.1. Oil refinery and petrochemistry
108
O-3.1-07
Replacing rare earth in FCC catalyst by alkaline earth
R. Bergstraesser1, S. Wellach1, S. Sirotin2, A. Vimont2,V. Valtchev2, J.-P. Gilson2 and A. Travert2
1 Grace GmbH & Co. KG, Worms, Germany, Ralf.Bergstraesser@grace.com
2 Laboratoire Catalyse et Spectrochimie, ENSICAEN – CNRS – Université de Caen, France
USY zeolites of different quality were used to prepare RE free systems with various contents of
alkaline earth (AE) elements. The samples were steam deactivated, characterized and evaluated in
catalytic cracking. Slight changes in the quality of the initial USY zeolite as well as AE exchange
levels have a strong impact on its catalytic activity; the latter is highest at an intermediate exchange
level, providing a high quality USY zeolite is used. This shows that rationally optimized production
processes are key for efficient RE-free FCC catalysts.
O-3.1-08
Commercial experience of operating FCC unit with decrease
in the catalyst/feed mass ratio
M.I. Levinbuk1, I.S. Maksimov2, S.E. Kuznetsov2
1RAS, A.V. Topchiev Institute of Petrochemical Synthesis, Moscow, Russia, levinbuk.mi@gmail.com
2JSC «Gazpromneft Moscow Refinery», Moscow, Russia
The distinguishing feature of the Moscow Refinery FCC unit is a high potential for the reactor
throughput which determines a catalyst/feed mass ratio of 4.0. During the special selection a series of
cracking catalysts with the stepwise reduced REO content and increased zeolite Y quantity have
maintained the high gasoline yield, as well as olefins yields of C3 and C4, when the catalyst/feed mass
ratio was steadily reduced from 5.7 to 4.5, without extensive modernization of the existing unit
equipment. The report also outlines the possible options of zeolite Y modification or increasing the
quantity of zeolite Y in the FCC catalyst with the purpose of the further reduction of REO content in
the catalyst while maintaining the hydrothermal stability of the zeolite and the target products yields.
O-3.1-09
Mesostructured Y Zeolites: First Refinery Results of
a Hierarchical FCC Catalyst
M. Rico1, A. Grau1, Kunhao Li,2 J. Garcia-Martinez1,2
1Molecular Nanotechnology Lab., University of Alicante, Alicante, Spain, www.nanomol.es
2 Rive Technology, Inc., Monmouth Junction, New Jersey, USA www.rivetechnology.com
Zeolite Y has been the primary active component of fluid catalytic cracking (FCC) catalysts since its
first commercial introduction about 50 years ago. We recently developed a novel and versatile
surfactant-templating process for introducing highly-controlled mesoporosity into any zeolite of any
Si/Al ratio. Herein, we report the scaling up of mesostructured zeolite Y from lab scale to commercial
scale (∼30 ton) with excellent hydrothermal stability and catalytic cracking performance in a
commercial refinery. The FCC catalyst made from the mesostructured zeolite Y showed excellent
hydrothermal stability in both laboratory deactivation and a trial in a full scale commercial FCC unit.
The catalyst also yielded much improved product selectivity compared to the incumbent catalyst,
even at a moderate change-out level of 66%. The results represent the most advanced development to
date of mesostructured zeolite Y in catalytic cracking of petroleum, which suggests the promising
future of mesostructured zeolites in this large scale industrial application.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.1-10
Synthesis and application of zeolite W in the catalyst for
FCC gasoline hydro-upgrading
Huan Niu, Aijun Duan*, Zhen Zhao*, Guiyuan Jiang, Jian Liu, Yuechang Wei, Huifang Pan
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, P.R.
China
*Corresponding author. TEL: (+8610) 89732290, Fax: (+8610) 69724721
Email: duanaijun@cup.edu.cn; zhenzhao@cup.edu.cn
Zeolite W possesses a micro- and mesoporous structure was successfully synthesized with no
template added by hydrothermal crystallization method using the low price solid silica-alumina
microsphere as the silica and alumina sources. The catalysts containing zeolite W showed the
excellent performances of deep desulfurization, aromatization, isomerization and RON reservation in
the hydro-upgrading process for the feedstock of full-range FCC gasoline. Zeolite W will be a
potential candidate additive to the catalyst system for hydro-upgrading FCC gasoline.
3.2. Non-oil fossil feedstocks into end products
110
O-3.2-01
Non-oxidative aromatization of methane: assessment of zeolite framework effects by catalyst
descriptors from microkinetic modeling.
C. Martínez1, M.T. Portilla1, K.S. Wong2, J.W. Thybaut2, E. Tangstad3, M. Stöcker3, G.B. Marin2.
1 Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia-Consejo
Superior de Investigaciones Científicas, Av. de los Naranjos s/n, 46022 Valencia, Spain.
2 Laboratory for Chemical Technology, Ghent University, Krijgslaan 281-S5, B-9000 Ghent, Belgium
3 SINTEF Materials and Chemistry, Process Chemistry Department, N-0314 Oslo, Norway.
Dehydroaromatization of methane is an attractive approach for methane valorization. Here, Mo/ZSM5, Mo/IM-5, Mo/TNU-9 and Mo/MCM-22 are tested and assessed by a dynamic microkinetic model
to study the effect of the zeolite structure via catalyst descriptors. The activity of the four investigated
Mo-zeolites can be, therefore, interpreted as the result of a complex interplay between the number of
acid sites and their susceptibility to deactivation, the latter being determined mainly by the zeolite
topology, as evident from the hexene physisorption enthalpy.
O-3.2-02
Photocatalytic Conversion of Small Organic Molecules in Zeolitic Materials
Lu Li1,2, Guo-Dong Li2, Yi-Yu Cai1, Kai-Xue Wang1, Jie-Sheng Chen1
1School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240,
China, chemcj@sjtu.edu.cn
2College of Chemistry, Jilin University, Chgangchun 130012, China
Effective conversion of small molecules such as methane to more valuable hydrocarbons under mild
conditions is a great scientific and practical challenge. Compared to techniques powered by thermal
energy, approaches that use photonic energy have substantial advantages, such as the capacity to
minimize coking at room temperature. We demonstrate that a zinc-modified ZSM-5 zeolite catalyst
exhibits superior photocatalytic activity for methane conversion to ethane and hydrogen under
irradiation of UV light even sunlight at room temperature. Furthermore, we found that a Ga3+modified ETS-10 zeolitic material in which the photogenerated hydroxyl radical and the
extraframework metal ion interact with the methane molecule to split the H3C-H bond in a synergistic
way under UV irradiation, and this material shows remarkable activity for the conversion of methane
to ethane.
O-3.2-03
Distillate-range products from non-oil based sources by catalytic cascade reactions
V. Hulea1, A. Lacarriere1, J. Robin1, D. Swierczynski1, A. Finiels1, F. Fajula1, F. Luck2
1Institut Charles Gerhardt Montpellier, UMR 5253 CNRS/ENSCM/UM2/UM1, 8, rue de l'Ecole
Normale, 34296 Montpellier Cedex 5 (France) ; vasile.hulea@enscm.fr
2TOTAL S.A., Scientific Developement Division, Catalysis & Process Engineering, 92069 Paris, La
Défense Cedex (France)
An original three-step catalytic process, including methanol to light olefins (over SSZ-13 zeolite),
ethylene oligomerization (over Ni-MCM-41) and co-oligomerization of C3+ olefins (over H-MCM41) is proposed as potential route for methanol conversion into distillate range products. Ethylene can
be selectively transformed into C4-C10 olefins with an even number of carbon atoms, at 150 °C over
Ni-exchanged porous materials with carefully controlled texture and concentrations of nickel sites.
The crucial variables affecting the catalyst productivity are the pore size and the number/type of
active sites. When the Ni-catalyzed oligomerization was assisted by a an acid catalyzed step over HMCM-41, olefins with chains longer than 10 carbon atoms were mainly produced with a productivity
of 180 g g-1 h-1.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.2-04
Morphology Induced Shape Selectivity in Zeolite Catalysis
Shewangizaw Teketel1, Lars F. Lundegaard2, Unni Olsbye1, Karl Petter Lillerud1, Stian Svelle1*,
Pablo Beato2*
1 inGAP Centre of Research based Innovation, Department of Chemistry, University of Oslo, P.O.Box
1033 Blindern, N-0315 Oslo, Norway, *stian.svelle@kjemi.uio.no
2 Haldor Topsøe, Nymøllevej 55, DK-2800 Kgs. Lyngby, Denmark, *pabb@topsoe.dk
In this contribution, we outline a new concept within zeolite shape selectivity. The SUZ-4 zeolite,
which has two interconnected channel systems of distinctly different geometrical size, has been
studied as catalyst for the conversion of methanol to hydrocarbons. By using bulk X-ray diffraction
analysis, TEM imaging, selected area electron diffraction (SAED), and simulations of crystal growth,
we demonstrate that the shape selectivity of SUZ-4 during the reaction is determined by crystal
morphology, not by framework topology. Crystal facets terminated exclusively by one of the two
channel systems are preferentially exposed, thereby leading to morphology induced shape selectivity.
The concept of morphology induced shape selectivity as presented herein may be extended to
different framework topologies and should be added to the conceptual toolbox in zeolite synthesis and
shape selective catalysis.
O-3.2-05
Regeneration for Promotion to Catalytic Activity of H-ZSM-5 for DME Conversion to Olefin
A. Muramatsu1, M. Nakaya1, K. Omata2, M. Yamada3, Y. Yamazaki1
1Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Japan,
2Interdisciplinary Faculty of Science and Engineering, Shimane University, Matsue, Japan, 3Akita
National College of Technology, Akita, Japan, mura@tagen.tohoku.ac.jp
Regeneration of H-ZSM-5 catalyst was tested on DME conversion to olefin. The catalyst life was
stabilized by the regeneration for a number of reactions. Since the decreases in both acid amount and
surface area were observed, the regeneration must cause the change of structure, that is,
dealumination. To confirm this assumption, dealuminated H-ZSM-5 was synthesized by steaming
treatment so that the catalyst life was prolonged. The dealumination from zeolite framework was
made progress via the formation "unstable Al species" and the their change to extra-framework.
O-3.2-06
Insights into the selective and catalytic oxidation of methane to methanol with Cu-promoted
Fe-ZSM-5 at mild conditions
C. Hammond,1,2* N. Dimitratos,2 H. Hagen,3 E. E. Stangland,4 D. J. Willock2 and G. J. Hutchings2
1ETH Zurich, Zurich, Wolfgang-Pauli-Str. 10, Switzerland.
2Cardiff Catalysis Institute, Cardiff University, CF10 4AT, UK.
3Dow Benelux B. V., Herbert H. Dowweg 5, Terneuzen (The Netherlands).
4National Corporate R&D, The Dow Chemical Company, MI 48674 (USA) *
ceri.hammond@chem.ethz.ch;
The selective oxidation of methane to methanol remains one of the most challenging targets of
catalysis research. We have recently demonstrated a highly active alternative route for the direct, onestep selective oxidation of methane to methanol. The reaction is performed in the aqueous phase, at
low temperature (50 ºC) and with H2O2 as terminal oxidant, and is mediated by a Cu- and Fecontaining MFI-type zeolite (CuFe-ZSM-5). During this presentation, an overview of the catalytic
and mechanistic cycles will be presented, along with an in-depth investigation concerning the precise
nature of the active species present within the catalyst.
3.2. Non-oil fossil feedstocks into end products
112
O-3.2-07
Methanol synthesis over Cu/ZnO nanoaggregates
encapsulated in carbon nanotubes and mesoporous silica
D. Großmann1, A. Dreier2, C. Lehmann2 W. Grünert1
1Laboratory of Industrial Chemistry, Ruhr-University Bochum, Germany, w.gruenert@techem.rub.de
2Max-Planck Institut für Kohlenforschung, Mülheim a. d. Ruhr, Germany
Cu/ZnO nanoaggregates were encapsulated in CNTs and mesoporous silica in order to investigate the
nature of active sites in methanol synthesis catalysts. The preparation was a particular challenge as
various known preparation methods failed. After extensive search the synthesis of monometallic
samples was realized; the bimetallic catalysts were prepared by consecutive routes.
First methanol synthesis measurements show less intrinsic activities for CNT-based catalysts
compared to SBA-15 based ones. Furthermore, CNT samples tending to alloy formation according to
in-situ XAFS studies were significantly less active that the ones with a Zn2+-Cu(0) interaction.
Further catalytic data will be presented and discussed in terms of their potential to allow reliable
conclusions on the nature of interaction and its role for catalysis.
17 IZC, 2013. ORAL COMMUNICATIONS
113
O-3.3-01
Mesoporous Carbon as a Superior Catalyst Support in One-pot Conversion
of Cellulose to Polyols
Aiqin Wang, Jifeng Pang, Yanhua Zhang, Mingyuan Zheng, Tao Zhang*
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, Dalian, China, aqwang@dicp.ac.cn; taozhang@dicp.ac.cn
Mesoporous carbons (MC), with tunable and uniform pore sizes in the range of 2 ~ 50 nm, large
surface areas and excellent hydrothermal stabilities, have shown great potentials as the catalysts
supports in the chemical transformation of lignocellulosic biomass. In this work, we present two
examples of MC acting as the catalyst supports for the one-pot conversion of cellulose to polyols.
One is the MC-supported tungsten carbide for the one-pot conversion of cellulose to ethylene glycol,
and the other is the MC-supported Ni-M (M represents noble metals such as Pt, Pd, Ir, Rh) for the
one-pot conversion of cellulose to hexitols. Both examples show the remarkable superiority of MC to
the conventional activated carbons (AC) in enhancing the activity and selectivity of the catalysts.
O-3.3-02
Decomposition of Hexose Sugars to Levulinic Acid Using Graphene Oxide Catalysts
with Brønsted Acid Sites
Pravin P. Upare,1,2 Ji-Woong Yoon,1 Hyo-Yoon Kang,1,2 Dong Won Hwang1, Young Kyu Hwang,*1-3
Harold H. Kung,3 and Jong-San Chang*1,2
1Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical
Technology(KRICT), 141 Gajeong-Ro, Yuesong, Daejeon 305-600, Korea
2Department of Green Chemistry,University of Science and Technology (UST),217 Gajeong-Ro,
Youseong, Daejeon 305-350, Korea
3Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL 60208–
3120, USA
Heterogeneous graphene oxide (GO)-based catalysts with sulfonic acid (SO3H) functional groups
(GO–SO3H) were used for selective decomposition of hexose sugars (glucose and fructose) to
levulinic acid (LA), which has been used as a platform chemical for various value-added derivatives.
The as-prepared GO–SO3H catalysts gave excellent yields of around 78% for LA for a reaction time
of 2 h, and showed compatibility of reuse with reliable performance. The chemical transformation
patterns for hexose sugar decompositions are affected by temperature, the density of acid sites, and
type of catalyst. The excellent catalytic performance of GO–SO3H has been determined to be the
result of higher density of Brønsted acid sites in GO, compared with the Lewis acid sites in other AC–
SO3H catalysts. The morphologies, surface characteristics, and other physiochemical properties were
evaluated using several characterization techniques.
3.3. Environmental catalysis and conversion of biomass
114
O-3.3-03
Zeolite water treatment in a thermochemical biofuel production process
A. Bosetti, G. Franzosi, C. Perego,
Eni S.p.A, Research Center for Non Conventional Energies, Istituto Eni Donegani, Via G. Fauser 4 –
28100 Novara, Italy. aldo.bosetti@eni.com
This work focus on a termochemical process to convert waste biomass into bio-oil, with particular
focus on a peculiar zeolite treatment of the residual water-phase in order to enhance the yield. The
process converts wet organic wastes to bio-oil that could be upgraded into renewable diesel.
Unfortunately, the residual water-phase exhibits a high content of C and N derivatives, rendering it
not adapted to be purified in conventional water treatment plant. A treatment step was evaluated in
order to adjust the C/N content, comparing zeolites and clays as sorbents. The purified water phase
was used as nutrient for a microorganism culture producing new biomass to be reused in the same
production of biofuel.
O-3.3-04
Application and Stability of Ru/H-USY Zeolites in Hot Liquid Water
J.A. Geboers1,2, T. Ennaert1, S. Van De Vyver1,3, K. Houthoofd1, P.A. Jacobs1 and B.F. Sels1
1 Center for Surface Chemistry and Catalysis, University of Leuven, Leuven, Belgium
2 Max Planck Institute for Coal Research, Mülheim an der Ruhr, Germany, geboers@mpimuelheim.mpg.de
3Massachusetts Institute of Technology, Cambridge, MA, USA
The potential of bifunctional Ru/H-(US)Y catalysts is assessed for conversions in hot liquid water.
Besides a thorough investigation of the material’s physicochemical stability, the long-time catalytic
performance of acid sites and noble metal functionality is studied via hydrolytic hydrogenation of
cellulose. On the one hand, stability of H-USY zeolites decreases with their Si/Al ratio. On the other
hand, extra-framework Al species are able to protect the zeolite framework against degradation.
These observations are combined in a conceptual framework describing the physcochemical stability
of Ru/(US)Y catalysts in hot liquid water. By exploiting these insights, cellulose can be converted
into hexitols with yields of up to 95 %.
O-3.3-05
The direct conversion of rapeseed oil over pilot Pd-Zn/MFI/Al2O3 catalyst
M. A. Gubanov, A. V. Chistyakov, M. V. Tsodikov
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, gubanov@ips.ac.ru
In this work the results relates to rapeseed oil one-step treatment into alkane–aromatic hydrocarbons
fraction over pilot Pd-Zn/MFI/Al2O3 catalyst are presented. Studied catalyst was found to be stable
during more than 48 hours on-stream. The influence of main process parameters on reaction
selectivity is discussed. Under found optimal conditions aim fraction yield of C3-C11 hydrocarbons
reached 95 wt.% herewith methane yield did not exceeds 2 wt.%. Glycerol fragment of feed oil was
supposed to convert completely into propane.
17 IZC, 2013. ORAL COMMUNICATIONS
115
O-3.3-06
Metal-substituted TUD-1 for the Synthesis of Valuable Chemicals from Glycerol and Related
Compounds
Li Li, Bert F. Sels, and Paolo. P. Pescarmona*
Centre for Surface Chemistry and Catalysis, Kasteelpark Arenberg 23, KU Leuven, 3001, Heverlee,
Belgium, Paolo.Pescarmona@biw.kuleuven.be
Metal-substituted silicates of the TUD-1 family are promising mesoporous materials thanks to their
straightforward synthesis and excellent catalytic activity in various reactions. In this study, Zr- and
the novel Hf-TUD-1 were synthesized and applied as catalysts for: (1) the conversion of
dihydroxyacetone (DHA) to ethyl lactate and (2) the condensation of glycerol with acetone to yield
solketal. These reactions provide attractive routes for the conversion of biomass feedstock to
industrial valuable chemicals.
Zr- and Hf-TUD-1 gave high conversion and excellent selectivity in both reactions. These results are
ascribed to their combination of strong Lewis and mild Brønsted acid sites, as characterized by FTIR
of adsorbed pyridine. The large specific surface areas, wide pores and relatively hydrophobic surface
of these materials are also beneficial to the reactions.
O-3.3-07
The Catalytic Conversion of Waste Glycerol to Value-Added Products
G. Sanchez, L. Harvey, J. Friggieri, B. Z. Dlugogorski, E. Kennedy, M. Stockenhuber
Priority Research Centre for Energy (PRCfE), The University of Newcastle, Callaghan, NSW 2308,
Australia, Michael.Stockenhuber@newcastle.edu.au
Increasing biodiesel production rates are predicted to trigger a dramatic reduction the market value of
glycerol, the primary byproduct. As such, the application of zeolites (particularly modified H-ZSM-5
and TS-1) and other heterogeneous catalysts in selectively producing valuable products (namely
glycidol) has been investigated. It was found that certain compounds, when present in the synthesis
of glycidol, adversely affect the reaction, calling for the selectivity to desirable intermediates to be
improved. It was found that this could be achieved by modifying the ZSM-5 with transition and
alkali metals.
O-3.3-08
Hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-zeolite and
Pt-heteropolyacid catalysts
M.A. Alotaibi, E.F. Kozhevnikova, I.V. Kozhevnikov
Department of Chemistry, University of Liverpool, Liverpool L69 7ZD, United Kingdom
Methyl isobutyl ketone (MIBK) can be viewed as a key intermediate for the conversion of biomassderived acetone, the by-product of biobutanol production, to transportation fuel. Pt/H-ZSM-5 is
demonstrated to be a highly efficient catalyst for the gas-phase hydrogenation of MIBK to
methylpentane with >99% yield at 200oC. Similarly, Pt loaded on acidic heteropoly salt
Cs2.5H0.5PW12O40 is a highly active and selective catalyst for the hydrogenation of MIBK and
diisobutyl ketone to the corresponding alkanes at 100oC with 97-99% yield. The reactions are shown
to proceed via bifunctional metal-acid catalysed pathway. The catalysts do not show any deactivation
for at least 16 h on stream.
3.3. Environmental catalysis and conversion of biomass
116
O-3.3-09
Selective hydroconversion of acetic acid over indium-doped Ni-zeolites
Sz. Harnos1, Gy. Onyestyák1, Sz. Klébert1, A. Kaszonyi2, M. Štolcová2, D. Kalló1
1Inst. of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian
Academy of Sciences, Budapest, Hungary, harnos.szabolcs@ttk.mta.hu
2Dep. of Organic Technology, Slovak University of Technology, Bratislava, Slovak Republic
Fully and partly amorphous aluminosilicate supported Cu- and Ni-catalysts and the In-doped
derivatives thereof were obtained by reducing the metal cationic form of crystalline alumina-rich
zeolites with H2 at elevated temperature. The catalysts were tested in the hydroconversion of biomass
derived carboxylic acids. The Ni-catalysts were of higher activity and lower selectivity for the
formation of acetaldehyde, ethanol, and ethylacetate than the corresponding Cu-catalysts. Indium
doping increased the activity and improved the selectivity of all catalyst preparations by generating
active bimetallic nanoparticles. The activity was shown to be affected also by the properties of the
aluminosilicate support that had relation to the structure of the parent zeolite.
O-3.3-10
Selective catalytic reduction (SCR) of nitrogen oxides over Fe zeolites.
New insights into active sites and reaction mechanisms
I. Ellmers1, R. Velez2, A. Brückner2, U. Bentrup2, H. Huang3, V. Schünemann3, W. Grünert1
1Laboratory of Industrial Chemistry, Ruhr-University Bochum, Germany, w.gruenert@techem.rub.de
2Leibniz-Institute for Catalysis e.V., Rostock, Germany
3 FB Physics, Technical University Kaiserslautern, Germany
Fe-ZSM-5 catalysts for the SCR of nitrogen oxides by NH3 were studied with the goal of identifying
active sites and mechanistic features of reactions related to NOx abatement: NO oxidation, standard
and fast SCR. Catalytic studies with catalysts of different preparation were combined with
characterization by EPR, UV-Vis, Moessbauer, and IR spectroscopy.
It was found that all three reactions use different sites. Standard SCR does not proceed via NO2
formation. Freshly prepared Fe-ZSM-5 may exhibit low NO oxidation activity, which increases
strongly after the sites have undergone redox cycles. Therefore, NO oxidation rates over fresh
catalysts are irrelevant for mechanistic discussions regarding standard SCR.
O-3.3-11
Effect of ammonia addition on copper electronic state and DeNOx reactivity
of Cu-substituted ZSM-5
S. A. Yashnik, N.T. Vasenin, V.F. Anufrienko, Z.R. Ismagilov
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia, yashnik@catalysis.ru
The copper structures with extra-lattice oxygen are supposed to be more active in DeNOx processes
than the isolated ions. For their formation, the ion-exchange is carried out with water-ammonia
solutions of copper salts or added ammonia to the suspension after the ion exchange procedure.
The present work studies a possibility to regulate the electronic state of copper ions and the structure
of magnetic associates of copper ions by varying the ammonia to copper ratio at preparation of the
Cu-ZSM-5 catalysts by the ion-exchange. The redox properties and reactivity in N2O decomposition
and NO selective catalytic reduction by propane of the Cu-modified ZSM-5 catalysts were examined
in order to find correlation between structures of the Cu-active sites and performance in DeNOx of
these catalysts.
It was shown that the addition of ammonia to copper solution has different effect on DeNOx
reactivity; it is positive for NH4+/Cu2+ ratios close to 6.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.3-12
Sulfur stable precious metal loaded zeolites for CH4 combustion
Arno Tißler, Frank Klose, Olga Manoylova
Clariant Produkte (Deutschland) GmbH, Bruckmühl, Germany, arno.tissler@clariant.com,
Precious metal loaded zeolites are well known as catalysts in petrochemical and environmental
applications. But only little information is available on the location of the metal clusters and their
interaction with the zeolite affecting catalytic properties. A method based on IR spectroscopy of
adsorbed CO and selective poisoning of “external” precious metal clusters by large nitriles was
developed to distinguish between metal clusters inside and outside of the zeolite pore system. The
location of precious metal clusters is determined by the module and the calcination environment. The
most active catalysts (80 % CH4 conversion at 400 °C and 40.000 h-1) were obtained from Pt/Pd
loaded high SAR BEA zeolite. These catalysts exhibit high resistance against thermal stress and
poisoning by SO2.
O-3.3-13
Catalytic activity of NixSiBEA and NixHAlBEA in conversion of 1,2-dichloroethane
A. Śrębowata1,*, I.I.Kamińska1, D.Łomot1, D. Lisovytskyi1, R. Baran2,3, T. Onfroy,2
S. Dzwigaj2,*
1Institute of Physical Chemistry, PAS, ul. Kasprzaka 44/52, PL-01224 Warszawa, Poland,
asrebowata@ichf.edu.pl
2Laboratoire de Reactivite de Surface UMR 7197, CNRS, UPMC, Site d'Ivry - Le Raphaël, 3, rue
Galilée, 94200 Ivry-sur-Seine, France
3AGH University of Science and Technology, Al. A. Mickiewicza 30, 30-059 Krakow, Poland
*Corresponding authors: asrebowata@ichf.edu.pl, stanislaw.dzwigaj@upmc.fr
NixSiBEA and NixHAlBEA prepared, respectively, by two steps post-synthesis method and classical
wet impregnation are active and stable in hydrodechlorination of 1,2-dichloroethane at low reaction
temperatures (523, 543 K). Catalytic behavior of these materials depends on their acidity, nickel form
and the dispersion of metal phase. NixSiBEA showed very high, (> 90 %) selectivity to ethylene and
NixHAlBEA produce ~100% of vinyl chloride.
O-3.3-14
Iron-functionalized silica nanoparticles
as highly efficient catalyst for decomposition of VOCs
M. Popova1, A. Ristić2, K. Lazar3, D. Maučec2, M. Vassileva1 N. Novak Tušar2,4
1 Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences,
Sofia, Bulgaria,
2National Institute of Chemistry, Ljubljana, Slovenia,
3Centre for Energy Research, Institute of Isotopes, Hungarian Academy of Sciences, Budapest,
Hungary, e-mail: natasa.novak@ki.si
Catalytic oxidation is one of the most important industrially applicable processes for the
decomposition of volatile organic compounds (VOCs) in polluted air. Recently, many efforts have
been made to design combined adsorption-catalytic unit with optimal activity. In this work we discuss
that iron-functionalized silicate nanoparticles with interparticle mesoporosity act as a highly efficient
adsorbent and catalyst for toluene oxidation in gas phase. By combined use of catalytic tests and
spectroscopic techniques the direct evidence is given that the superior activity of the catalyst is
attributed uniquely to isolated iron incorporated into silica matrix.
3.3. Environmental catalysis and conversion of biomass
118
O-3.3-15
CO2 hydrogenation into CH4 on Ni zeolite based catalysts
I. Graça, L.V. González, C. Henriques, J.M. Lopes, M.F. Ribeiro
IBB, Institute for Biotechnology and Bioengineering, Centre for Biological and Chemical
Engineering, Instituto Superior Técnico, UTL, Av. Rovisco Pais, 1049-001 Lisboa, Portugal,
filipa.ribeiro@ist.utl.pt
The CO2 hydrogenation into methane was performed over catalysts containing nickel and cerium
species supported on a Y zeolite, using an H2/CO2 ratio of 4 and temperatures ranging from 250 to
450ºC. Interesting CO2 conversions and CH4 selectivities were found for the Ni-Y catalysts, mainly at
higher temperatures, which increased with the Ni content. A further enhancement of the catalysts
performances was noticed by adding small quantities of Ce. Furthermore, almost no deactivation was
observed after 10h of reaction at 400ºC. Hence, these results showed that the zeolites have great
potential to be used as catalysts in the CO2 methanation reaction.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.4-01
Intramolecular carbon shifts in carbohydrates catalyzed by microporous tin-containing solid
Lewis acids with borate salts in aqueous media
William R. Gunther†, Yuran Wang†, Yuewei Ji†, Vladimir K. MichaelisŦ, Robert G. GriffinŦ and
Yuriy Román-Leshkov*†
†Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, United States
ŦDepartment of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of
Technology, Cambridge, Massachusetts 02139, United States
yroman@mit.edu
Carbohydrate epimerization is an essential technology for the widespread production of rare sugars.
In contrast to other enzymes, most epimerases are only active on sugars substituted with phosphate or
nucleotide groups, thus drastically restricting their use. Here we show that Sn-Beta zeolite in the
presence of sodium tetraborate (SB) catalyzes the selective epimerization of aldoses in aqueous
media. Specifically, a 5 wt% aldose (e.g., glucose, xylose, or arabinose) solution with a 4:1
aldose:SB molar ratio reacted with catalytic amounts of Sn-Beta yields near equilibrium
epimerization product distributions. The reaction proceeds by way of a 1,2 carbon-shift wherein the
bond between C-2 and C-3 is cleaved and a new bond between C-1 and C-3 is formed, with C-1
moving to the C-2 position with an inverted configuration. This work provides a general method of
performing carbohydrate epimerizations that surmounts the main disadvantages of current enzymatic
and inorganic processes.
O-3.4-02
Simple and scalable synthesis of highly active Lewis acidic Sn-β
C. Hammond1, S. Conrad1, C. Aellig1, P. Wolf1 and I. Hermans1
1ETH Zurich, Zurich, Wolfgang-Pauli-Str. 10 (Switzerland) ive.hermans@chem.ethz.ch
Lewis acids are a class of catalysts that perform many essential transformations, such as oxidations
and isomerizations. Of particular interest are Lewis acidic zeolites, such as TS-1 and Sn-β, which are
important catalysts in the area of sustainable chemistry. Nevertheless, some significant practical
hurdles currently prohibit greater utilisation of these promising materials. Amongst these, the lengthy
and complicated synthesis procedure and the low amount of active metal incorporated into the
catalyst remain most prohibitive.
During this talk, we will present an attractive alternative route to hydrothermal synthesis, whereby the
Lewis acid is incorporated into the vacant sites of a pre-dealuminated framework. Not only does this
approach avoid the long synthesis times of the conventional routes, but it also allows for the synthesis
of a material with smaller crystallite sizes, higher metal content, and more favourable catalytic
properties.
3.4. Chemicals and fine chemicals
120
O-3.4-03
Promotive effects of alkylation of nitrogen atom doped in silicate framework on the basic
properties of porous silica materials
M. Ogura, K. Sugino, Y. Furukawa, S. Fukunaga
Inst. Ind. Sci., The University of Tokyo, Tokyo, Japan, oguram@iis.u-tokyo.ac.jp
A simple technique could be demonstrated successfully for modification, improvement, and
adjustment of basic characters obtained by nitridation of porous silica materials by alkylation of the N
atom doped in the silicate framework. The materials obtained in such a way showed a unique
catalytic performance for base-catalyzed reactions such as Knoevenagel condensation.
O-3.4-04
Selective formation of hydroquinone in the phenol oxidation with H2O2 over Ti-MCM-68 zeolite
catalyst
S. Inagaki, Y. Tsuboi, K. Mamiya, Y. Kubota
Division of Materials Science and Chemical Engineering, Yokohama National University, Yokohama,
Japan, sinagaki@ynu.ac.jp
Titanium-substituted molecular sieves are utilized as an oxidation catalyst in the selective oxidation
of a wide range of organic substrates using hydrogen peroxide. We report herein the improvement of
catalytic activity and para-selectivity of Ti-MCM-68 in the phenol oxidation. The thermal treatment
after Ti-insertion significantly enhanced the catalytic activity of Ti-MCM-68 mainly due to the
increase in hydrophobic nature inside pores. It should be noted that Ti-MCM-68 modified by
Ph2SiCl2 treatment and the following Ti-insersion and calcination showed higher para-selectivity in
the phenol oxidation, in particular, the use of EtOH as a solvent in the reaction induced the most
excellent para-selectivity as well as turnover number in the modified Ti-MCM-68.
O-3.4-05
Cyclohexene oxidation by TAPO-5 catalysts prepared with Ti(III) source
Almudena Alfayate, Manuel Sánchez-Sánchez, Joaquín Pérez-Pariente*
Instituto de Catálisis y Petroleoquímica, ICP-CSIC, Madrid, Spain. jperez@icp.csic.es
Ti-zeolites and TAPO materials have been widely used as heterogeneous catalysts in different
oxidation processes. However, Ti-zeolites have been paid much more attention due to their higher
catalytic performance, which could be related with a favorable titanium environment. However,
AlPO4 materials have the advantage of being able to incorporate heteroatoms through different
mechanisms. It has not been yet explored in the case of Ti.
We have prepared TAPO-5 using Ti(III) source in order to get materials having catalytically active Ti
centers different from those present in Ti-zeolites and conventional TAPO materials prepared with
Ti(IV). Indeed, they have an outstanding conversion in cyclohexene oxidation and a high selectivity
to allylic products.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.4-06
Tailoring faujasitic frameworks for the sustainable synthesis of nylon
M.E. Potter1, S. Newland1, R. Leithall1, M. Carravetta1, R. Raja1, A. Levy2
1Dep. of Chemistry, University of Southampton, Southampton, UK, mep106@soton.ac.uk
2Honeywell LLC, Morristown, USA
Currently 4 million tonnes of ε-caprolactam are synthesised yearly using hazardous reagents, while
producing vast amounts of inorganic waste. A zeolite catalyst offers many advantages but this
requires temperatures over 300 oC, increasing energy demands. Within we describe for the first time,
our strategy for designing nanoporous materials capable of performing the sustainable lowtemperature Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam in the liquid-phase
with industrially applicable yields. Further, we discuss how we target the active site and probe the
materials surface, enabling structure-property links to optimise the catalytic activity of these systems.
O-3.4-07
MPVO reduction of crotonaldehyde over Zr containing molecular sieves
V.L. Sushkevich1, E. Taarning2, S. Tolborg2, I.I. Ivanova1,3
1Dep. of Chemistry, Lomonosov Moscow State University, Moscow, Russia,
vitaly.sushkevich@gmail.com
2 Haldor Topsøe A/S, Nymoellevej 55 2800 Kgs. Lyngby, Denmark
3A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia
The Zr-containing molecular sieves and zirconia supported on different oxides were studied in the
Meerwein-Ponndorf-Verley-Oppenauer reduction of crotonaldehyde with ethanol. The active sites of
the catalysts were investigated by FTIR spectroscopy of adsorbed carbon monoxide. The catalytic
activity was found to increase in the following order of catalysts: ZrMFI(200) Zrδ+ Lewis acid sites in the samples. The best catalytic performance was observed over ZrBeta(100)
which showed 70% selectivity to buten-3-ol-1 at the conversion of 36% at 200ºC.
O-3.4-08
High-selective direct amination of primary alcohols using a Pd/cryptomelane catalyst
M. Ousmane,1 G. Perrussel,1 J-M. Clacens,1 M. Pera-Titus,1 F. Decampo1
1Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS/Rhodia, Shanghai,
China, marc.pera-titus-ext@ap.rhodia.com
Manganese octahedral molecular sieves (OMS) constitute a crystalline variety of amorphous
manganese oxide with defined tunnel structures and a panel of oxidation states of Mn. Until now, the
reported studies on OMS catalysts have pointed out the preferential generation of imines by N-alkylation of
aromatic and aliphatic alcohols, but with no amine formation. Here we show for the first time the direct
amination of primary alcohols over a Pd/K,H-OMS-2 catalyst via a hydrogen borrowing mechanism. The
catalyst behaves as a tandem tri-functional catalyst, oxidizing the primary alcohols to aldehydes, behaving as a
Lewis acid for imine formation, and finally reducing the imine to the secondary amine.
3.4. Chemicals and fine chemicals
122
O-3.4-09
Mesoporous MIL-101 metal-organic frameworks as heterogeneous catalysts
for liquid-phase selective oxidation
N.V. Maksimchuk1, I.D. Ivanchikova1, K.A. Kovalenko2, V.P. Fedin2, O.A. Kholdeeva1
1Boreskov Institute of Catalysis, Novosibirsk, Russia, nvmax@catalysis.ru
2Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Russia
The mesoporous zeotype chromium and iron terephthalates, Cr- and Fe-MIL-101, demonstrated
superior catalytic activity and selectivity in the oxidation of alkenes, including natural terpenes, to the
corresponding α,β-unsaturated ketones as well as oxyfunctionalization of antracene or cyclohexane
with environmentally benign oxidants − O2 and tBuOOH. The elaborated MIL-101 materials kept
their structure under turnover conditions, were stable to active metal leaching, behaved as true
heterogeneous catalysts, were easily recovered by filtration and reused several times without loss of
the catalytic performance.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.5-01
In-depth Study of Surface Resistances in Nanoporous Materials
by Microscopic Diffusion Measurement
Jörg Kärger1,
1University of Leipzig, Germany, kaerger@physik.uni-leipzig.de
The application of micro-imaging by IR and interference microscopoy, in combination with pulsed
field gradient NMR, is shown to provide information about nature, intensity and functionality of the
transport resistances on the surface of nanoporous materials which, so far, have been inaccessible by
direct experimental evidence. The novel information thus provided includes information on surface
morphology, sticking probabilities and options for the fabrication of transport-optimized materials.
O-3.5-02
Understanding Stimuli-Induced Structural Transitions
in Metal-Organic Frameworks From the Unit Cell to the Crystal
F.-X. Coudert1, A. Boutin2, A. V. Neimark3, A. H. Fuchs1
1 CNRS & Chimie ParisTech, Paris, France, fx.coudert@chimie-paristech.fr
2 École normale supérieure, Paris, France
3 Rutgers, The State University of New Jersey, USA
Structural transitions induced in metal-organic frameworks (MOF), induced by stimuli such as
adsorption, mechanical stress or temperature variations, have attracted a lot of attention from material
scientists, who discovered and explored potential practical applications the field of adsorptive
separation (for instance). We present thermodynamic and mechanical models and simulation methods
these physicochemical and mechanical mechanisms. Such models are successful at describing
adsorption-induced structural transitions, mixture coadsorption in flexible MOFs, and influence of
temperature and mechanical compression. Using molecular modeling, thermodynamic models and
elastic framework models, we can describe the stimuli-induced transitions from the unit cell scale all
the way to the behavior of the whole crystal.
O-3.5-03
Equilibrium and kinetics of water adsorption on the pure and substituted aluminophosphates:
application for energy transformation
I.S. Girnik1,2, Yu.I.Aristov1.
1 Novosibirsk State University, Pirogova st, 2 Novosibirsk, Russian Federation, girnikis@gmail.com
2 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk, Russian Federation
This communication is addressed to studying the equilibrium and kinetics of water adsorption on
AlPO4-5, AlPO4-11, AlPO4-31, SAPO-11 and SAPO-31. Isotherms of water adsorption were
measured at temperature 20, 35, 50 oC and vapor pressure 0 - 40 mbar using an Isothermal
Differential Step method. Adsorption kinetics was measured using a Large Temperature Jump method
under conditions of the isobaric stages of an AT cycle. Analysis of the thermodynamic cycles of
adsorptive heat transformation based on AlPO4-5 and AlPO4-11 as adsorbates demonstrates feasibility
of these materials for adsorptive transformation of low temperature heat.
3.5 Adsorption and separation
124
O-3.5-04
Storage of oxygen and hydrogen in zeolites and their release behaviors
M. Fujiwara,1 Y. Fujio,1 H. Sakurai,1 H. Senoh,1 T. Kiyobayashi,1 I. Kumakiri2
1National Institute of Advanced Industrial Science and Technology, Kansai Center (UBIQEN),
Ikeda, Osaka, Japan, m-fujiwara@aist.go.jp
2 SINTEF, Oslo, Norway; Present address: Faculty of Engineering, Yamaguchi University, Ube,
Yamaguchi, Japan
Pressurized oxygen or hydrogen was filled into 1,4-bis(hydroxydimethylsilyl)benzene impregnated
zeolite materials, H-mordenite and H-ZSM-5, respectively. These zeolites were heated at 150°C to
seal the outlet of their micropores. According to online GC or mass spectrometry analyses, the
heating procedures of these zeolite materials storing oxygen or hydrogen discharged the respective
molecules over 200°C by the decomposition of the disilane compound that sealed their micropores.
These storage technologies of oxygen and hydrogen molecules in small dimension will create their
novel applications.
O-3.5-05
A Novel Titano-Silico-Alumophosphate for Heat Management
Silke Sauerbeck1, Arno Tißler1, Rolf Kurzhals2
1Clariant Produkte (Deutschland) GmbH, Bruckmühl, Germany, silke.sauerbeck@clariant.com,
2Clariant Produkte (Deutschland) GmbH, Bitterfeld-Wolfen, Germany
Zeolites are commercially produced since the 60th of the last century either as catalysts, ion
exchangers or as adsorbents. During the last decade the interest in zeotypes increased for various
applications, amongst others for their use as adsorbent in heat exchangers. One of the most interesting
materials is SAPO-34, due to its high water adsorption capacity, its hydrothermal stability against
steam and its ad- and desorption of water in a narrow temperature range. Disadvantage of SAPO-34 is
its low hydrothermal stability in aqueous phase at temperatures above 50 °C, which makes its
processing difficult. In this work we present a SAPO-34 analogue with improved stability in water
and comparable water adsorption properties: TiAPSO-34.
O-3.5-06
Adsorption of sulfonamide antibiotics into high silica zeolites from water: A combined
structural, spectroscopic and computational approach
I. Braschi1,3, S. Blasioli, M. Cossi2,3, L. Marchese2,3, A. Martucci4, S. Quartieri5
1 Dep. Agricultural Science, University of Bologna, Bologna, Italy; ilaria.braschi@unibo.it
2 Dep. Advanced Science and Technologies and 3 Interdisciplinary Nano-SiSTeMI Centre, University
of Eastern Piedmont A. Avogadro, Alessandria, Italy,
4 Dep. Physics and Earth Sciences, University of Ferrara, Ferrara, Italy,
5 Dep. Physics and Earth Sciences, University of Messina, Messina, Italy
High silica zeolites (Y, MOR, ZSM-5) were tested for their capability to extract sulfonamides from
water. Kinetics, capacity and reversibility of the adsorption process were studied along with
sulfonamide arrangment into zeolite porosities. The main host-guest & guest-guest interactions and
the tautomeric form embedded into zeolite Y were defined. MOR at 65°C gave rise to a reaction
product of sulfachloropyridazine with 100% selectivity. Regeneration of exhausted zeolites was
obtained upon thermal treatment and solvent extraction.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.5-07
Amine-Containing Nanoporous Materials for CO2 Removal
A. Sayari
Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, K1N
6N5 Canada
Amine-containing nanoporous materials gained tremendous popularity in recent years as adsorbents
for CO2 removal [1,2]. Amine-functionalized materials exhibit high adsorption capacity, fast CO2
adsorption and desorption, and low-energy requirements for recycling compared to amine solutions
[3]. Amines may occur as grafted or impregnated species, typically on large surface area mesoporous
materials, and more recently as amine-appended metal-organic frameworks [4]. This work deals with
the following issues (i) importance of the pore size/pore volume, (ii) optimization of grafting
conditions, (iii) CO2 adsorption capacity and rate, (iv) tolerance to moisture in the feed, (v) selectivity
toward CO2 vs. other adsorbates such as N2, O2, H2, CH4, H2S, and SO2 and (vi) adsorptiondesorption cycling, (vii) stability in the presence of moisture, (viii) oxidative degradation, and (ix) dry
CO2-induced deactivation and mitigation thereof. The effect of the pore length and surface
hydrophobicity on diffusion resistance will also be demonstrated.
O-3.5-08
n- and cyclohexane separation on the UiO-66 Metal-Organic Framework
Belgin Bozbiyik a, Tim Duerinck a, Gino V. Baron a, Dirk E. De Vosb , Pieterjan Valvekensb and Joeri
F.M Denayer a
a Department of Chemical Engineering, Vrije Universiteit Brussel, 1050 Brussels, Belgium,
bbozbiyi@vub.ac.be
b Centre for Surface Chemistry and Catalysis, Katholiek Universiteit Leuven, 3001 Leuven, Belgium
In the present work, we report a case of inverse shape selectivity on UiO-66, a Zirconium MetalOrganic Framework having a highly stable Zr-oxo-hydroxy Secondary Building Unit. With this MOF,
a preferential adsorption of cyclohexane over n-hexane is observed in pulse GC and breakthrough
experiments. In our work, we will discuss how this remarkable selectivity can be explained in terms
of molecular confinement in the small and large cavities present in the UiO-66 structure.
O-3.5-09
Effect of Room Temperature Ionic Liquids on the Gas Adsorption in Cu-BTC Metal-Organic
Framework: A Simulation Study
J. M. Vicent-Luna, J. J. Gutiérrez-Sevillano, J. A. Anta, and S. Calero
Department of Physical, Chemical, and Natural Systems. University Pablo de Olavide, Ctra. Utrera
km. 1, 41013, Seville, Spain. jmviclun@upo.es
Room Temperature Ionic Liquids (RTILs) and metal-organic frameworks (MOFs) have been
proposed as potentially good systems for CO2 capture and separation. In this study we use a
combination of ionic liquids containing the cation 1-ethyl-3-methylimidazolium and Cu-BTC MOF.
The effect on the adsorption of carbon dioxide, methane, nitrogen, and their mixtures has been
investigated when the ionic liquid molecules (ion pairs) are located in the pores of Cu-BTC. We
performed molecular simulations to analyze the effect exerted on the separation of CO2/CH4 and
CO2/N2. Two alternatives were considered: (1) change of the anion and (2) vary the concentration of
RTIL within the Cu-BTC pores. The results show that the presence of RTIL in the pores enhances the
separation capabilities of the MOF in both CO2/N2 and CO2/CH4 mixtures.
3.5 Adsorption and separation
126
O-3.5-10
Synthesis of DNL-6 with high concentration of Si (4Al) species and its good performance
for CO2 separation
Xiong Su1, 2, Peng Tian1, Dong Fan1, 2, Yue Yang1, Shutao Xu1, & Zhongmin Liu1*
1 Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, P.R. China, suxiong@dicp.ac.cn, liuzm@dicp.ac.cn
2 University of Chinese Academy of Sciences, Beijing 100049, P.R. China
Microporous crystalline materials with intrinsic aperture size of molecular dimensions have shown
potential applications in gas separations. DNL-6, an isomorphous crystal of RHO zeolite with SAPO
composition, which was recently reported by our group, possesses large pore volume (0.36 cm3/g)
and good thermal stability. In this work, we report a novel method to synthesize DNL-6 with a high
concentration of Si (4Al) environment and its excellent behaviors in CO2/CH4 separations.
O-3.5-11
Cation gating and selective carbon dioxide adsorption in flexible zeolite Rho
M.M. Lozinska1, P.A. Wright1, J.P.S. Mowat1, X. Hu2, S. Brandani2, M. Palomino3, J.L. Jorda3, S.
Valencia3, F. Rey3
1School of Chemistry, University of St Andrews, St Andrews, UK, paw2@st-andrews.ac.uk
2Institute for Materials and Processes, University of Edinburgh, Edinburgh, UK
3Instituto de Tecnologia Quimica, Universidad Politecnica de Valencia, Valencia, Spain
CO2 adsorption in zeolite Rho has been related to the zeolite’s framework structure and its extraframework cation sites. High uptakes for CO2 and good selectivities for CO2 over CH4 and N2 have
been observed, and the structure measured by in situ XRD. Structural changes including concerted
cation movements and breathing of the zeolite framework are observed, and in most cases adsorption
occurs by CO2-mediated movement of cations away from the 8MR window sites to allow its
diffusion, followed by return of the ‘gating’ cation to its original site. Selective adsorption is possible
due to adsorbate-dependent cation gating. This is expected to be a widespread mechanism for
selective adsorption over zeolites.
O-3.5-12
Effective Separation of Hydrocarbon Mixtures by Zeolitic Imidazolate Frameworks-8 (ZIF-8)
Membranes
Yichang Pan, Zhiping Lai
Advanced Membrane and Porous Materials Center, King Abdullah University of Science and
Technology, Thuwal, 23955-6900, Kingdom of Saudi Arabia, Yichang.pan@kaust.edu.sa
The separation of hydrocarbon mixtures is an important but challenging process in the petrochemical
industry. Thermally and hydrothermally stable microporous membranes with intrinsic high
permeability and selectivity are highly demanded. ZIFs are microporous materials and belong to the
new class of metal–organic frameworks (MOFs). ZIF-8 is formed by bridging 2-methylimidazolate
anions and zinc cations resulting in a sodalite (SOD) topology with a pore size of about 0.34 nm.
Herein, it was demonstrated that ZIF-8 membranes synthesized in aqueous solutions exhibited
effective separation of ethane/propane and propylene/propane binary mixtures. The process is more
economical and green compared to other synthesis procedures that are conducted in organic solvents.
The performance for separation of propylene/propane is far beyond the “upper-bound trade-off line”
of both ploymeric and carbon membranes.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.5-13
Adsorption and differential heats of adsorption of hexane isomers on ZIF-8
A. Ferreira1, M. Mittelmeijer-Hazeleger2, M.A. Granato1, V.F.D. Martins1, A. Rodrigues1, G.
Rothenberg2
1 LSRE, Faculty of Engineering, University of Porto, Porto, Portugal, aferreir@fe.up.pt
2HIMS, University of Amsterdam, Amsterdam, The Netherlands
We study the adsorption equilibrium isotherms and differential heats of adsorption of hexane isomers
on ZIF-8. The studies are carried out at 373 K using a manometric set-up combined with a microcalorimeter. The linear and mono-branched isomers adsorb well, but 2,2-dimethylbutane is totally
excluded. Plotting the differential heat of adsorption against the loading shows an initial plateau for nhexane and 2-methylpentane, followed by a slow rise indicating adsorbate–adsorbate interactions. For
the di-branched isomers the differential heat of adsorption decreases with loading. To gain insight
into the adsorption of these isomers in the ZIF-8 pores, we ran molecular simulations using the
GCMC approach. Comparing the simulation and the experimental results shows that the ZIF
framework model requires blocking of the cages, since 2,2-DMB cannot fit through the sodalite-type
windows. Our results prove the potential of ZIF-8 as a new adsorbent that can be employed in the
upgrade of the Total Isomerization Process for the production of high octane number gasoline, by
blending di-branched alkanes in the gasoline.
O-3.5-14
Investigation of Small Pore Zeolites Via Vapor Phase Adsorption of n-Hexane
C.Y. Chen and S.I. Zones
Chevron Energy Technology Co., Richmond, California 94802, USA, cychen@chevron.com
The present paper reports our recent studies on n-hexane adsorption in a series of small pore zeolites
such as K-LTA (3A), Na-LTA (4A), Ca-LTA (5A), ITQ-29 (pure-silica LTA), Na-chabazite, SSZ-17
(LEV), H-ZK-5, K-ZK-5, H-Rho, Na/Cs-Rho, ITQ-12, SSZ-16, SSZ-36 and SSZ-50 to investigate
their effective pore structures. The effects of zeolite compositions and crystal sizes on the adsorption
kinetics are investigated with some of these zeolites. The adsorption kinetics of n-hexane provides
useful information on the effective pore sizes/volumes of zeolites. It is a useful tool to distinguish
between small pore zeolites and larger ones as well as among small pore zeolites. Crystal sizes and
zeolite compositions play a considerable role on its adsorption kinetics.
O-3.5-15
Towards the Computational Screening of MOFs for Xylene Separation
M. Lennox, P.Z. Moghadam, A.D. Gellan, T. Düren
Institute for Materials and Processes, University of Edinburgh, UK, M.Lennox@ed.ac.uk
The C8 alkylaromatics are of vital importance in a number of chemical processes, as is the separation
of para-, ortho-, and meta-xylene and ethylbenzene mixtures into their individual components.
Several metal-organic frameworks (MOFs) have been identified which exhibit a strong adsorptive
preference for either o- or p-xylene, providing a promising alternative to existing zeolite-based
separations.
Given the vast number of published MOFs, it is desirable to limit experimental efforts to only the
most promising materials. Here we present a methodology capable of correctly predicting xylene
selectivity in a range of MOFs using simple and fast computational tools. It will be shown that the
preference of the material is closely linked to the size and shape of the pore structure.
3.6. Novel applications (health, electronics, sensors)
128
O-3.6-01
A Photoconductive Covalent Organic Framework Showing Light-Induced Charge Transfer
Towards Included Fullerene
Mirjam Dogru, Matthias Handloser, Florian Auras, Thomas Kunz, Dana Medina, Achim Hartschuh,
Paul Knochel* and Thomas Bein*
Department of Chemistry and Center for Nano Science (CeNS), University of Munich (LMU),
Germany, bein@lmu.de
We have created a Covalent Organic Framework (COF) containing stacked thieno[2,3-b]thiophenebased building blocks acting as electron donors (TT-COF), with high surface area and a 3 nm open
pore system. This open framework takes up the well-known fullerene electron-acceptor PCBM, thus
forming a novel structurally ordered donor-acceptor network. Spectroscopic results demonstrate lightinduced charge-transfer from the photoconductive TT-COF donor network to the encapsulated PCBM
phase in the pore system. Moreover, the first COF-based photovoltaic device could be assembled with
these components. The organization of the molecular building blocks into a crystalline framework
with defined conduction paths provides a promising model system for ordered and interpenetrated
networks of donors and acceptors at the nanoscale.
O-3.6-02
Enhancement of catalysis by the localized surface plasmon resonance of
size- and color-controlled Ag prepared using microwave and mesostructure
Koujiro Fuku1, Ryunosuke Hayashi1, Takashi Kamegawa1, Kohsuke Mori1,2, Hiromi Yamashita1,2
1Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka
University, 2ESICB, Kyoto University, Japan. e-mail : yamashita@mat.eng.osaka-u.ac.jp
Ag nanoparticles can increase the surface charge density by localized surface plasmon resonance
(LSPR) under the light irradiation, and the LSPR can change absorption wavelength depending on its
particle-size and morphology. The efficient catalytic performance can be expected under various
light environments induced by the LSPR of size- and morphology-controlled Ag. In this study, the
size- and morphology-control of Ag was prepared on SBA-15 mesoporous silica by rapid and uniform
heating with microwave (Mw) and its catalytic enhancement by the LSPR was observed.
O-3.6-03
Ultrafast optical study on silver nanoparticles stabilized in zeolite Beta colloidal suspensions
F. A. Kawtharani1,2, V. De Waele1, R. Retoux3, S. Mintova2, G. Buntinx1
1Laboratory of Infrared and Raman Spectroscopy (LASIR), CNRS-University of Lille1, 59650
Villeneuve d’Ascq, France, e-mail: vincent.dewaele@univ-lille1.fr
2Laboratory of Catalysis and Spectroscopy (LCS), ENSICAEN, CNRS, University of Caen, 6 Bd
Maréchal Juin, 14050 Caen, France
3CRISMAT, ENSICAEN, CNRS, University of Caen, 6 Bd Maréchal Juin, 14050 Caen, France
Plasmonic-metal nanostructures are highly desirable for efficient light-driven chemistry. In this work,
femtosecond pump-probe measurements were carried out on nanometer-sized silver particles
stabilized in zeolite beta in colloidal suspensions. The presence and high dispersion of silver
nanoparticles was assessed by HRTEM and X-ray measurements. The ultrafast dynamics of the hot
electrons in the conduction band of the metal nanoparticles was induced by excitating at 400 nm with
100 fs laser pulses, and the transient spectra were recorded for different excitation energies. From the
analysis of the transient spectra and of the kinetics, it is demonstrated that the plasmonic response is
governed by an efficient energy transfer from the hot electrons to the molecules at the surfaces of the
metal. The potential of metal containing nanosized zeolite for “hot electron femtochemistry” is
discussed.
17 IZC, 2013. ORAL COMMUNICATIONS
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O-3.6-04
NH2-MIL-101 as adsorbent for potential application in nuclear medicine
P. Serra-Crespo1, H.G.M.E. van Ostaay1,2, .A.G. Denkova2, H.Th. Wolterbeek2, F. Kapteijn1,
J. Gascon1
1Catalysis Engineering, Chemical Engineering Department, Delft University of Technology,
Julianalaan 136, 2628 BL Delft, The Netherlands. P.SerraCrespo@tudelft.nl
2Radiation, Radionuclides & Reactors, Delft University of Technology, Mekelweg 15, 2629 JB Delft,
The Netherlands
Metal-organic frameworks have been tested in the adsorption of molybdates for their use as
adsorbents in 99Mo/99mTc generators. In particular, NH2-MIL-101(Cr) brings together the advantages
of a very large pore volume with the amine functionalization of the organic linker. At low pH
conditions protonation of the amines results in very high affinities for molybdates resulting in higher
uptakes than any other previously reported material. Such excellent performance highlights the
potential of functionalized MOFs as adsorbents in 99Mo/99mTc generators for medical imaging.
O-3.6-05
Ordered Mesoporous Silicas for Drug Delivery in Dermatological Applications
B. Onida*1, 2, R. Mortera1, B. Camarota1, D. Caldarola1, G. Chieregatti2, A. Gignone1
1 Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Corso Duca degli Abruzzi
24, 10129 Torino, Italy, barbara.onida@polito.it
2 Miso S.r.l, Corso Castelfidardo 30/a, 10129, Torino – Italy
Ordered Mesoporous Silicas (OMSs) have been widely investigated as drug carriers in several fields,
from tissue engineering to cancer therapy. A promising area of application is the topical therapy of
dermatological diseases, wounds, sores and burns. We present the incorporation and sustained release
of three different APIs (Active Principle Ingredients), i.e. salyciclic acid, clotrimazole (antifungal)
and amikacin (antibiotic) in OMSs for the production of medical devices (creams, ointments or gels)
ensuring a constant therapeutic concentration of API at the application site for a controlled time, in
order to reduce the number of applications, so to obtain a higher efficacy of the therapy and a better
patient compliance.
O-3.6-06
Influence of the silica support morphology on the long-term corticoid release.
R.A. García, V. Morales and P.E. Gonzalez.
Department of Chemical and Environmental Technology, ESCET, Universidad Rey Juan Carlos, C/
Tulipán s/n, 28933 Móstoles, Madrid, Spain rafael.garcia@urjc.es
Silica-based mesoporous materials have unique structural characteristics, with an amorphous silica
network forming the walls of a well-ordered arrangement of pores and cavities. Silica-based ordered
mesoporous materials can be employed as local controlled delivery systems of drugs. In this work, a
variety of porous materials have been compared in terms of corticoid loading and drug delivery rate in
the methylprednisolone liberation under different body fluid pH. From this fact, 13C and 29Si
HETCOR-NMR has been used to study the onset of interactions between the Urbason,
(Methylprednisolone, synthetic steroid, glucocorticoids used in medicine for immunosuppressive and
anti-inflammatory effects) and different silica supports. We can conclude that materials with cubic
structure confined corticoid with higher interaction drug-silica wall, resulting in a better control of the
drug delivery. SBA-16 shows stronger interactions between Q sites and the drugs proton in the
bidimensional 29Si-1H NMR spectra.
3.6. Novel applications (health, electronics, sensors)
130
O-3.6-07
Control of dye fluorescence by encapsulation into 1D nanochannels
Virginia Martínez-Martínez1, Raquel García2, Luis Gómez-Hortigüela2, Joaquín Pérez-Pariente2,
Íñigo López-Arbeloa1
1Departamento de Química Física, Universidad del País Vasco, UPV/EHU, Bilbao,
Spain.virginia.martinez@ehu.es
2Instituto de Catálisis y Petroleoquímica, ICP- CSIC.Madrid, Spain.
This work shows how the fluorescence properties of a dye can be fine-tuned by its encapsulation in
Mg-containing nanoporous aluminophosphates with one-dimensional nanochannels of different size
and topology. Pyronine Y (PY) molecules are forced to rearrange from undesirable H-type dimer in
MgAPO-5 (AFI structure) to the red emissive J type aggregate in MgAPO-36 (ATS). PY/ATS
crystals show a multicolor emission, offering an interesting material for energy transport. Finally, the
total suppression of the aggregation is accomplished in MgAPO-11 (AEL) due to its reduced channel
size and particular topology, attaining a high fluorescent hybrid system with a strong alignment of the
chromophores for potential application in optics.
O-3.6-08
Maya Blue analogs prepared with various zeolite matrices
S. Kowalak, A. Zywert, M. Szyld
Faculty of Chemistry, A. Mickiewicz University, Poznań, Poland, skowalak@amu.edu.pl
The pigments analogous to Maya Blue can be obtained by entrapment of indigo or its derivatives into
zeolites of appropriate pore size. The preparation consists in grinding of zeolite with dye and heating
the mixture above 100 oC. The hue of resulting pigments depends on type of zeolite matrix and on
cations introduced into zeolite. The fast pigments are formed when dye molecules are accommodated
inside the zeolite inner voids. The dye adsorbed on outer surface (e.g. in zeolite A) is easily removed
by solvent extraction or sublimation.
O-3.6-09
Energetic performances of channel and cage-type zeosils
L. Tzanis, M. Trzpit, M. Soulard, T.J. Daou, J. Patarin
Univ. de Haute Alsace (UHA), CNRS, Equipe Matériaux à Porosité Contrôlée (MPC), Institut de
Science des Matériaux de Mulhouse (IS2M) LRC 7228, ENSCMu, 3bis rue Alfred Werner, 68093
Mulhouse Cedex, France, Joel.patarin@uha.fr
The energetic performances of various channel (AFI, MTW and TON-type zeosils) and cage-like
(CHA, STT, and DDR) zeosils were determined using water intrusion-extrusion experiments. In
particular the “MEL-water” system will be described All the “zeosils-water” systems display a spring
molecular behavior. A correlation was found between the intrusion pressure and the pore diameter for
channel systems and the largest cage size for cage systems.
17 IZC, 2013. ORAL COMMUNICATIONS
131
O-3.6-10
Effect of Hydrophobic Tail Length of Polysorbate Surfactants on
Properties of MFI-type zeolite Ultra-Low-k Films
Ting-Yi Li, Chun-Hsien Yu, Hsin-Yan Lu, and Ben-Zu Wan*
Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan,
benzuwan@ntu.edu.tw
Porous silica low-k films have been prepared from solutions composed of MFI-type zeolite
nanoparticles and polysorbate surfactants (Tween 20, Tween 40, or Tween 60) with different
hydrophobic tail lengths, in which the critical micelles concentration (CMC) and the hydrophilic
property of the surfactants are both decreased with the increase of tail length. In this research it is
found that more pore volume can be generated in the samples prepared by using surfactant with
longer tail length, because of the formation of more micelles in the coating solution. However, the
film prepared by using the surfactant with shortest tail length (i.e., Tween 20) can possess the lowest k
value. A stronger interaction between silica nanoparticles and the surfactant with shorter tail length
(which possesses higher hydrophilic property) has been detected. The presence of residual silanol
groups within the films after a hexamethyldisilazane (HMDS) surface modification treatment can be
decreased substantially by the decrease of surfactant tail length. It has been concluded that the less
remaining of silanol groups can cause the film to possess lower k values, lower leakage current
densities, and higher breakdown fields.
POSTER COMMUNICATIONS
SECTION 1:
“ORDERED POROUS MATERIALS:
SYNTHESIS AND MODIFICATION”
1.1. Zeolites and zeotypes
134
P-1.1-01
Microporosity of amorphous aluminosilicate precursors of zeolites
A. Morsli1,2, R. Arletti3, A. Bengueddach2, F. Quignard4 and F. Di Renzo4
1Département de Chimie, Faculté des Sciences, USTO « M.B », B.P.1505 Elmenaouar, Oran, Algeria.
morsli_amine@yahoo.fr
2Laboratoire de Chimie des Matériaux, Université Oran Es-Senia, B.P 1524 Elmenaouar, Oran,
Algeria. abengueddach@gmail.com
3Dipartimento di Scienze della Terra, Università degli Studi di Torino, Via Valperga Caluso 35,
10125 Torino, Italy. rossella.arletti@unito.it
4Institut Charles Gerhardt, UMR 5253 CNRS-UM2-ENSCM-UM1, Matériaux Avancés pour la
Catalyse et la Santé, ENSCM, 8 rue Ecole Normale, 34296 Montpellier Cedex 5, France.
direnzo@enscm.fr
The hydrothermal gels formed as intermediates in zeolite synthesis present a high sodium content,
which results from charge compensation of both lattice anions and deprotonated silanols. The
hydration water of the alkali cations is expected to correspond to a potential microporosity, as in the
case of crystalline zeolites. Supercritical drying of the gels allows to retain a fraction of the potential
microporosity, unless a too high fraction of silanols weakens the aluminosilicate framework and
prevents the retention of microporosity upon drying.
P-1.1-02
Effect of SDA on FAU-CHA Interzeolite Conversion
Naoki Yamanaka1, Masaya Itakura1, Yoshimichi Kiyozumi2, Masahiro Sadakane1, and Tsuneji
Sano1*
1Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University,
Higashi-Hiroshima 739-8527, Japan
2National Institute of Advanced Industrial Science and Technology, Sendai 983-8551, Japan
*Corresponding author, e-mail tsano@hiroshima-u.ac.jp, fax +81-82-424-5494
FAU-CHA interzeolite conversion was investigated in the presence of BTMA+ and TMAda+ as SDAs.
Although TMAda+ has the high abilities of both decomposition/dissolution of starting FAU-type
zeolite and transformation of generated nanoparts into CHA-type zeolite, CHA-type zeolite
synthesized using BTMA+ exhibited higher acid stability. It was confirmed again that the interzeolite
conversion route is an alternative strategy for zeolite synthesis.
P-1.1-03
Hydrothermal synthesis of zeolite SSZ-16 (AFX) from optimized synthesis solutions
P. Hrabanek1, A. Zikanova1, J. Drahokoupil2, O. Prokopova1, L. Brabec1, I. Jirka1, V. Fila3, J.
Cookney3, M. Kocirik1
1J. Heyrovský Institute of Physical Chemistry of the ASCR, v.v.i.; Dolejškova 2155/3, 18223 Prague
8, Czech Republic, pavel.hrabanek@jh-inst.cas.cz
2Institute of Physics of the ASCR, v.v.i.; Na Slovance 2, 18221 Prague 8, Czech Republic
3Institute of Chemical Technology Prague, Technická 5, 16628 Prague 6 Dejvice, Czech Republic
Zeolite SSZ-16 belongs to AFX framework type containing 8-membered oxygen rings (isotopic with
SAPO-56 and MAPSO-56). The work was focused on the optimization of synthesis procedure to
prepare uniform micrometer size SSZ-16 particles. The optimization was aimed to reduce duration of
crystallization and replace fumed silica with colloidal one. The ageing period was prolonged and
carried out at elevated temperature (80°C) inside silicon oil bath under vigorous stirring. Larger
population of nuclei was expected to be formed prior hydrothermal crystallization. Zeolite samples
were characterized with XRD and SEM.
17 IZC, 2013. POSTER COMMUNICATIONS
135
P-1.1-04
Comparison of Properties between Zeolites Heated
by Microwaves and Electric Oven
T. Ohgushi1, S. Ando1 and M. Susaki2
1 Institute of Liberal Arts and Sciences, Toyohashi University of Technology, Toyohashi, Japan,
ohgushi@las.tut.ac.jp
2 Dep. of Industrial Systems Engineering, Osaka Prefecture University College of Technology, Osaka,
Japan
An influence of microwave heating (MW) on properties of zeolites (Na-X, K-L) was investigated in
comparison with the heating with electric oven (EO). The zeolites were heated at Ttr (=373K-673K)
for 1 h. Any heated zeolites showed no structural changes and de-Al. An adsorption capacity of K-L
definitely decreased at Ttr=373K in MW but only began to decrease at Ttr>473K in EO. Na-X and K-L
decreased degrees of ion-exchange at Ttr=473K and 373K, respectively, in MW but showed no
change at such temp. in EO. It was concluded that the changes of properties by the heating were
caused by migrations of cation, which were promoted by MW more than by EO.
P-1.1-05
Fluorine-Free Synthesizing Fluoride-Caused AlPO4-34
Jinxiong Wu, Huiru Zhao, Niu Li,*Qianqian Luo, Chunqian He, Naijia Guan, Shouhe Xiang
Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, College of
Chemistry, Nankai University, Tianjin, China, liniu@nankai.edu.cn
A new synthetic method for the preparation of microporous crystalline triclinic AlPO4-34 has been
developed. Fluorine free triclinic AlPO4-34 phase, namely AlPO4-34FF has been prepared in the
absence of fluorine. It has been found that controlling the extent of hydrolysis and condensation
during the crystallization is the key for the formation of AlPO4-34FF. The mixing solvent of glycol
and water can be used to achieve this performance. The fluorine-free crystallization of AlPO4-34FF
avoiding the use of toxic HF acid, would be advantageous in potential scale up. Meanwhile, the
modified procedure affects the crystal composition. In the new product each hydroxyl group replaces
a fluoride atom coordinated to two aluminum knots.
P-1.1-06
An efficient method to synthesize IM-5 zeolite
Junwen Chen, Chao Zhang, Yongrui Wang1, Xuhong Mu
State Key Laboratory of Catalytic Material and Reaction Engineering , Research Institute of
Petroleum Processing, SINOPEC, Beijing, P. R. CHINA, wangyr.ripp@sinopec.com
IM-5 zeolite, with a bidimensional 10 membered ring channels, has shown a potential use in
petroleum and petrochemical industries because of its good thermal and hydrothermal stability. Thus
far, only few studies have been reported on synthesis of IM-5 zeolite. The product yield per reactor is
too low (n(H2O)/n(SiO2)=40) and time of crystallization is too long (10~14days). This paper
investigated the effect of water content on synthesis of IM-5 zeolite. With the water content
reduction, concentration of silicon aluminate increases. Probability of radical polymerization ring
formed by silicon aluminate increases, which enhances the formation of crystal nucleus. Also,
concentration of template increases, probability of template contact with silicon aluminate increases,
which enhances the growth of crystal nucleus. IM-5 zeolite can be prepared with high product yield
per reactor (n(H2O)/n(SiO2)=10~20) and 5~6 days, which is a suitable way to be applied in industry.
1.1. Zeolites and zeotypes
136
P-1.1-07
Isomorphous substitution of Nb and Ta into Y-type zeolite as a tool
for creation of new surface properties
Anna Wojtaszek1,2, Maciej Trejda1, Frederik Tielens2, Maria Ziolek1
1Adam Mickiewicz University, Poznan, Poland;
2UPMC Univ Paris 06, UMR7574 Lab. de Chimie de la Matière Condensée, Paris, France
Substitution of zeolite silicon atoms by different metal ions, is of great importance because it can
generate unique properties of the materials obtained. In this work we focus on efficiency of metal
incorporation using different synthesis procedures, as well as the creation of new surface properties of
zeolites. Both experimental and theoretical tools were applied for evidence of surface properties
changes upon isomorphous substitution. The highest efficiency was reached by the use of two-steps
procedure with gel heating in oven. Ta is easier to include into the faujasite structure than Nb,
independently of the methods of gel preparation and thermal treatment. Introduction of Nb and Ta
into FAU structure changes surface properties of zeolites into the enhancement of basicity of bridged
oxygens (X-O-Si or Si-O-Al).
P-1.1-08
Ionothermal Synthesis of Zinc Phosphate or Phosphite framework Materials
Lei Liu*, Sanying Li and Jinxiang Dong
Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan, China,
liulei@tyut.edu.cn
Ionothermal synthesis has been used with great success for the preparation of hitherto unknown
materials, for the improved preparation of previously synthesized materials, and for mechanistic
studies. Herein we use tetramethylammonium acetate as a solvent and SDA provider, two different
ZnPO framework materials, N(CH3)4·ZnH3(PO4)2 and [(CH3)4N]2Zn3(HOPO3)4, were synthesized.
The crystalline solid products were characterized by XRD, SEM, FT-IR and TG.The experimental
result shows that the P-OH or P-H plays an insignificant role in the condensation of phosphate (or
phosphite) precursors into extended solids. For the two compounds, the TMA cation acts a templating
role to induce the resulting framwork, finally which is occluded into the pore channels to balance the
framework charge.
P-1.1-09
Li+ Exchange into Zeolite Na-Y from Aqueous Methanol Depends upon Water Content
H. S. Kim1, W. T. Lim1,*, K. Seff2,*
1Department of Applied Chemistry, Andong National University, Andong 760-749, Korea,
wtlim@andong.ac.kr
2Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822-2275, USA
The ion exchange of Li+ into zeolite Na-Y, |Na75|[Si117Al75O384]-FAU, was attempted using methanolwater mixed solvents. Four solvents ranging in composition from as-purchased methanol (water
concentration 0.02 M) to pure water were used. Four single crystals of Na-Y were treated with 0.1 M
LiNO3 in each of the four solvents at 333 K, followed by vacuum dehydration at 673 K. Their
structures were determined by single-crystal synchrotron X-ray diffraction techniques at 100(1) K in
the space group Fd 3m. In the four structures, Li+ and Na+ fill sites I’ and II; the remaining cations,
when they can be found, occupy III’ sites. The greatest degree of exchange of Li+ for Na+, 96%, was
achieved from undried methanol under the conditions employed. The extent of Li+ exchange
decreases with increasing water content.
17 IZC, 2013. POSTER COMMUNICATIONS
137
P-1.1-10
Synthesis of ZSM-22/ZSM-23 intergrowth zeolite
K.B. Chi1, Z.J. Tian2, L.J. Yan1, B.C. Wang2, S. Hu1, M.W. Tan1, Y.F. Liu1, S.B. Gao1
1Petrochemical Research Institute, PetroChina Company Limited, Beijing, China,
yanlj@petrochina.com.cn
2 Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Hydroisomerization catalysts and its zeolites has been much attached importance by the international
oil companies and research institutions. In this work, we presented a novel dual-template strategy for
the synthesis of ZSM-22/ZSM-23 intergrowth zeolite. The dual-template system consisting of
ethylamine (EA) and diethylamine (DEA) was used as structure-directing agent in the synthesis
process. We investigated the influence of template agent, SiO2/Al2O3 mole ratio and alkali sources on
the synthesis process. The results indicated that well-crystallized ZSM-22/ZSM-23 intergrowth
zeolite could be synthesized with the above-mentioned dual-template system. And the intergrowth
zeolite has new topology structure, which was different from ZSM-22 and ZSM-23. The synthesis
region was wider when using KOH as alkali source than NaOH.
P-1.1-11
Synthesis and characterization of zeolite ZSM-5 in the presence of ammonia and phosphate
Jianzhun Jiang, Jing Feng, Mingsen Zhang, Li Ke, Yuanyuan Ji
Beijing Research Institute of Chemical Industry, SINOPEC, Beijing 100013, P.R. China
Email: jiangjz.bjhy@sinopec.com; fengj.bjhy@sinopec.com
Zeolite ZSM-5 was synthesized using tetrapropylammonium hydroxide as template in the presence of
ammonia and phosphate with silica sol and alumina isopropoxide as the silica and alumina sources.
The influence of pH value and the content of phosphate in the solution on the synthesis were carefully
investigated. The results show that a much higher pH value is required to synthesize zeolite ZSM-5
in the presence of phosphate. The critical pH value is generally higher than 10.0 and goes up with the
increase of the content of phosphate. Amorphous products would be obtained when the pH values are
lower than the critical one. Moreover, SEM characterization illustrates that ZSM-5 crystal particles
might grow along b-axis in topology when the pH value of the mixture is within 10.0 to 11.0. The
basic strength of the mixture might have a positive contribution to both the crystallization and the baxis growth when the concentration of phosphate is fixed.
P-1.1-12
Estimation of acid site distribution in pores of H-ZSM-5 zeolite prepared with various
structure-directing agents
Hiroshi Mochizuki, Toshiyuki Yokoi, Seitaro Namba, Junko N. Kondo and Takashi Tatsumi
Chemical Resources Laboratory, Tokyo Institute of Technology,Yokohama, Japan,
ttatsumi@cat.res.titech.ac.jp
H-ZSM-5 zeolites with Si/Al=40-50 were synthesized by using various structure-directing agents
with and without Na+. These H-ZSM-5 zeolites exhibited little difference in the strength of Brønsted
acid and the n-hexane cracking activity. On the other hand, activitis and activation energies for 3methylpentane cracking over these H-ZSM-5 were significantly different. The 3-methylpentane
cracking is a suitable reaction to obtain the information about the distribution of the acid sites located
in the micropores of H-ZSM-5, because the bulky transition state is necessary. The acid sites in HZSM-5 prepared by using tetrapropylammonium+ without Na+ collected at the pore intersection.
1.1. Zeolites and zeotypes
138
P-1.1-13
Ionothermal synthesis, crystal structure and magnetic properties of a new manganese phosphite
with intersecting structure
Miao Yang1,* Peng Chen2, Xinjie Li1, Chang Wang1, Peng Tian1,* Meiqi Zhang2, Peifang Yan1 and
Qingshan Liu1
1Dalian Institute of Chemical Physics, Chinese Academy of Science, Zhongshan Road 457, 116023
Dalian, P. R. China, yangmiao@dicp.ac.cn, tianpeng@dicp.ac.cn.
2 Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang
University, Xuefu Road 74, 150080, Harbin, P. R. China
Ionothermal synthesis, as a new route to prepare inorganic microporous materials, has received more
and more attention. Recently, two room temperature ionic liquid N,N,N-triethyl-propylamine
bis(oxalato)borate and N,N,N-triethyl-butylamine bis(oxalato)borate ([N222n][BOB], n = 3, 4) were
prepared and used to synthesize metal phosphite, and a new manganese phosphite
(H3O)Mn12[H2PO3]9[HPO3]8 (1) with compact intersecting structure was obtained. The title
compound crystallizes in noncentrosymmetric space group I-43d with lattice parameters of a =
21.6812(2) Å, V = 10191.72(18) Å3. The compound is an antiferromagnet. Investigation on its
second-order nonlinear optical properties is still in progress.
.
P-1.1-14
Synthesis of ZSM-5 from natural rectorite minerals activated by different methods
H.Y. Liu1, W.W. Wang2, T. Shen2 and X.J. Bao1,2
1State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, P. R.
China, baoxj@cup.edu.cn
2The Key Laboratory of Catalysis, China National Petroleum Corp., China University of Petroleum,
Beijing 102249, P. R. China
Using natural rectorite minerals activated by different methods as the starting material, a series of
ZSM-5 were hydrothermally synthesized. The characterization results showed that both the alkali
fusion activation and the high-concentration alkali solution (HCAS) activation are more effective for
the depolymerization of the SiO4 tetrahedra in rectorite than the conventional thermal treatment.
Especially, the ZSM-5 derived from the HCAS activated rectorite has much smaller crystal size and
significantly different morphology, which is difficult to achieve in the conventional synthesis.
P-1.1-15
Synthesis and study of the structural and adsorption properties of synthetic zeolite ECR-18
with paulingite structure
O. Yu. Golubeva, N. Yu. Ulyanova, A. V. Yakovlev
Grebenshchikov Institute of Silicate Chemistry, RAS, 199034, Russia, St. Petersburg, nab. Makarova,
2, ternovayanatali@gmail.com
This work was directed on the study of synthesis conditions of zeolites ECR-18 and its structural and
sorption characteristics investigation. The effects of various factors on the synthesis ECR-18 and their
influence on the final product of crystallization were studied. The optimization of synthesis
technology was carried out. As a result the significant reduction of the synthesis duration (from 22
days up to several hours) has been achieved. Structure, physicochemical and thermal properties of
zeolites synthesized were investigated by using differential thermal analysis (DTA), X-ray diffraction
(XRD), infrared spectroscopy (IR). The specific surface area was determined by the method of
adsorption / desorption of nitrogen. Calculations by BET equation were performed. Benzene
adsorption was studied. The sorption kinetics of lead ions from the model solutions by samples
synthesized was investigated.
17 IZC, 2013. POSTER COMMUNICATIONS
139
P-1.1-16
Seed-assisted Synthesis of VET-type zeolite
without the Use of Organic Structure-Directing Agents
Kenta Iyoki, Keiji Itabashi and Tasuya Okubo
Department of Chemical System Engineering, The University of Tokyo, Tokyo, Japan,
okubo@chemsys.t.u-tokyo.ac.jp
OSDA-free synthesis routes of industrially important zeolites have been strongly desired for the
reasonable production as well as the saving of energy and the protection of environment. In this study,
our recent success in the synthesis of VET-type zincosilicate zeolites is reported by seed-assisted
method without the use of organic structure-directing agents (OSDAs). The H+-form products show
similar pore characteristics to the ones of the calcined seed crystals. Mixed alkaline metal cation
system of Na and Li is effective and these cations play an important role in OSDA-free system, not
only as feed source of OH-. Several characterizations performed by XRD, ICP-AES, FE-SEM, 29Si
MAS NMR and N2 adsorption-desorption measurement reveal that the highly crystalline products are
obtained by this strategy.
P-1.1-17
A study on dry gel conversion of silicas of different nature into Silicalite-1
M. S. M. Kamil 1, K. Manikandan 1, S. P. Elangovan 2, K. K. Cheralathan 1,*
1Materials Chemistry Division, School of Advanced Sciences, VIT University, Vellore, India,
cheralathan.k@vit.ac.in,
2Nippon Chemical Industrial Co. Ltd, Kameido, Koto-ku, Tokyo, Japan
Different silicas such as SBA-15 and SBA-16 mesoporous silicas, fumed silica and gel from
tetraethyl orthosilicate (TEOS) were converted into Silicalite-1 by steam-assisted dry gel conversion
in the presence of tetrapropylammonium hydroxide (TPAOH) as structure directing agent. The
influence of the nature of silicas, silica to TPAOH ratio and reaction time on the crystallization
behavior and morphology of the obtained Silicalite-1 has been investigated. Apart from the
crystallization parameters such as silica to TPAOH ratio and crystallization period, structure and
morphology of the silica sources also have profound effect on the crystallization behavior and
morphology of Silicalite-1.
P-1.1-18
Aminothermal Synthesis of CHA-SAPO Molecular Sieves with High Solid Yield and their
Catalytic Performance in MTO Reaction
Dong Fan1 , 2, Peng Tian1, Xiong Su1, 2, Dehua Wang1, 2, Yangyang Yuan1,2, Chan Wang1,2 and
Zhongmin Liu1*
1 Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, P. R. China,
fandong08@dicp.ac.cn, liuzm@dicp.ac.cn
2 University of Chinese Academy of Sciences, Beijing, P. R. China
The silicoaluminophosphates with the CHA topology (CHA-SAPOs) have been attracting great
attention due to its good performance in the MTO reaction. A novel synthetic strategy using organic
amines as both solvent and template was proposed and designated as aminothermal synthesis by our
group. Herein, aminothermal synthesis of SAPO molecular sieves was further investigated on a
variety of organic amines. Three amines including DIPA, DPA and TMEDA could direct the
crystallization of SAPO-34 with quite high solid yield. SAPO-44 was obtained using HMI template
for the first time. The high purity and good crystallinity of the products was confirmed by multiple
characterization techniques. MTO evaluation results showed that the CHA-SAPOs possessed good
catalytic properties.
1.1. Zeolites and zeotypes
140
P-1.1-19
Study on the crystallization of the hollow titanium silicalite zeolite
Min Lin1,Bin Zhu1, Xingtian Shu1, Chunfeng Shi1, Guofan Li2, Gang Shen2, Bin Li2, Hua Li3
1State Key Laboratory of Catalytic Materials and Reaction Engineering , Research Institute of
Petroleum Procesing, SINOPEC, Beijing, P. R. CHINA,minlin@tom.com
2HunanJianchang Petrochemical Co., LTD, Yueyang Hunan, P. R. CHINA
3Changling Company, SINOPEC, Beijing, P. R. CHINA
In order to investigate the crystallization of the hollow titanium silicalite zeolite(HTS), the X-ray
diffractometry and FT-IR spectrometry were applied to track the process of crystallization of HTS.
The results revealed that at the initial stage of crystallization the interactions between silica gel and
titania gel in the polymer blend could gradually lead to the formation of tiny crystal nuclei with
complicated structure that could slowly grow up to form zeolite. Quite different from the
conventional zeolites that use the acid sites as the catalytically active centers, the oxidative reactivity
of HTS was not proportional to its crystallinity and is associated with the oxidative centers of titanium
contained in the zeolite.
P-1.1-20
Green synthesis of zeolites from submolten salt depolymerized aluminosilicate minerals
Xiaojun Bao1, Ning Li1, Haiyan Liu2, Tiesen Li2, Yuanyuan Yue2
1 State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249,
China, baoxj@cup.edu.cn
2 Key Laboratory of Catalysis, China National Petroleum Corporation, China University of
Petroleum, Beijing 102249, China
A novel submolten salt (SMS) method for depolymerizing natural aluminosilicates has been put
forward. Based on the SMS depolymerization method, we have successfully synthesized zeolite Y
from natural kaolinite and diatomite minerals without the use of any other aluminum- and siliconcontaining chemicals. We have also extended this methodology to the template-free synthesis of
hierarchical sodalite that excludes the use of any silicon- and aluminum-containing chemicals. Our
results sheds a light for the zeolite manufacture industry to switch its raw materials from chemicals to
natural aluminosilicates.
P-1.1-21
Synthesis of beta zeotypes by a method of microwave drying of gels
Farlán Taborda
Independent Consultant, on leave from Environmental Catalysis Research Group, Universidad de
Antioquia, SIU, Cra. 53 No. 61-30 Medellín, Colombia.
farlanta@gmail.com, efata020@udea.edu.co
In memory of Professor Consuelo Montes
Zeotypes with beta framework were synthetized by means of a novel method which uses mild
microwave drying of gels prepared in fluoride medium, followed by conventional thermal treatment
under autogenous pressure at 140 °C. Samples were characterized by PXRD and X-ray fluorescence.
PXRD patterns of calcined samples revealed that pure beta zeotypes were obtained. In addition, it was
observed that the first peak has a small spur at the low-angle side, which is usually attributed to
polymorph A enrichment. Therefore, the polymorphic A enrichment was ascertained by peak
deconvolution of PXRD patterns in the low-angle region. Calculations showed polymorphic
enrichments about 70%, which are greater than those obtained by conventional methods. Ti and Zr
loadings in the final solids are quite low if they are compared with other synthesis methods.
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P-1.1-22
Preparation and Crystal Structure of Ga42Tl9.3-Si121Al71O384 (Zeolite Y, FAU)
Containing Ga57+, Ga+, Ga2+, Ga3+, and Tl+
N.H. Heo,1,* J.J. Kim,1 C.W. Kim,1 J.Y. Kim,1 K. Seff2,*
1Dept. of Applied Chemistry, Kyungpook National University, Daegu, Korea nhheo@knu.ac.kr
2Dept. of Chemistry, University of Hawaii, 2545 The Mall, Honolulu, Hawaii, USA
The extraframework gallium cations Ga57+, Ga+, Ga2+, and Ga3+ have been introduced into zeolite Y.
Ga,Tl-Y ((Ga5)5.8Ga12.9Tl9.3|[Si121Al71O384]–FAU) was prepared by the reaction of Tl71-Y with Ga0
under anhydrous conditions at 623 K. Its structure was determined by single-crystal crystallography
with synchrotron X-radiation and was refined in the space group 3Fd m (a = 24.527(1) Å) with all
1126 unique data; (R1/wR2 = 0.074/0.2308). Ga0 replaced 87% of the Tl+ ions in the zeolite. Ga57+
ions occupy 73% of the sodalite cavities. The remaining Ga ions are 5.6 Ga+, 4.8 Ga2+ and 1.5 Ga3+
per unit cell. All Tl+ ions occupy a supercage site.
P-1.1-23
Design Synthesis of Efficient Catalysts from Layered Zeolite Precursors
Hao Xu, Jingang Jiang, Boting Yang, Jianggan Wang, Haihong Wu, Yueming Liu, Peng Wu
1Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal University, Shanghai, China, pwu@chem.ecnu.edu.cn
We will report in this presentation the structural modifications, catalytic and adsorption properties of
layered zeolites with the topologies of MWW, FER, NSI etc. MWW-type metallosilicates containing
tetrahedral Ti, Sn or Al have been fully or partially phase delaminated as well as interlayer expanded
by silylation technique, resulting in the catalysts with large porosity useful for processing bulky
molecules. Amine-assisted reversible structure conversion from 3D MWW to 2D lamellar precursor
is useful for post-incorporating catalytic active metal species into the MWW framework and enhances
the hydrophobicity and catalytic activity of Ti-MWW effectively. In addition, post-silylation of the
lamellar precursors with monomeric or dipodal silanes leads to large-pore zeolites which are
beneficial to the accessibility and diffusion for the bulky molecules.
P-1.1-24
Synthesis of a Fe-MFI zeolite with super-micropores by using potassium hexacyanoferrate(III)
as an iron source
Baoshan Li*, Junqing Xu, Chunying Han
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical
Technology, Beijing 100029, PR China, bsli@mail.buct.edu.cn
Abstract:Zeolite Fe-MFI possessing super-micropores has been synthesized by a direct
hydrothermal method using potassium hexacyanoferrate(III) as the iron source. X-ray diffraction and
scanning electron microscopy provided evidence that the as-synthesized material has a highly
crystalline MFI zeolite structure. Nitrogen sorption isotherms and the pore size distribution curve of
the sample showed the presence of super-micropores. Electron paramagnetic resonance results
indicated that the iron was present in the form of tetrahedrally coordinated Fe3+ ions incorporated in
the zeolite network. The stability of Fe-MFI was investigated by thermogravimetric analysis,
differential scanning calorimetry and H2 temperature-programmed reduction. The super-microporous
Fe-MFI exhibited good catalytic performance in the hydroxylation of phenol by H2O2.
1.1. Zeolites and zeotypes
142
P-1.1-25
Synthesis and modification of small-crystal titanium silicalite-1: The active species in titanium
silicalite-1
Yi Zuoa, Min Liua, Wancang Songa, Haiying Jianga, Luwei Honga, Xiangsheng Wanga, Xinwen
Guoa*, Yongsheng Chenb*, Pengyu Zhub, Cherno Jayec, Daniel Fischerc
aState Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of
Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China,
guoxw@dlut.edu.cn
bEMS Energy Institute, and Department of Energy & Mineral Engineering, Pennsylvania State
University, University Park, PA 16802, USA, yzc2@psu.edu
cNational Institute of Standards and Technology, Gaithersburg, MD 20899, USA
Small-crystal titanium silicalite-1 (TS-1) with a size of 600 nm × 400 nm × 250 nm was synthesized
in a TPABr-ethylamine hydrothermal system using the mother liquor of nano-sized TS-1 as seed. The
small-crystal TS-1 was modified with different bases. The modified catalysts were characterized with
XPS, Raman and XANES, and were evaluated in the propene epoxidation. The small-crystal TS-1
extrudates showed an excellent performance in a long term test of propene epoxidation. The
improvement of catalytic performance was due to the protection for framework Ti, recrystallization of
silica and generation of pentahedrally coordinated Ti.
P-1.1-26
Synthesis of zeolite from waste materials at low temperature
Claudia Belviso1, Francesco Cavalcante1, Antonio Lettino1, Simone Pascucci1, Stefano Pignatti1,
Saverio Fiore1
1Laboratory of Environmental and Medical Geology, IMAA–CNR, Tito Scalo (PZ), Italy,
claudia.belviso@imaa.cnr.it
Fly ash is a by-product of thermal power plants partly used in concrete and cement manufacturing but
more than half of it is disposed of in landfills. Red mud is a waste material formed during the
production of alumina when the bauxite ore is subject to caustic leaching. In this study, both waste
materials and mixtures of fly ash and red mud were used to synthesize zeolite by hydrothermal
activation. The data document that it is possible to form zeolite starting from both waste materials in
an economical way at low temperature. Moreover it is possible to drive the final product by mixing
fly ash and red mud taking into account their chemical starting composition.
P-1.1-27
Synthesis of MSE-type zeolite without using organic structure-directing agent
and its catalytic application
Y. Kubota1, K. Itabashi2, S. Shinoda1, R. Komatsu1, S. Inagaki1, T. Okubo2
1Dvision of Materials Science and Chemical Engineering, Yokohama National University, Yokohama,
Japan, kubota@ynu.ac.jp
2Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
Tokyo 113-8656, Japan
The synthesis of MCM-68 (MSE topology) without using organic structure-directing agent (OSDA)
was successful for the first time by utilizing the working hypothesis based on composite building
units. The as-synthesized OSDA-free MSE was not stable and significantly collapsed during the acidtreatment, while the framework was stabilized by steaming. Acid-treatment after steaming afforded a
high-silica MSE-type material that shows excellent catalytic performance in the cracking of nhexane.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.1-28
Influences of sodium salts on crystallization of large mordenite crystals
Koji Nishi*, Kenjiro Sadamori, Masahiro Kasukawa, Minako Mizobuchi, Kosei Makino, Natsumi
Kamiya and Yoshinobu Yokomori
Department of Applied Chemistry, National Defense Academy, Yokosuka 239-8686, Japan
*Corresponding author, e-mail knishi@nda.ac.jp
The influences of sodium salts on the synthesis of mordenite (MOR) single crystal were investigated.
Large single crystals of MOR were obtained using sadium chloride additives. The results definitely
show that the sodium ion plays two roles in crystallization of large mordenite. The introduced
sodium ions should play such a structure-directing role. They also make a dense aluminosilicate gel
yielding an increase the crystal growth rate.
P-1.1-29
Polymorphism in organic-free precursor mixtures
H. Awala1, R. Retoux2, J. Toufaily3, S. Mintova1,*
1Laboratoire Catalyse et Spectrochimie (LCS), ENSICAEN, Université de Caen, CNRS, 6 boulevard
du Maréchal Juin, 14050 Caen France; e-mail: hussein.awala@ensicaen.fr
2CRISMAT, ENSICAEN, Université de Caen ,14050 Caen France
3Laboratory of Materials, Catalysis, Environment and Analytical Methods (MCEMA), Lebanese
University, Hadath, Beirut, Lebanon
One of the critical challenges in organic-free synthesis of zeolites is the formation of side products or
polymorphs. To address this challenge, we investigated the influence of three parameters on zeolite
crystallization (temperature, time and chemical composition) in well-defined organic-free precursor
mixtures to tailor zeolite structure, size and crystal habit. The phase transformation process in
template-free system and the crystallization of eight zeolites with EMT, FAU, BPH, GIS, EDI, SOD,
CAN and JBW- type structures are studied. By controlling the type and the ratio between the alkali
cations in the initial mixtures and changing the synthesis temperature, the transformation from less
stable zeolites (BPH and EMT) to more dense structures (JBW and CAN) was observed.
P-1.1-30
Nucleation events in alumosilicate hydrogels of different density
Ana Palčić1, Valentin Valtchev2, Josip Bronić1
1Ruđer Bošković Institute, Zagreb, Croatia, ana.palcic@irb.hr
2Laboratoire Catalyse et Spectrochimie, CNRS-ENSICAEN, Caen, France
Five alumosilicate hydrogels, having chemical composition adjusted for the synthesis of zeolite A,
were prepared. Different density (viscosity) of the gels was obtained by changing the ratio SiO2/H2O,
while the ratios Na2O/H2O and SiO2/Al2O3 remained constant. Freshly precipitated hydrogels were
hydrothermally treated at 80 °C. The course of the reaction was monitored by XRD, chemical
analysis, microscopy, and by thermogravimetry. Crystal size distribution curves of the end products
were measured, while according curves of nuclei distribution within gel matrix and specific number
of crystals were calculated. The obtained data about zeolite A nuclei formation, were commented
from the viewpoint of the autocatalytic nucleation theory.
1.1. Zeolites and zeotypes
144
P-1.1-31
On the true symmetry of pure silica ITQ-7
J.-L. Paillaud1, B. Marler2, L. Tzanis1, J. Patarin1, H. Gies2
1 Institut de Science des Matériaux de Mulhouse (IS2M), Equipe Matériaux à Porosité Contrôlée
(MPC), LRC CNRS 7228 – UHA, ENSCMu, 3A rue Alfred Werner, F-68093 Mulhouse Cedex,
France, jean-louis.paillaud@uha.fr
2 Institute for Geology, Mineralogy and Geophysics, Ruhr-University Bochum, 44780 Bochum,
Germany
Pure silica ITQ-7 (topology ISV) possesses a 3D 12-MRs pore system; it is synthesized in fluoride
media with two different structure-directing agents. The ISV symmetry is tetragonal and is described
in space group P42/mmc. The structures of calcined and as-made ITQ-7 zeolite were also solved in
P42/mmc space group. In both cases this space group was not supported by solid state 29Si MAS NMR
spectroscopy which allows the determination of a minimum number of non equivalent
crystallographic framework T sites. Here, from 29Si solid state NMR spectroscopy and Rietveld
analysis, the necessity to lower the symmetry from P42/mmc to P42 is confirmed.
P-1.1-32
In-situ Calorimetric Study on Y Zeolite Synthesis
Jihong Zhou, Yibing Luo, Xuhong Mu, Xingtian Shu, Minjiang Gao
State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of
Petroleum Processing, SINOPEC, Beijing 100083, zhoujh.ripp@sinopec.com
Synthesis of Y type Zeolite from mixtures of silicate and aluminate solutions of (1.6Na2O-Al2O37SiO2-90H2O, kaolin solid-liq) and ( 2.8Na2O-Al2O3- 9SiO2-210H2O, gel-sol) was studied using an
in-situ calorimetric method (Calvet C-80) at a constant temperature T = 367.15K (94℃). Obviously
exothermal peak was obtained and the calculated enthalpy change was -1786.2 kJ/mol and -513.71
kJ/mol respectively. The effect of raw material feed ratio (by changing H2O/ Al2O3 ratio) on enthalpy
change was investigated. The product crystallinity as a function of time was also investigated by XRD
for both two synthesis systems, which have a good agreement with the in-situ calorimeter
measurements.
P-1.1-33
Morphology Control of Silicalite-1 by Adding NH4F
Xiaoqiang Yao1, Xiangyu Xu1, Zhi Lv1, Jiaqing Song1,*, Zhaofei Li2, Qian Wang2, Lijun Yan2, and
Mingyuan He3
1State Key Lab of Chemical Resource Engineering, Beijing University of Chemical Technology,
Beijing, 100029, P. R. China
2Petrochemical Research Institute of Petrochina, Beijing, 100195, P. R. China
3Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal
University, Shanghai, 200062, P. R. China.
*Corresponding author, e-mail songjq@126.com, fax +86-10-6442-3325
Silicalite-1 with different morphologies were synthesized in the SiO2-TPAOH-H2O-NH4F system.
The morphologies and their channel lengths along the b axis were successfully controlled by
modifying the NH4F amount and the resulting pH values. The sample morphologies changed from
ellipse-like to the plate-like ones and the particle length along the b axis decreased as the NH4F/Si
ratio increased. This facile control approach might shed light on their applications.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.1-34
A perspective in the industrial applications of beta by OSDA-free synthesis: Improved
hydrothermal stability, despite of its high aluminum content
S. P. Elangovan1,*, K. Itabashi2, T. Hieda1, M. Yamamoto1, K. Momma3, M. Ogura3, Y.Yamazaki1
and T. Okubo2.
1Nippon Chemical Industrial Co. Ltd, 9-11-1 Kameido, Koto-ku, Tokyo 136-8515, Japan;
elango@nippon-chem.co.jp
2Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku,
Tokyo 113-8656, Japan.
3Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505,
Japan.
Zeolite beta synthesized in the absence of organic-structure directing agent (OSDA) has led wideopening to evaluate their properties, especially, its hydrothermal stability for possible use as
hydrocarbon trap in the automobile applications. It was reported that conventional beta loses its
hydrocarbon trap performances marginally after hydrothermal treatment (aging). The present study
brings out the hydrothermal stability of beta by OSDA-free synthesis including the performance of
Fe-exchanged beta compared to conventional beta for use as hydrocarbon trap. Zeolite beta
synthesized in the absence of OSDA, being Al-rich material, offers advantage of exchanging more
metals and it is further possible to fine-tune the metal contents (transition and alkali) in addition to the
acid site, for the desired applications.
P-1.1-35
Controllable intergrowth of EU-1/ZSM-48 zeolite using EU-1 seed
Yafei Zhang, Yanjun Gong*, Xiaoling Liu, Tao Dou
The Key Laboratory of Catalysis of CNPC, China University of Petroleum, Beijing, China.
gongyj@cup.edu.cn; zhangyafei186189@163.com
Intergrowth zeolites, especially micro/microporous zeolites, have attracted great attentions due to the
synergistic performance in catalytic reaction. A series of EU-1/ZSM-48 intergrowth zeolites with
various proportions were synthesized by a seeded method and the samples were characterized by Xray diffraction (XRD), scanning electron microscopy (SEM) and NH3-TPD. The EU-1 zeolite, which
served as seed, could partial transfer into ZSM-48 and induce the formation of both EU-1 and ZSM48 zeolites simultaneously in our synthetic system. Each crystal phase of EU-1/ZSM-48 intergrowth
zeolites could be adjusted via changing seed content in the precursor gel and the intergrowth zeolites
shows different acid property compared to EU-1, ZSM-48 and the mixture samples.
P-1.1-36
Effect of seeds on crystallization on zeolite FER by method VPT modifying the OSDAs and Al
source
L.M.O. Ribeiro1, P.P. Modesto Neto1, T.R.D. Mendonça1, B.J.B. Silva1, T.P.M. Costa1, L.V. Sousa
Junior1, A.O.S. Silva1, M.M. Urbina1.
1Dep. of Chemical Engineer, Federal University of Alagoas, Maceio, Brazil,
liviaribeiro02@gmail.com
The present study addressed the evaluation of the formation and crystal growth of the ferrierite
through the use of seeds by the method of vapor phase transport for fixed conditions of temperature,
ratio of Si/Al and crystallization time. With the addition of seed bulk of the material synthesized
exhibited high percentage crystalline, with values greater than 90% compared with the commercial
standard. The results indicated that there is an outstanding influence of the source of aluminum about
the crystallization of the ferrierite in the pyrrolidine, however when used the ethylenediamine this fact
is almost imperceptible.
1.1. Zeolites and zeotypes
146
P-1.1-37
Synthesis of ZSM-22/-23 intergrowth zeolite and the hydroisomerization performance of longchain paraffins
Bingchun Wang, Huaijun Ma, Zhijian Tian, Renshun Xu, Peng Li, Wei Qu, Lin Wang, Jianqiang
Han, Zhusheng Xu, Liwu Lin
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, P.R.China, wangbc@dicp.ac.cn
Zeolites are widely used in modern chemical industry, especially petrochemical industry. The
intergrowth zeolite is new topology structure zeolite different from zeolite bound zeolite or composite
zeolite, which has uniform structure in framework. Due to different pore and surface properties, it
possesses unique performance different from the mother materials. In present work, the intergrowth
ZSM-22/-23 is synthesized with only dimethylamine (DMA) as single structure-direction agent, and
evaluated in the hydroisomerization of n-docecane for the catalytic performance. The as-synthesized
intergrowth zeolite displayed excellent hydroisomerization performance of long-chain paraffins, and
was successfully applied in the lubricant oil manufacture.
P-1.1-38
Processing line for the synthesis of zeolites from fly ash
W. Franus1, M. Wdowin2, R. Panek1
1Department of Geotechnics, Civil Engineering and Architecture Faculty, Lublin University of
Technology, Nadbystrzycka 40, 20-618 Lublin, Poland, w.franus@pollub.pl
2Mineral and Energy Economy Research Institute of The Polish Academy of Sciences, Wybickiego 7,
31-261 Krakow, Poland
The paper concerns a prototype line for zeolites synthesis on ¼ technical scale, which consists of 4
processes blocks: block of the reactor loading, the reaction block, the reaction products separation
block, the final material processing block. On the basis of described line a series of chemical reactions
were conducted. The final product was dependent on the following process parameters: the ash type,
its amount in relation to NaOH aqua solution, NaOH concentration, process temperature and reaction
duration. As a result of the reaction, the following zeolitic materials were observed: Na-P1, Linde-A,
Na-X.
P-1.1-39
The role of lithium cations in a novel synthesis of a low silica KFI type aluminosilicate
L. Van Tendeloo, K. Lauwers, Y. Lorgouilloux, J.A. Martens, C.E.A. Kirschhock
Center for Surface Chemistry and Catalysis, Dept. M2S, KULeuven, Leuven, Belgium.,
leen.vantendeloo@biw.kuleuven.be
A new method to synthesize a low silica KFI type zeolite was realized. The synthesis procedure
made use of both inorganic cations (lithium, sodium and potassium) and organic cations
(tetramethylammonium) as structure directing agents. To our knowledge, this is the first time that a
KFI type zeolite with a Si/Al ratio as low as 1.67 is obtained and fully characterized by techniques
including XRD, SEM, TEM, 27Al and 29Si MAS NMR spectroscopy and chemical analyses. The very
high Al content in the KFI framework induced a symmetry reduction of the Ca-KFI structure from
cubic to monoclinic, that could be explained by an ordering of Al atoms. It can be assumed that the
presence of lithium in the medium enables the formation of zeolites with unusual high Al content.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.1-40
New Zeolitic Phases Obtained using 1,8-diazabiciclo[5.4.0]undec-7-eno Derivatives as Structure
Directing Agents
E. M. Diaz-Canales and M. J. Diaz-Cabañas
Instituto de Tecnología Química (ITQ, UPV – CSIC), Avda. Los Naranjos S/N, 46022, Valencia,
Spain. mdiazca@itq.upv.es
A family of 1,8-diazabiciclo[5.4.0]undec-7-eno derivatives (methyl, ethyl and benzyl) have been used
as structure directing agents in the synthesis of zeolites using High-Throughput synthesis and
analytical techniques. The starting experimental factorial design included 72 experiments in which
Si/Ge, H2O/Ge, TIII/(Si+Ge) and F-/(Si+Ge) were the synthesis variables, following the general
formula:
x GeO2 : (1-x) SiO2 : y Al2O3 (B2O3) : z SDA : v NH4F : w H2O
Two new zeolitic materials have been synthesized using a family of SDAs increasing in size. The
structure of Phase 1 and Phase 2 has not yet determined, although both of then occluded a
considerable amount of organic matter inside, suggesting open structures.
P-1.1-41
In-situ generation of silver oxide nuclei for the
size control of zeolite crystals
F. Hamidi1,2, F. Boukli-Hacène1,2, T. Cacciaguerra3, A. Bengueddach2 and F. Di Renzo3.
1Département de Chimie, Faculté des Sciences, USTO-MB, B.P. 1505 El-Menaouer, 31000 Oran,
Algeria. fatihamidi@yahoo.fr
2Laboratoire de Chimie des Matériaux, Université d’Oran, B.P. 1524 El-Menaouer, 31000 Oran,
Algeria.
3Institut Charles Gerhardt, UMR 5253 CNRS-UM2-ENSCM-UM1, Matériaux Avancés pour la
Catalyse et la Santé, ENSCM, 8 rue Ecole Normale, 34296 Montpellier Cedex 5, France, tel. +33
607508148, direnzo@enscm.fr
In-situ generation of silver oxide nuclei in the synthesis batches appear as a valuable method to
decrease the crystal size of zeolites by heterogeneous nucleation. The procedurte does not affect
phase selectivity and yield of the crystallization process and applies to a large panel of zeolite types,
including zeolites A, LSX, X, Y, L, and beta.
P-1.1-42
Synthesis of AlPO4-5 molecular sieve in the absence of water
H. J. Ma, Z. J. Tian, B. C. Wang, W. Qu, R. S. Xu, P. Li, D. E. Wang, Z. D. Pan
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian, China, mahj@dicp.ac.cn
Ionothermal synthesis explored new fields of molecular sieve synthesis. We introduced microwave
heating into ionothermal synthesis. However, only a mixture of AlPO4-5 and AlPO4-11 was obtained
in [Bmim]Br. In the present work, We prepared pure AlPO4-5 by adding ammonia aqueous solution,
indicating that low H+ content of the synthesis system favors the preparation of pure phase of AlPO45. Furthermore, AlPO4-5 was also prepared successfully in the absence of any dissociative water by
using NH4H2PO4 and NH4F. NH4F decomposed to NH3 and HF. The later reacted with AlOOH, and
formed fluoroaluminium complexing species, which were well soluble in the ionic liquids and acted
as reaction nutrients. Some role of the trace amount of water, which might been produced in the
crystallization proess and/or been adsorped into the mixture from air, can not be purely precluded.
1.1. Zeolites and zeotypes
148
P-1.1-43
The Zeolite adsorbent NewSieve ANT-4A with nano-structured protective layer with a high
mechanical strength, adsorption capacity and resistance to condensed moisture
Sergey Fastov1, Ilya Fastov2
1CEO «MT&NM» CJSC, Moscow, Russia, zmtpp@mail.ru
2CEO «NT&I» СJSC, Moscow, Russia
CJSC "MT&NM" developed and successfully producing on the basis of zeolite LTA a dehumidifier
with nano-structured protective layer NewSieve ANT-4A, surpassing domestic dehumidifiers on a
number of parameters. Production of adsorbents is carried out on unique patented technology, which
includes a complete synthesis of zeolite-A and operations of the nanostructure activation.
Technology provides zeolite with developed transport microstructure, high mechanical strength and
adsorption capacity for water vapors. Thanks to the protective nanostructured layer adsorbent
resistant to condensed moisture and is not destroyed by repeated contact with a liquid water.
NewSieve ANT-4A can be used to dry the air in the complex purification units, for the safe
conduction of cryogenic ASU processes, for drying of gases produced in the process of air separation.
P-1.1-44
Synthesis of zeolite X-carbon from coal bottom ash
Nurul Widiastuti, Didik Prasetyoko, Hamzah Fansuri, Mila Zhely Nurul Hidayah
Dep. of Chemistry, Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia,
nurul_widiastuti@chem.its.ac.id
This paper aims to synthesis zeolite X-carbon (composite materials consisting of activated carbon and
zeolites X) from coal bottom ash. The main components (SiO2 and Al2O3) with contains unburned
carbon of ca. 11,58 mass% as a source material from coal bottom ash were activated by NaOH fusion
treatment at 750 °C under N2 atmosphere, and subsequently converted into zeolites X-carbon by
hydrothermal treatment. In order to determine the optimum conversion condition, the hydrothermal
temperature was examined at 90°C with interval time about 8 until 22 hours. The prepared materials
were characterized by XRD and SEM to evaluate its crystallinity and morphology of the zeolitecarbon. The surface area and pore characteristic or textural properties of NaX zeolite-carbon were
investigated by using nitrogen gas sorption analyzer. In this report, zeolite X-carbon with good
crystallinity were successfully prepared at 90°C for 15 hours.
P-1.1-45
Rapid Synthesis of Sn-Beta for the Isomerization of Cellulosic Sugars
C.C. Chang1,2, W. Fan1,2
1Dep. of Chemical Engineering, University of Massachusetts Amherst, Amherst, The United States of
America, wfan@ecs.umass.edu
2Catalysis Center for Energy Innovation, U.S. Department of Energy
Sn-Beta is a highly active Lewis acid catalyst for isomerization of cellulosic sugars. It was found that
the morphology and dispersion status of zeolite seeds in the synthesis gel can substantially affect the
crystal growth kinetics of Sn-Beta. By uniformly distributing well-crystalline zeolite beta seeds in the
synthesis gel, high-quality Sn-Beta can be synthesized in only 2 days with a nearly complete
conversion (> 90 %) of the provided silica source. The use of hydrofluoric acid was also avoided in
the synthesis approach. The Sn-Beta catalyst synthesized by this approach is highly active for the
isomerization of triose (C3), pentose (C5) and hexose (C6) sugars.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.1-46
Synthesis of FAU- and EMT-type zeolites using novel templates designed by molecular
modelling
T.J. Daou1, J. Dhainaut1,2, A. Chappaz1,3, N. Bats2, B. Harbuzaru2, G. Lapisardi2, H. Chaumeil3, A.
Defoin3, L. Rouleau2, J. Patarin1
1 Univ de Haute Alsace (UHA), CNRS, Équipe Matériaux à Porosité Contrôlée (MPC), Institut de
Science des Matériaux de Mulhouse (IS2M) LRC 7228, 68093 Mulhouse Cedex, France,
jean.daou@uha.fr
2 IFP Energies nouvelles, BP3, 69360 Solaize, France
3 Univ de Haute Alsace (UHA), Laboratoire de Chimie Organique et Bioorganique (COB), EA 4566,
ENSCMu, 68093Mulhouse Cedex, France
Molecular modelling is a growing science which allows to calculate short range forces between
zeolite frameworks and organic compounds. By using a steric approach, it is possible to design
templates matching closely with an inorganic framework. Herein, the design, synthesis and successful
application of several mono and di(azacrown ether) templates to direct the formation of EMC-1 and
EMC-2 zeolites is reported. Following a high throughput experiment design, the synthesis gel
composition was optimized to obtain crystallized materials.
P-1.1-47
Interzeolite conversion of MCM-49 zeolite into ZSM-35 zeolite
S.J. Xie1, S.L. Liu1, K.F. Liu1, 2, N.N. Gao1, 2, X.J. Li1, Y. Gao1, L.Y. Xu1
1 State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, Dalian, PR China, sjxie@dicp.ac.cn
2 University of Chinese Academy of Sciences, Beijing, PR China
The interzeolite conversion of MCM-49 zeolite into ZSM-35 zeolite in the systems of
“Cyclohexylamine (CHA)-Hexamethyleneimine (HMI)-Na2O-H2O” was investigated in detail. Both
CHA and HMI, whether they are added in the initial material or occluded in the as-made MCM-49,
play important roles in directing the interzeolite conversion of MCM-49 towards ZSM-35, and the
conversion speed is much faster in system containing CHA than in that containing HMI. Even if in
the Na2O-H2O system without any organic amine, the interzeolite conversion of MCM-49 still can
take place, but the product composition becomes complicated. Also, in the Na2O-H2O system,
alkalinity has been proved a crucial factor influencing the conversion trend of MCM-49. ZSM-5 and
mordenite will appear in the product besides ZSM-35 with the increase of the alkalinity.
P-1.1-48
Synthesis of SAPO-34 molecular sieve using piperazine as a template
Huiru Zhao, Yue Ding, Niu Li, * Naijia Guan, Shouhe Xiang
Institute of New Catalytic Material Science, College of Chemistry, Nankai University, Tianjin , China,
liniu@nankai.edu.cn
In the new reproducible route, piperazine was used as the template to synthesis microporous
silicoaluminophosohates, it was found that SAPO-34 could be prepared with high crystallinity, and
large crystal. The crucial factors of the synthesis of SAPO-34 has been formulated as follows, the
concentration of piperazine, temperature. Molar composition of the reaction mixture was 1.0Al2O3:
2H3PO4: 1.0SiO2: 1.8piperazine: 100H2O. Certainly SAPO-34 with diff erent concentration of the
silicon can also be prepared with different formula. The presence of two piperazine molecules per unit
cell was indentified by single-crystal refinement. Then there are four positive charges in each
chabazite cage, they directly correspond to four bronsted acid sites, which make SAPO-34 more
active than ever before.
1.1. Zeolites and zeotypes
150
P-1.1-49
Synthesis of porous aluminophosphates using self-assembling 1,3-diphenylguanidine as
structure-directing agent
Teresa Álvaro-Muñoz, Joaquín Pérez-Pariente and Luis Gómez Hortigüela*
Instituto de Catálisis y Petroleoquímica-CSIC. c/ Marie Curie 2, 28049 Madrid, Spain. Contact
email: lhortiguela@icp.csic.es
In an attempt to produce new very-large pore microporous aluminophosphates, 1,3-diphenylguanidine
(DPG) was rationally selected as structure-directing agent because of its potential for self-aggregation
due to the presence of distinguishable polar and apolar groups, aromatic rings that self-assemble
through π-π type interactions and high conformational flexibility. This strategy has enabled the
crystallization of three different unknown porous aluminophosphates as a function of the organic
content in the synthesis gel. A full characterization of these phases as well as a computational study of
the aggregation behavior of DPG will be presented in the conference.
P-1.1-50
Effect of the alumosilicate gels pH on zeolite phase composition for the co-crystallization
of BEA/MOR zeolites in Na2O-ТЕАBr-Al2O3-SiO2-H2O system
Anastasia F. Gizetdinova1, Svetlana A. Skornikova2, Sergey S. Kolesnikov2,
Marina I. Tselyutina1, Irina D. Reznichenko1
1JSC «Angarsk Catalysts and Organic Synthesis Plant», 665830, Angarsk, Irkutsk region,
e-mail: GizetdinovaAF@anhk.rosneft.ru
2Irkutsk State Technical University, 664074, Irkutsk, Lermontov st., 83.
e-mail: zeolite@mail.ru
Pure phases of BEA and MOR zeolites are widely used as acid catalysts in petrochemical industry.
Even more, depending on synthesis conditions these zeolites are able to be formed from same initial
gels with TEABr or TEAOH structure directing agents. It is not industrial catalysts based on the cocrystalline BEA/MOR zeolites because of it is difficult to regulate the BEA/MOR phase ratio in these
materials. However, by virtue of their complex properties, such as acidity and porous structure, these
zeolites containing the co-crystalline phases of BEA/MOR are attractive in the processes using the
catalysts, which based on the pure phases BEA or MOR zeolites.
Zeolites BEA, MOR and BEA/MOR co-crystalline zeolites were synthesized from xNa2O · yТЕАBr
∙ Al2O3 · zSiO2 ∙ nH2O alumosilicate gels, where x=3-8, y=7-10, z=10-25, n=500-600. Resulting
zeolites were studied based on the SEM, XRD and chemical analysis. Porous structure of these
zeolites was investigated by nitrogen low-temperature adsorption.
Based on the results was illustrated that regulation of the phase composition is possible due to
variations of hydrogen-ions concentration of the initial alumosilicate gels.
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P-1.1-51
Influence of preparation procedure on state and distribution of Co species
in modified BEA zeolite
R. Baran1, 2, S. Casale2, T. Grzybek1, S. Dzwigaj2
1AGH University of Science and Technology, Faculty of Energy and Fuels, Al. A. Mickiewicza 30, 30059 Krakow, Poland, rafalbaran@onet.eu
2Laboratoire de Reactivite de Surface UMR 7197, CNRS, UPMC, Site d’Ivry – Le Raphaël, 3, rue
Galilée, Ivry-sur-Seine, France
A CoSiBEA zeolite is prepared by a two-step postsynthesis method that consists of first creating
vacant T-sites with associated silanol groups by dealumination of TEABEA zeolite with nitric acid
and then impregnating the resulting SiBEA zeolite with an aqueous solution of Co(NO3)2. The
incorporation of Co into lattice sites of SiBEA is evidenced by XRD. Presence of pseudo-tetrahedral
Co(II) species in SiBEA matrix is evidenced by diffuse reflectance UV-vis spectroscopy The
reduction of CoxSiBEA zeolite leads to the formation of well dispersed small Co(0) particles
measured by TEM.
P-1.1-52
Mild desilication synthesis of hollow zeolite microtubes
Z.C. Liu1, Y.D. Wang1, H.X. Gao
1 Shanghai Research Institute of Petrochemical Technology, Shanghai, P. R. China,
lotuslzc@yahoo.com & wangyd.sshy@sinopec.com
Hollow microcapsules are of great interest because of their diverse applications for microreactors,
catalysis, drug delivery or controlled release, optical or electrochemical architectures, etc. But there
are few reports on the zeolite microcapsules.
Herein, firstly, a new starch-assisted hydrothermal method were used to synthesize 1D chain-like
microarchitecture, which consist of zeolite (ZSM-5) crystal units bonded together face to face. Then
the zeolite chains were submitted to a mild desilication process with Na2CO3 solution, which resulted
in the formation of zeolite microtubes with thin intact shell and large hollow core. The physical
characterizations reveal that the intrinsic crystalline properties of alkaline treated zeolite are well
preserved. The synthetic method involves in the selective desilication process preferentially from the
centre of zeolite crystals. It is expected that this kind of zeolite microtubes will not only be used on
some catalysis reaction relative to their nano-sized walls, but also on microreactors or drug carriers
relative to their large hollow voids.
P-1.1-53
Thermal stability of the pillaring structure in silylated MCM-22 zeolite
N. Gao1, 2, S. Xie1, S. Liu1, X. Li1, L. Xu1
1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, Dalian 116023, PR China, gaoningning@dicp.ac.cn
2University of Chinese Academy of Sciences, Beijing 100049, PR China
In order to investigate the thermal stability of the interlayer pillaring structure, silylated MCM-22 was
thermally treated at 600, 650, 700 and 750 oC, respectively, followed by the characterizations of Xray diffraction and N2 adsorption. The results showed that most of the interlayer pillaring structure
could withstand the thermal treatment below 650 oC. With further increase of the thermal treatment
temperature, the interlayer pillaring structure was destroyed gradually and disappeared at 750 oC,
leading to gradual decrease of micropore volume/area and BET surface area.
1.1. Zeolites and zeotypes
152
P-1.1-54
Synthesis of novel layered silicates HUS-2, HUS-3 and HUS-4: their ability of the precursor of
zeolite and incorporation of aluminum
Nao Tsunoji1, Takuji Ikeda2, Yusuke Ide1, Masahiro Sadakane1, and Tsuneji Sano1,*
1 Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, HigashiHiroshima 739-8527, Japan
2 Research Center for Compact Chemical Systems, National Institute of Advanced Industrial Science
and Technology, AIST Tohoku, Sendai, Miyagi 983-8551, Japan
*Corresponding author, e-mail tsano@hiroshima-u.ac.jp, fax +81-82-424-5494
The novel layered silicate of HUS-2, HUS-3 and HUS-4 was obtained from a SiO2-choline
hydroxide-NaOH-H2O system. Structural analyses by powder X-ray diffractometry and solid-state
magic-angle-spinning (MAS) NMR spectroscopy revealed that HUS-2 had a layered structure, which
was composed of four-, five-, and six-membered rings. The framework topology was partially similar
to that of a HEU-type zeolite including bre (10T)-type composite building units. In order to clarify
the potential of obtained layered silicates as a zeolite precursor, transforming HUS-2, 3, and 4 into
zeolites by calcination was examined. It was found that HUS-3 and HUS-4 were converted into a
CDO-type zeolite by calcination. In addition it was demonstrated incorporation of aluminum on HUS2. From 27Al MAS NMR and SEM/EDX analysis, Aluminum incorporated on HUS-2 was in
tetrahedral coordination and dispersed throughout the interior of silicate particle.
P-1.1-55
Multistep Cluster Synthesis: A Novel Zeolite Modification Method
A.B. Ponomaryov1, V.E.Vakhmistrov1, M.V.Shostakovsky1, A.P.Kosolapova1, V.N.Kalinin1,
E.S.Mortikov2
1Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia, abponomg@gmail.com
2 Zelinskii Institute of Organic Chemistry RAS, Moscow, Russia
A general approach has been proposed for incorporating high concentrations of modifier metals into
channels and pores of zeolites. The process referred to as multistep cluster synthesis (MCS) involves
a sequence of chemical reactions between a reagent located in the pores of a zeolite and external
reagents. Various combinations of up to 4 elements were introduced by successive MCS
modification. Most of elements often used in catalysis was introduced as cation or as anion. Benefits
of materials obtained were shown in the reactions of aromatization of gasoline fractions,
dehydrogenation of saturated hydrocarbons and hydroisomerization of normal hydrocarbons.
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P-1.1-56
Alkylation of toluene with methanol over phosphorous and silica modified IM-5 zeolite
Junwen Chen, Chao Zhang, Yongrui Wang, Xuhong Mu1
Research Institute of Petroleum Processing, SINOPEC, Beijing, P. R. CHINA,
muxuhong.ripp@sinopec.com
IM-5 is a kind of zeolite with new structure. It has two-dimensional pore system consisting of 10-ring
channels. Researchers have studied its catalytic performances in catalytic cracking, isomerization and
selective catalytic reduction of NO. This paper investigated the catalytic properties of H-IM-5 and
P/Si modified IM-5 samples in the reaction of toluene alkylation with methanol. Phosphorus
modification decreases the surface area and pore volume of micropores and covers strong acid sites.
Silica deposition doesn’t influences micropores but reduces external surface acid sites. Phosphorus
modification together with silica deposition modifies both internal and external surface acid sites.
Therefore, p-xylene selectivity is increased to 55% and the selectivity of xylene to 95% when toluene
conversion is about 10%.
P-1.1-57
Highly Accessible, Stable and Active Sn Catalysis in Partially Dealuminated Beta Zeolites
J. Dijkmans, D. Gabriëls, F. De Clippel, M. Dusselier, P. Van Elderen, B.F.Sels
Center for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Kasteelpark Arenberg
23, 3001 Heverlee, Belgium, Jan.Dijkmans@biw.kuleuven.be
Sn-beta zeolite is a powerful catalyst Lewis acid catalyst. Even in water this catalyst shows great
activity, as was recently shown in carbohydrate-related conversions. But the synthesis of this catalyst
is not straightforward, long hydrothermal synthesis times and the corrosive hydrogen fluoride are
needed. Here we present a simple way to synthesize a Sn-containing zeolite by grafting of SnCl4 onto
partially dealuminated beta zeolites. The presence of aluminium results in Brønsted acitiy, the present
tin yield Lewis acidity. The catalytic activity of the catalyst was tested in different reactions, and
compared to the traditional synthesized Snβ. Catalysts synthesized by the grafting procedure show
very high activities for all the tested reactions, with turnover frequencies per Sn up to 10 times higher
than the original Snβ.
P-1.1-58
Bead-Milling and Post-Milling Recrystallization: An Organic Template-Free Methodology
for the Production of Nano-Zeolite X
Toru Wakihara, Koki Sato, Kaku Sato, Junichi Tatami, Katsutoshi Komeya, Takeshi Meguro
Graduate School of Environment and Information Sciences, Yokohama National University, Japan,
wakihara@ynu.ac.jp
In general, the fabrication of nano zeolites has been achieved by a bottom-up approach, which
involves controlling zeolite nucleation and crystal growth during hydrothermal synthesis. These
efforts have yielded the synthesis of many types of nano zeolites, including zeolite X and Y. The use
of organic compounds has resulted in many advances in synthesizing nano-zeolites but suffers from a
number of drawbacks, such as high production cost and low crystalline yield. Therefore, a new
method of synthesizing nano-zeolite without organic templates is strongly desired. In the present
study, a top-down approach has been applied to the preparation of nano zeolite X by the combination
of bead milling and post-milling recrystallization, giving nano zeolite X approximately 60 nm in size
with high crystallinity for the first time. The characteristic point of the present method is that
templating organic compounds are not required to control zeolite nucleation and crystal growth.
Furthermore, nanosized zeolite can be obtained almost without loss of material.
1.1. Zeolites and zeotypes
154
P-1.1-59
Depolymerization and Reorganization of Faujasite Y
P. Pérez-Romo, H. Armendáriz-Herrera, J. S. Valente, M.L. Guzmán-Castillo, F. Hérnández-Beltrán
and J. Fripiat.
Mexican Petroleum Institute, México D.F., Mexico, pperezr@imp.mx
The networks of zeolites and mesoporous high-surface area silicates undergo a deep depolymerization
process in glycerol. With 1h, X-ray diffraction analysis amorphous gels are obtained. Nevertheless,
depending on temperature some local ordering subsists. The residual organization could be
investigated indirectly by the recrystallization of this gel in the presence of structure-directing agents.
The final calcined solid exhibited high surface area and large pore volume in the mesoporous
domaine. Furthermore, this procedure reduces the sodium content in the final material.
P-1.1-60
Synthesis, modification, and characterization of zeolite A and some cation-exchanged forms
L.Wang1, I. Spiess1, H. Lührs1, W.H. Baur2, R.X. Fischer1
1 Fachbereich Geowissenschaften, Universität Bremen, Germany, li@uni-bremen.de
2 Western Springs, IL 60558, USA
Zeolite Na-A (idealized Na12Al12Si12O48 ˑ 27H2O) is one of the most important zeolites due to its
outstanding ion-exchange properties. Powder samples and single crystals of hydrated and dehydrated
K, Ca, Sr, Ba, and Pb exchanged zeolites as well as solid solution series of partially and fully
ammonium exchanged zeolite A were investigated. The samples were studied by means of singlecrystal and powder X-ray diffraction, thermal analyses, scanning electron microscopy, energy
dispersive X-ray spectroscopy, X-ray fluorescence analyses, IR and MAS NMR spectroscopy. The
investigations covered the dehydration behavior, the description and comparison of the crystal
structure with Na-A and the stability range for the NH4 exchanged form. In addition correlations
between chemical composition, crystal sizes, crystal forms, and lattice parameter a are presented.
P-1.1-61
Effect of ion exchange preparation variables on the reduction
of Co metalloxo clusters in zeolites.
O.A. Kirichenko, G.I. Kapustin
N.D. Zelinskiy Institute of Organic Chemistry RAS, Moscow, Russia, okiriche@ioc.ac.ru
Co-ZSM-5 is active catalyst for the SCR of NOx with CH4 or C3H8, and for ammoxidation of alkanes,
the catalytic properties depending on the redox behavior. In the present work, Co oxoclusters of a
different size and redox properties were prepared on ZSM-5 and β- zeolites. The samples were
characterized with ICP, XRD, UV-vis, TPR. Ion exchange for H-, NH4-ZSM-5 in ≤ 2.5 mM CoAc2
solution at pH=5.5 resulted in isolated Co ions reducible only at ≥900oC. The Co4Oy species were
prepared using step-by-step growth of “-Co-C2O4-Co-“ clusters, and exhibited a TPR peak with
maximum at 830oC. Introduction of NH3·H2O into CoAc2 solution before and during IE increased the
amount of Co introduced and Con+ reducibility, and shifted the TPR maximum to 730-760oC. The
sharp peaks with maximum at 260 – 380oC, which coincide with that of the Co3O4 particles of a
different size ≥7 nm, were observed if conditions for oversaturation with respect to Co(OH)2 were
realized.
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P-1.1-62
Framework Sites Preferred by Aluminum in Zeolite ZSM-5.
Structure of a Fully Dehydrated, Fully Cs+-exchanged ZSM-5 Crystal (MFI, Si/Al = 24)
Cheol Woong Kim1, Hyeon Seung Lim1, Nam Ho Heo*,1, and Karl Seff*,2
1Laboratory of Structural Chemistry, Department of Applied Chemistry, Kyungpook National
University, Daegu, 702-701 Korea, kimcw@knu.ac.kr
2Department of Chemistry, University of Hawaii, 2545 The Mall, Honolulu, Hawaii 96822-2275,
USA.
The preference of Al atoms among the T sites of the ZSM-5 framework has been identified by Cs+
occupancies and Cs–O bond lengths in a single crystal structure of Cs-ZSM-5 (Cs3.8Al3.8Si92.2O192,
Si/Al = 24) determined using synchrotron X-radiation. A total of 3.5(2) Cs+ ions were found per unit
cell scattered among 11 crystallographically distinct positions. Using all Cs–O bonds shorter than
3.35 Å, the preferred order for Al among the T sites appears to be T7 (most preferred) > T10 > T8 >
T2. The two most highly populated positions (T7 and T10, summing to 1.09(12) Cs+ ions per unit
cell) are in the cove at the side of the intersection volume. T7 is on the wall of the intersection
volume; T10 is on the wall of just the zig-zag channel.
P-1.1-63
Synergistic Effect of Lanthanum and Phosphorus on the Aromatization Activity of Zn/ZSM-5
H.Y. Long1, F.Y. Jin1, X.S. Wang1,2
1Dep. of Catalytical Chemistry and Engineering, Dalian University of Technology, Dalian, China,
wangxs137@163.com
2State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China
The addition of La into Zn/ZSM-5 improved the dispersion degree of zinc species, increased the zinc
species-support interaction and the amount of [Zn(OH)]+ species and improved the aromatization
activity. The addition of P increased the amount of the zinc species located in the channels of
nanoscale HZSM-5 and enhanced the stability of the catalyst. The synergistic effect of La and P
increased the amount of [Zn(OH)]+ species, decreased the loss of zinc species and consequently
increased the aromatization activity and the stability of the catalyst. The FCC gasoline upgrading
results showed that olefins can be converted into aromatics over ZnLaP/HZSM-5 to compensate the
loss of octane number in the hydrodesulfurization unit.
P-1.1-64
B-, Al-, Ga- and Fe-containing extra-large pore zeolites with UTL topology: synthesis,
structure and catalytic properties
O.V. Shvets1, M.V. Shamzhy1, M.V. Opanasenko1, P.S. Yaremov1, M.V. Solomakha1, L.Kurfiřtova2,
W.J.Roth2.
1L.V. Pisarzhevskiy Institute of Physical Chemistry, National Academy of Sciences of Ukraine, pr.
Nauky, 31, Kyiv 03028, Ukraine, alexshvets@ukr.net
2 J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of Czech Republic, v.v.i.,
Dolejškova 3, 182 23 Prague 8, Czech Republic
The influence of various synthesis parameters (gel composition, pH of RM, duration of
crystallization) on the phase selectivity of zeolite formation in germanosilicate reaction mixture in the
presence of different three-valent heteroatoms E (E = B, Al, Ga, Fe) was systematically studied. The
influence of the nature of isomorphous substituent on structure, heteroatoms localization, adsorption,
acid and catalytic properties of the prepared extra-large pore UTL zeolites was established.
1.1. Zeolites and zeotypes
156
P-1.1-65
Framework transformation of FAU-type zeolite in high alkalinity
L. Van Tendeloo, E. Gobechiya, E. Breynaert, J.A. Martens, C.E.A. Kirschhock
Center for Surface Chemistry and Catalysis, Dept. M2S, KULeuven, Leuven, Belgium.,
leen.vantendeloo@biw.kuleuven.be
Faujasite (FAU) type zeolites of different size and composition were treated with 1 M MOH (M = Li,
Na, K, Rb, Cs) at 95°C. The strong stabilizing effect of the alkali cations on specific zeolite
frameworks was confirmed. A detailed study confirmed the crucial role of potassium in the formation
of chabazite (CHA).
The observation of the structural wealth accessible by simple framework transformation of zeolite Y
not only could lead to a better understanding of the influence of inorganic cation in zeolite formation,
but also offers a simple route to synthesis. In addition, the study also indicates frameworks having an
inherent alkaline stability that could be promising candidates for use in such detrimental conditions.
P-1.1-66
Influence of the framework Li+ distribution on the thermal stability of Low silica Zeolite X
M.H. Fan, S.Y. Bai*, B. Ren, J.H. Sun*
Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineer
ing, Beijing University of Technology, Beijing 100124, P. R. China. E-mail: sybai@bjut.edu.cn
Li-contained Low silica zeolite X (Li-LSX) with the Si/Al molar ratio around 1 has the wide industry
applications in the air separation fields. Their skeleton stabilities are necessary to withstand the
extreme conditions involved in pressure swing adsorption technology and regeneration. However, two
points about the stability of Li-LSX compared with that of Na-LSX, are presently not consistent with
each other and even opposite. In this work, the thermal behaviors about LSX Zeolite with different
Li+ amount and hydroscopicity performances were investigated by the thermogravimetric analysis
(TG-DSC) and in-situ high temperature X-ray diffraction (HTXRD) technique. The results
demonstrated that the effects of adsorbed water and framework Li+ distribution in the LSX skeleton
on their thermal stability would be remarkable.
P-1.1-67
Cu/zeolites catalysts obtained by impregnation and milling mechanics
Geovanni R. Melchor1, Beatriz Zeifert1, José L. Contreras-L3 , José Salmones2
1Departamento de Metalurgía, ESIQIE IPN, Av. IPN s/n Lindavista, 07738, México D, F.
2,*Laboratorio de Catálisis y Materiales, A. C., ESIQIE IPN, Av. IPN s/n Col. Lindavista, 07738,
México D, F. México. E-mail: jose_salmones@yahoo.com.mx
3Universidad Autónoma Metropolitana Az., Av. Sn Pablo 180, Col. Reynosa, México D, F.
The zeolite type Y (Na56 [(AlO2)56 (SiO2)136] 250 H2O) has a high content of Si and can be applied in
many catalytic processes. Large cavities formed inside the zeolite permit reversible dehydration takes
place, enabling a high degree of ionic exchange. The exchange aspect is of great importance since the
activity of a zeolite catalyst is related with cation type deposited on the structure.
This paper reports the synthesis of Cu impregnated Y zeolite using two methods of agitation magnetic
(AM) and milling mechanics (MM) at different Cu concentrations.
The magnetic conventional technique (AM) was used to contact metal ions in aqueous solution with
the zeolite by controlling the rate of agitation, temperature and contact time. The second technique,
milling mechanics (MM), was used to carry out the impregnation, which has not been reported in the
literature.
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P-1.1-68
Highly Dispersed Silver Nanoparticles in Beta Suspensions
F. A. Kawtharani1,2, S. Thomas1, R. Retoux3, V. De Waele2, S. Mintova1
1Laboratory of Catalysis and Spectroscopy (LCS), ENSICAEN, CNRS, University of Caen, 6 Bd
Maréchal Juin, 14050 Caen, France, e-mail: farah.kawtharani@ed.univ-lille1.fr
2Laboratory of Infrared and Raman Spectroscopy (LASIR), CNRS-University of Lille1, 59650
Villeneuve d’Ascq, France
3CRISMAT, ENSICAEN, CNRS, University of Caen, 6 Bd Maréchal Juin, 14050 Caen, France
Here we report on the preparation of silver nanoparticles within the micropores of zeolite Beta
stabilized in colloidal suspensions. The silver is introduced in the Beta zeolite via ion exchange and
then chemically reduced with either triethylamine or sodium borohydride. The highly dispersed silver
nanoparticles (above 80 %) with a size of 1 nm are embedded in the channels of zeolite Beta. It is
revealed that the triethylamine plays a dual role, as a reducing and stabilizing agent. The size,
dispersion and stability of the silver nanoparticles in various zeolite suspensions are systematically
investigated.
P-1.1-69
Ruthenium Nanoparticles Encapsulated Disordered Titanosilicate ETS-10
Melda İşler1, S. Galioglu1, Burcu Akata Kurç1,2
1Micro and Nanotechnology Department, Middle East Technical University, 06800 Ankara, Turkey,
meldasler@gmail.com
2Central Laboratory, Middle East Technical University, 06800 Ankara, Turkey
Engelhard Titanosilicate (ETS-10) a member of crystalline microporous material consisting of TiO6
octahedra and SiO4 tetrahedra. Each negative charge due to octahedra titania unit is balanced with
exchangeable cations, which are Na+ and K. The increase in micropore volumes of ETS-10 was
observed after the post-synthesis treatments with aqueous solutions of H2O2 due to partial removal of
the structural Ti atoms. Ru nanoparticles formed by chemical reduction was investigated to see
whether any changes were induced during the formation of such metal nanoparticles within the pores
of ETS-10. It was seen that the formation of Ru nanoparticles let to further distortion of ETS-10
structure.
P-1.1-70
Incorporation of fluoride in as-made zeolites: new developments and applications
X. Liu, A. Tuel
IRCELYON, UMR 5256 CNRS-Université de Lyon 1, 2 Av. A. Einstein 69626 Villeurbanne Cedex,
France, alain.tuel@ircelyon.univ-lyon1.fr
The possibility to reversibly introduce fluoride species in the structure of zeolites in the presence of
templating molecules has recently opened new opportunities in the preparation of materials with
specific properties and in the characterization of substituted frameworks. The presentation will give
an overview of the possibilities offered by this new concept, from the possibility to tune the
hydrophobic/hydrophilic character of all-silica zeolites to the detailed description of Ge species in
zeolite frameworks. In particular, we shall show that silicalite-1 nanocrystals (ca. 150 nm) can be
obtained with a density of framework connectivity defects similar to those obtained on large crystals
obtained in fluoride media. Moreover, for germanosilicates, incorporated fluoride species will be used
as a NMR probe to evaluate the population, distribution and evolution of Ge atoms in the framework,
particularly in the small D4R units of ITQ-17 and ITQ-24.
1.1. Zeolites and zeotypes
158
P-1.1-71
Using InCl Vapor to Ion Exchange Indium into Zeolite Na–X. Two Single-Crystal Structures
of Fully Dehydrated Inn+-Exchanged Zeolite X
D. Sen,1 N.H. Heo,1 K. Seff,2 H.-C. Kang,3 and M.K. Park4
1Department of Applied Chemistry, Kyungpook National University, Daegu 702-701, Korea
sendipak25@knu.ac.kr
2Department of Chemistry, University of Hawaii, Hawaii 96822-2275, USA
3Green Chemistry Division, Korea Research Institute of Chemical Technology, Daejeon 305-600,
Korea
4SebitChem, Recycling Chemicals, Gimcheon 740-170, Korea
Indium ions have been introduced into zeolite X (FAU, Si/Al = 1.09) by an anhydrous vapor phase
ion exchange (VPIE) method. In6.4[(In8Cl8)16+]1.73(In10Cl)13+(Na+)45.6–X and In14(In57+)4(Na+)50–X
(approximate formulas) were prepared with 0.003 Torr and 13 Torr of InCl(g) at T = 623 K and 673
K, respectively. Their structures were determined using single-crystal crystallography and were
refined in the space group 3Fd to the final error indices R1 /wR2 = 0.066/0.186 and 0.076/0.214,
respectively. InCl(g) replaced about half of the Na+ ions in zeolite Na92-X, with In57+ and In+ in first
structure and In57+–Cl–In57+, (In8Cl8)16+, and In+ cations in the latter.
P-1.1-72
Single Gold nanoparticle in Single crystal hollow zeolite
S. Li, L. Burel, A. Tuel, C. Aquino, D. Farrusseng
1IRCELYON, CNRS-University Lyon 1 – 2, Av. Albert Einstein – 69626 Villeurbanne, France,
david.farrusseng@ircelyon.univ-lyon1.fr
Nanostructured Yolk-shell materials, which consist in metal nanoparticles cores inside hollow shells,
are ideal model catalysts. In the case of gold Yolk-shell catalysts, shells are made of oxides (SiO2,
ZrO2, and TiO2) or amorphous carbon based materials. Shells are generally mesoporous which allow
substrates to diffuse through and finally react at the catalytic nanoparticle. However, mesoporous
shell is powerless for the sieving of molecular species prior to catalytic conversion.
In this work, we report for the first time the preparation of Au@silicalite-1 Yolk-shell material with a
monocrystalline zeolitic shell, hereafter called “nanoboxes”. The preparation method enables to get
one single gold nanoparticle (5-10 nm) in a hollow nanoboxe. The size of the gold particles can be
easily controlled. The shell is entirely microporous which shall enable molecular sieving of substrates
of different sizes. The synthesis method has been extended for the preparation of Au@ZSM-5
nanoboxes. Catalytic activity will be presented and compared with that of conventional Au supported
catalysts.
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P-1.2-01
Regularities of sorption pyridoxine hydrochloride on native clinoptilolite tuff
Kotova D.L., Fam Thi Gam, Krysanova T.A., Vasilyeva S.U. Timchenko U.A.
Russia, Voronezh, Voronezh State University, sv_vasileva@mail.ru
The analysis of equilibrium in the system was carried out by separating the areas of ion exchange and
non-exchange fixing specimen. In the field of dilute solutions of the isotherm has a linear plot, and
then reaches a plateau. Exchange capacity of vitamin B6 is 0.28 mmol/g. The low value of the
exchange capacity compared to the capacity determined by the ammonium ions, may be due to the
inaccessibility of the charged centers of the sorbent matrix cations pyridoxine hydrochloride. The use
of Langmuir equation in a linear fashion allowed to determine maximum monolayer capacity and the
coefficient of sorption equilibrium. After the formation of the monolayer as the concentration of the
solution increases the content of the drug fixed on clinoptilolite tuff, with the ion-exchange sorption
component does not change. The maximum number of sorbed vitamin B6 on natural clinoptilolite tuff
is 0.53 mmol/g and is reached.
P-1.2-02
CO2 adsorption on Erionite exchanged with Ca 2 +, Mg 2 +, K +, Na + and H +
M. A. Hernández1, Corona1, F. Rojas2, R. Portillo3
1Dep de Investigación en Zeolitas, Instituto de Ciencias de la Universidad Autónoma de Puebla,
México. vaga1957@gmail.com
2Dep de Química, Universidad Autónoma Metropolitana-Iztapalapa, México 09340 D.F. 3Facultad
de Ciencias Químicas, Universidad Autónoma de Puebla. México.
Adsorption processes are now a valuable option to remove certain types of fluid contaminants from
gas streams. In many industrial applications that have pores of solids near the molecular dimensions
are used as selective adsorbents because they display physicochemical specificity in contrast to most
common mesoporous adsorbents. In this work natural zeolites from Mexico have been used as
adsorbents for selectively adsorbing this potential gas under conditions similar to those reported when
synthetic zeolites are used, specific cases are reported using ERI, HEU and MOR zeolites. The goal
of the present work is to study and compare the experimental results obtained CO2 adsorption by
erionite zeolites static method: natural, decationated and exchanged to establish the order of
selectivity for this gas of zeolites under study.
P-1.2-03
Cobalt-exchanged natural zeolites (Australian and Indonesian) for catalytic oxidation of phenol
solutions
Hongqi Sun1, Edy Saputra1,2, Ha Ming Ang1, Moses O. Tadé1, Shaobin Wang1
1Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA6845,
Australia, Email: shaobin.wang@curtin.edu.au
2Department of Chemical Engineering, Riau University, Pakanbaru, Indonesia
Indonesian (InZ) and Australian (AuZ) natural zeolites were employed to prepare cobalt exchanged
catalysts. The samples were thoroughly analyzed by a variety of techniques, such as XRD, SEM,
TEM, UV-Vis and BET. The efficiencies of phenol removal on the catalysts were evaluated by the
catalytic oxidation of phenol with sulfate radicals. Cobalt-exchanged natural zeolite catalysts showed
higher phenol removal than adsorption, oxone self-oxidation, and unmodified zeolites. Zero-order
kinetics was found better to describe the reactions, and the activation energies were evaluated to be
59.5 and 44.1 for Co/AuZ and Co/InZ, respectively. This study provides a novel application of natural
zeolites for environmental remediation.
1.2. Natural zeolites
160
P-1.2-04
Use of zeolitites from Central Italy in an integrated cycle aimed at water and chemical
fertilizers saving
(ZEOLIFE - LIFE+10ENV/IT/000321)
M.F. Brigatti1, A. Laurora1, D. Malferrari1, E. Passaglia, G. Vezzalini1
1Dep. of Chemistry and Geology, University of Modena and Reggio Emilia, Modena, Italy,
mariagiovanna.vezzalini@unimore.it
The project “ZEOLIFE-Water pollution reduction and water saving using a natural zeolitite cycle”
has been conceived to test an innovative integrated zeolitite employment to reduce the NH4 content in
livestock effluents and correct agricultural soils, with improvement of the yield and economization of
water for irrigation and fertilizers. The first goal of the project was the choice of the most suitable
zeolitite. The quarry material was selected basing on zeolite content (species and amounts), type and
amount of exchangeable cations,CEC,density, and water retention. The zeolitite from the Sorano
resulted to be a first-rate material for the project purposes. It is in fact a K-rich, Na-poor zeolitite
characterized by high zeolitic content (with dominant chabazite and very subordinate phillipsite), as
well as by high CEC value.
P-1.2-05
Activated Natural Zeolite Supports Human Health and Physical Performance as an Antioxidant
T. Oberwinkler1, D. Maurer1, K. Pavelić2, S. Kraljević Pavelić2, M. Lamprecht3,4, I. Triebnig5, N.
Bachl6
1Panaceo International Active Mineral Production GmbH, Finkensteinerstr. 5, 9585 VillachGödersdorf, Austria/Europe, oberwinkler@panaceo.com
2Department of Biotechnology,University of Rijeka, Radmile Matejcic 2, 51000 Rijeka, Croatia
3Green Beat - Institute of Nutrient Research and Sport Nutrition, Graz, Austria
4Institute of Physiological Chemistry, Centre for Physiological Medicine, Medical University of Graz,
Graz, Austria
5Surgeon, Accompanying Cancer Therapy, Villach, Austria
6Institute of Sports Sciences, Department of Sport Physiology, University of Vienna, Vienna, Austria
The natural zeolite clinoptilolite, a medical device, acts as an antioxidant and its bio-physical
properties are increased using a special micronisation process. This was investigated in animal and
human studies.
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P-1.2-06
Removal of radionuclides by zeolite-bearing rocks
D.A. Shushkov1, O.B. Kotova1, I.I. Shuktomova2
1Institute of Geology, Komi Science Center, Ural Branch, RAS, Syktyvkar, Russia,
dashushkov@geo.komisc.ru
2Institute of Biology, Komi Science Center, Ural Branch, RAS, Syktyvkar, Russia
The study of the removal of radioactive elements (uranium, radium and thorium) in static conditions
from aqueous solutions by different sorbents (clinoptilolite- and analcime-bearing rocks, pure
analcime) was carried out. The high removal efficiency of radium, thorium and uranium by analcimebearing rocks was determined. Clinoptilolite-bearing rocks removed thorium and radium almost
completely, but the removal efficiency of uranium from solution was less. Analcime was efficient in
removing of thorium only.
According to the results of radionuclides extraction, thorium was retained most strongly, its
insignificant extraction to solution by distilled water and ammonium acetate processing was observed.
Analcime retained uranium quite strongly, while zeolite-bearing rocks retained it strongly only during
distilled water processing. The high radium extraction (about 50 % from zeolite-bearing rocks and
more than 60 % from analcime) was probably caused by its inclination to ion exchange.
P-1.2-07
Elimination of Fluoride using Natural Zeolites from Ethiopia
Luis Gómez-Hortigüela1*, Joaquín Pérez-Pariente1, Yonas Chebude2 and Isabel Díaz1,2
1 Instituto de Catálisis y Petroleoquímica, CSIC, Madrid, Spain. Contact email:
lhortiguela@icp.csic.es
2 Chemistry Department, Addis Ababa University, Addis Ababa, Ethiopia.
Natural zeolites locally available in Ethiopia have been tested for defluoridation of water; this
represents an endemic problem in this country, especially in the Rift-Valley area, where 41 % of the
drinking-water have fluoride concentrations exceeding the limit of 1.5 mg/L imposed by the World
Health Organization. Among a set of 10 different samples tested, one of them, which is mainly
composed of mordenite and analcime zeolites but also contain some other minor phases, has shown a
particularly promising defluoridation capacity, being able to lower the fluoride concentration beyond
the WHO limit. An ample study of the defluoridation capacity of this particular sample will be
presented in the conference.
1.2. Natural zeolites
162
P-1.2-08
About Possibility of Using Modified Natural Zeolite in Catalytic Cleaning of Exhaust Gases
from NO and CO
L.Akhalbedashvili1, G. Maisuradze2, A. Mskhiladze3, Sh. Sidamonidze2
1 Iv. Javakhishvili Tbilisi State University,Tbilisi,CIMR,Georgia; aklali@yahoo.com
2 Holy Apostle St. Andrew the First-Called Georgian University of Georgian Patriarchate, Tbilisi,
Georgia;
3 Sukhumi State University, Tbilisi, Georgia
Reduction of nitrogen oxide with different reducing agents (CO, NH3, H2, CH4) was carried out on
the natural zeolite clinoptilolite (CL) from deposit of Georgia, which was modified with ions of
copper and iron after preliminary thermal and chemical treatment. It was found that introducing ions
of iron to CuCL structure increase the catalytic action of catalyst and influence on the mechanism of
reaction NO + CO.
It was suggested that reducing of nitrogen oxide proceed through the dissociative adsorption of NO,
and the Cu+ →Cu2+ and Fe2+→Fe3+ oxidation process occurs. The following reduction of isolated ions
and Cu2+ - O - Cu2+ bridging complexes easily occur in the area 473-593K. So, catalytically active
centers of zeolites cannot be homogeneous because they are characterized by disordered distribution
of atoms of aluminum, silicon, and exchangeable cations.
P-1.2-09
Investigation and mathematical modeling of Sr2+ ion-exchange kinetics from surface drinking
water on natural clinoptilolite
V.A.Nikashina1, М.G.Tokmachev2, I.B.Serova1, T.G.Kuzmina1, I.A.Roschina1, .A.Tikhonov2
1Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia
nikashina_v@mail.ru
2 Department of Physics, Moscow State University, Moscow, Russia
Sr2+ sorption kinetics from the surface drinking water by the natural clinoptilolite of Khonguruu
deposit was studied by the “thin layer” method as the continuation of researches of the dynamic ion
exchange processes on the natural zeolites. Previously developed mathematical model of the twostage sorption kinetics on the clinoptilolite have been applied for analysis of experimental results. The
values of the kinetic coefficients of the first and second stages were determined. The comparison of
kinetics coefficients values obtained from the dynamic breakthrough curves and from the kinetics
experiments in ”thin layer” indicates, that the partical diffusion coefficients values are distinguished
in 10 times (the first stage), that is probably stipulated by low Sr 2+ concentration in the initial
solution (0.2 mg/l), the determined value of kinetic coefficient γ≤10-9 s-1 (the second stage) remains
the same.The results obtained confirm the applicability of the suggested model.
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P-1.2-10
The characterization of geomorphic molecular sieve particles using Zero Length Column
chromatography
S.A. Hosseinzadeh Hejazi1, J. Sawada1, G. Dechaine1, S. Kuznicki1
1 Dep. of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada,
alirezahejazi@ualberta.ca
Understanding the transport mechanism of gas molecules in zeolites is a significant step in
characterizing and exploiting them for industrial applications. Zero-length column (ZLC) technique
has been widely used to measure intracrystalline diffusivity and mass transfer kinetics in porous
materials. In this study ZLC is used to identify the optimal particle size for composite membranes for
gas separation applications. A wide range of natural zeolite particle sizes was prepared and tested at
cryogenic conditions. The results suggest that it is possible to achieve consistent zeolite diffusion
behavior over a range of particle sizes. This can lead us to understand the significance of monolithic
natural zeolite over a wide range of particle sizes made from dense geomorphic molecular sieve.
P-1.2-11
Natural iron exchanged Mordenite: FTIR study and Catalytic Activity in NO Reduction
I. Rodríguez Iznaga1, D. Tito Ferro2, V. Petranovskii3, F. Castillon Barraza3, A. Simakov3, B.
Concepción Rosabal1, F. Chávez Rivas4, I. E. Tellez León4, G. Berlier5
1Instituto de Ciencia y Tecnología de Materiales (IMRE) - Universidad de La Habana, Cuba
2Centro Nacional de Electromagnetismo Aplicado, Universidad de Oriente, Cuba
3Centro de Nanociencias y Nanotecnología – UNAM, México
4Departamento de Física, ESFM-IPN, México, fchavez@esfm.ipn.mx
5Dipartimento di Chimica I.F.M., Università di Torino, Torino, Italy
Purified natural mordenite (PZ) from Palmarito de Cauto deposit, Cuba, was subject of studies of Fe2+
and Fe3+ exchange, FTIR coupled to NO adsorption and catalytic activity in NO reduction with
CO/C3H6 of the exchanged samples. Fe2+ exchange is less favored than Fe3+ exchange. All exchanges
raise the surface area to PZ, but, area and volume of micropore decrease. FTIR, show the presence of
isolated Fe2+ and nanoparticles of iron oxides on the samples. The FTIR analysis and catalytic activity
suggest that main active centers in NO reduction are linked with Fe2+.
P-1.2-12
Adsorption of urea onto Iranian natural phillipsite and stilbite zeolites
C. F. Linares1, L. Uray1, F. Ocanto1, X. Cardozo1, S. Yazdani2
1 A Unidad de Síntesis de Materiales y Metales de Transición, Facultad de Ciencias y Tecnología,
Departamento de Química, Universidad de Carabobo, Valencia. Edo. Carabobo, Venezuela,
clinares@uc.edu.ve
2 University of Teheran, Islamic Azad University, Iran
Iranian natural phillipsite and stilbite zeolites were obtained and purified from North Central of Iran.
Zolites were characterized by the XRD, FT-IR and BET surface area. These solids were contacted
with urea solutions at different concentrations and contact times. Then, these solids were separated
from the solutions by centrifugation and the obtained supernatants were analyzed by UV-Visible
spectroscopy in order to get the possible adsorption models: Langmuir or Freundlich. The urea
maximum sorption was 26% and 10% for phillipsite and stilbite respectively. On the other hand,
equilibrium contact times were reached at 3 hours for both studied solids. After contact with urea
solutions, solids were washed, dried at room temperature and analyzed by FT-IR. Results did not
show characteristics bands of urea molecules adsorbed on the zeolite surfaces which shows that solidurea interactions were weak
1.2. Natural zeolites
164
P-1.2-13
Mechanical activation of zeolite powders for improving efficiency of sorption
of oil spills on water surface
L. Y. Atyutskaya1, A. G. Bebia2
1Dep. "physical-chemistry processes and materials" Ugra State University, Khanty-Mansiysk, Russia,
Liliya_atyuckaya@mail.ru
2Dep. "physical-chemistry processes and materials" Ugra State University, Khanty-Mansiysk, Russia,
Bebiya.nastya@mail.ru
The problem of increasing specific surface area of zeolites is challenging for active combat with
environment pollution by hydrocarbons. The dependence of specific surface area of clinoptilolite
particles on the time of mechanical activation is evidenced. The optimal time of mechanical
activation which could result in maximum adsorption ability of clinoptilolite toward hydrocarbon is
recommended. As evidenced experimentally, the mechanical activation of clinoptilolite is a way to
improve its adsorption properties.
P-1.2-14
Zeolitized tuff as raw material for alkali activated binders
B.Liguori1, C. Ferone2, I. Capasso2, R. Cioffi2 and C. Colella1
1Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università
Federico II, Naples, Italy. carmine.colella@unina.it
2 Dipartimento di Tecnologie, Università Parthenope, Naples, Italy
Geopolymers have long been studied as an alternative of traditional cements, and are now attracting
increased attention for their low CO2 emissions, durability, good mechanical properties, and low
production costs. Among the pozzolanic materials natural zeolites, due to their large availability and
reasonable properties, are gaining increasing importance as additive and/or aggregate in the cement
industry. This work aims at studying a phillipsite-rich tuff as raw material for alkali activated binders,
evaluating the effect of firing and curing time on its interaction with alkaline solutions of various
concentrations. Leaching by alkaline attack results in the following decreasing order:
Metakaolin>Tuff>Fly ashes. Among the tuff samples, the best performance was obtained with the
untreated sample. The extent of dissolution increases with increasing the concentration of the NaOH
solution. Firing seems to affect negatively the reactivity of tuff, increasing its resistance to
dissolution.
P-1.2-15
The choice of optimal conditions for fixing α-tocopherol on acid activated clinoptilolite tuff
Vasilyeva S.Y., Kotova D.L., Krysanova T.A.
Russia, Voronezh, Voronezh State University
sv_vasileva@mail.ru
Showed the adsorption isotherms of α-tocopherol on acid activated clinoptilolite tuff from ethanol,
ethyl acetate and hexane. It is established, that the polarity of the solvent does not influence on the
form of the isotherm. Activated adsorbent has large selectivity to α-tocopherol by the absorption from
more polar ethyl alcohol. The experimental data in the linear form of the equation allowed determine
the maximum capacity of the monolayer and adsorption equilibrium coefficient. The temperature
change in the interval 283-333 K does not affect the type of isotherm. Lowering the temperature of
the process leads to an increase in the selectivity of the sorbent to vitamin E. The value of Gibbs free
energy of the adsorption process α-tocopherol, calculated from the adsorption equilibrium constants,
describes the process under study as energetically favorable. The average enthalpy of adsorption in
the temperature range 283-333 K is - 28.0 kJ/mol, which indicates an exothermic sorption.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.2-16
Application of natural zeolites for creation of polymer composite materials
I.N. Meshkova1 , T.M. Ushakova1, V.G. Grinev1, V.A.Nikashina2, T.A.Ladygina1, L.A.
Novokshonova1
1Semenov Institute of Chemical Physics RAS, Moscow, Russia, meshkova.in@yandex.ru
2Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia
The new composite materials on the base of finely dispersed (powdered) fractions of clinoptilolitebearing tuffs and ultrahigh-molecular-mass polyethylene UHMPE were developed. The synthesis of
composites was carried out by ethylene polymerization on a surface of zeolite fillers catalytic
activated by vanadium and zirconocene metalorganic complexes. Compositions with 30-40wt %
zeolite filler in the polymer matrix were used as wear-resistant, impact-resistant materials in friction
units operating at high loads. The polyethylene compositions with the ultrahigh content of the finely
dispersed natural zeolite (95-97 wt%) were used as organomineral ion-exchange sorbents for water
purification from radionuclides and heavy metals ions in sorption processes both under static and
dynamic modes
P-1.2-17
Zeolite-bearing rocks of the Komi Republic (Russian Federation)
D.A. Shushkov, O.B. Kotova
Institute of Geology, Komi Science Center, Ural Branch, RAS, Syktyvkar, Russia,
dashushkov@geo.komisc.ru
Zeolite-bearing rocks are wide spread in the Komi Republic (Russian Federation); zeolite
mineralization is represented by analcime and clinoptilolite. Although these rocks refer to poor zeolite
raw due to low zeolite content (from 1-3 to 20-30 %), these rocks are considered as sorption raw of
mixed composition because zeolites associate with clay minerals which are in amount of 50-70 % and
also possess sorption properties.
Mechanical, sorption, ion-exchange properties, thermostability and acid resistance have been studied.
It was found that it is possible to improve characteristics of physicochemical properties by thermal
and acid processing.
According to obtained results, zeolite-bearing rocks of the Komi Republic could be applied in various
industrial applications, including: filtering material for purification of industrial-drinking water
instead of quartz sand in rapid filters at water supplies; radionuclides removal from water; lightweight
materials for building industry.
P-1.2-18
EPR study of some modified clinoptilolites from deposit of Georgia
L.Akhalbedashvili, N.Kekelidze, R.Mirianashvili
Iv. Javakhishvili Tbilisi State University, Tbilisi, Georgi; alkali@yahoo.com
It have been made the attempts to study the localization, coordination and migrations of cations of
natural zeolite clinoptilolite (CL) by EPR-method in initial, decationated by acid treatment and Cucontained samples, hydrated and dehydrated at 473 and 723 K. It was found that study of СL –tuff by
a ESR method is complicated by presence of impurities of magnetic minerals in samples.
In spectrums of natural zeolites of Georgia - CL the wide signal with g = 4.310 belongs to isolated
ions Fe3+ in tetrahedral coordination.
The ions of copper in hydrated CuCL are as a hexa-aqua (ammonia)-complexes. At dehydration these
complexes break up and the Cu2+ ions connect to oxygen of a lattice of zeolite with symmetry of a
square pyramid or plane quadrate.
1.2. Natural zeolites
166
P-1.2-19
Investigation of Sulphur Dioxide (SO2) Adsorption Properties of Natural and Acid Modified
Clinoptilolites from Turkey
Burcu Erdoğan Alver1, Meryem Sakızcı1
1Department of Physics, Science Faculty, Anadolu University, 26470, Eskisehir, Turkey,
msakizci@anadolu.edu.tr
Sulphur dioxide (SO2) adsorption on clinoptilolite tuff from Gördes, Turkey and that of acid treated
forms were studied at 293 K using volumetric apparatus up to 100 kPa. The clinoptilolite mineral was
modified with 0.1, 0.5, 1 and 2 M HCl solutions at 70 oC during 3h. X-ray diffraction (XRD) and
N2 adsorption techniques were used for structural characterization. The XRD diffractograms were
obtained with a Rigaku, RINT-2200 model instrument, using CuKα radiation (λ=1.54 Å), 40 kV and
30 mA power supply. A volumetric-type apparatus (Autosorb 1C) was used to measure the nitrogen
(N2) and sulphur dioxide (SO2) adsorption capacities of natural and acid treated clinoptilolites. BET
surface areas were calculated from the first part of the N2 adsorption isotherm (0.05

obtained at liquid nitrogen temperature with high-purity (99.99%) N2. Clinoptilolite treated with 0.5
M HCl solution adsorbed SO2 most effectively.
P-1.2-20
Low-temperature behavior of the cancrinite-group minerals
G.D. Gatta1, P. Lotti1, V. Kahlenberg2
1Dep. of Earth Sciences, Università degli Studi di Milano, Italy, diego.gatta@unimi.it
2Inst. Mineralogie und Petrographie, Universität Innsbruck, Austria
The low-temperature behaviour of two isotypic minerals with CAN framework type (i.e. cancrinite
and balliranoite) was investigated by in-situ single-crystal X-ray diffraction down to 100 K. No
evidence of a phase transition was observed within the T-range investigated. The thermal expansion
coefficient are: αV = 3.8(7) •10-5 K-1 for cancrinite and αV = 4.6(4)•10-5 K-1 for balliranoite. The extraframework population does not show significant variations down to 100 K. The strong positional
disorder of the carbonate groups along the c axis persists within the T range investigated. The
structure evolution of cancrinite and balliranoite at low-T is mainly governed by the continuous
framework re-arrangement by tetrahedral tilting. The main difference between the two isotypic
materials is in the magnitude of deformation mechanisms. In cancrinite, the ditrigonalization of 6mR
parallel to (0001) is more pronounced. In balliranoite, the main mechanism is the cage-width
shortening along the O2-O2 diameters, leading to an isotropic compression of the cage. On the
contrary, a significant cage flattening along [0001] is observed in cancrinite.
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P-1.3-01
Micro-mesoporous materials prepared using zeolite nanoparticles as catalysts
for N2O decomposition and reduction
M. Rutkowska1, L. Chmielarz1, D. Macina1, Z. Piwowarska1, B. Dudek1, W. Roth2, L. Obalová3, C.J.
Van Oers4, P. Cool4
1Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland, rutkowsm@chemia.uj.edu.pl
2 J. Heyrovský Institute of Phisical Chemistry of ASCR, v.v. i., Prague, Czech Republic
3Technical University of Ostrawa, 17. listopadu 15, 708 33 Ostrava, Czech Republic
4University of Antwerpen Universiteitsplein 1, B-2610 Wilrijk, Belgium
The studies were focused on the synthesis of hybrid micro-mesoporous materials with the properties
of Beta and ZSM-5 zeolites. Two modern approaches were applied to obtain the hierarchical
materials. Both impregnation and non-templating methods resulted in the formation of materials with
hierarchical porous structure. The obtained materials were used as supports of catalysts for N2O
decomposition and reduction.
P-1.3-02
Improved catalytic performance of mesoporous zeolite ZSM-5 synthesized by desilication with
surfactants
F. Schmidt1, M. R. Lohe1,2, B. Büchner2, F. Giordanino3, F. Bonino3, S. Kaskel1
1Dep. of Inorg. Chemistry, Dresden University of Technology, Dresden, Germany,
stefan.kaskel@chemie.tu-dresden.de
2Leibniz Institute for Solid State and Materials Research, Institute for Solid State Research, Dresden,
Germany
3Dep. of Inorg. Phys. and Mater. Chem., University of Torino, Torino, Italy.
Hierarchical ZSM-5 zeolites were synthesized by alkaline desilication and a surfactant induced reassembly. Contrary to the purely alkaline desilicated zeolites a strong increase in external surface
area, a narrow pore size distribution of 3-10 nm could be achieved when using CTAB as a surfactant
throughout the alkaline treatment. The hierarchical pore system lead to an improved catalyst lifetime
in the methanol to olefin conversion. A further enhancement in catalyst lifetime was achieved by
introducing more surfactant molecules, leading to an increased catalyst porosity.
P-1.3-03
Pt(II) complex anchored onto mesoporous silica materials: correlation between
photoluminescence emission and visible-light driven photocatalytic activity
Kohsuke Mori1,2*, Kentaro Watanabe1, and Hiromi Yamashita1,2
1Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka
University, 2ESICB, Kyoto University, Japan, e-mail : mori@mat.eng.osaka-u.ac.jp
[Pt(tpy)Cl]Cl complex was successfully anchored to a series of APTMS-modified mesoporous silica
materials. At low Pt loading, the non-emissive Pt(II) complex exhibits strong photoluminescence at
room temperature due to 3MLCT transitions maximized near 530 nm, which was effective for the
selective photooxidation of styrene derivatives using O2. On the other hand, the 3MMLCT transition
was prominent at high Pt loading, in which H2-evolving reaction proceeded in aqueous media under
visible-light irradiation.
1.3. Mesoporous materials and hierarchical porous structures
168
P-1.3-04
Meso and microporous materials for confined space synthesis of noble metal catalysts to
address their sintering problems
R. Nandini Devi*, Atul Prashar, Anupam Samanta, Sumona Ghosh
Catalysis Division, CSIR- National Chemical Laboratory, Pune 411008, India nr.devi@ncl.res.in
Conventional oxide supported metal catalysts are plagued with problems of poor dispersion and
deactivation due to agglomeration which can be addressed by encapsulating metal nanoparticles
within oxide matrices. However, the oxide matrix should be porous to enable access of reactant
molecules to active surfaces. We have developed novel in-situ encapsulation of metal nanoparticles in
mesoporous silicas and microporosity generation after encapsulation to address this problem. The
catalysts are found to be highly stable till temperatures of the order of 750 °C and efficient catalysts in
hydrogenation, glucose detection etc.
P-1.3-05
Silylation and hydrothermal stability of composite materials based on MCM-41
E.O. Korabelnikova1, S.I.Karpov1, N.A. Belanova1, V.F. Selemenev1, F. Roessner2, A. Inayat3
1Dep. of Chemistry, Voronezh State University, Voronezh, Russia, karsiv@pochta.ru
2Industrial Chemistry 2, Carl von Ossietzky University, D-26111, Oldenburg, Germany
3Erlangen-Nurnberg University, Erlangen, Germany
The processes of silylation of MCM-41 using trimethylchlorosilane, dimetoxydimetylsilane,
trimetoxyoktylsilane, and dichlorometylphenylsilane are studied. Based on the data of the lowtemperature nitrogen adsorption-desorption the surface properties, the porosity of high ordered
mesoporous materials is considered. It is noted that the degree of grafting and the pore size, as well as
other bulk material properties vary with conditioning of temperature and modifying agent
concentration.
X-ray diffraction data indicates significant structural changes of MCM-41 after hydrothermal
treatment. The partial destruction of the hexagonal structure of mesoporous materials takes place.
Hydrothermal treatment of mesoporous composites based on MCM-41 does not change the structure
of the silica matrix.
The data of competitive adsorption of water and toluene shows the effect of the modification on the
sorption properties of mesoporous materials. The thermostability and change of hydrophilicity by the
silylation of composite materials based on MCM-41 was considered by TGA/DT analysis.
P-1.3-06
Synthesis of mesoporous graphic C3N4 using cross-linked bimodal mesoporous SBA-15
as a hard-template
H.-M. Zhao, Y. Chun*, L. Ji, Q.-H. Xu
Key Laboratory of Mesoscopic Chemistry of the Ministry of Education, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing 210093, China, ychun@nju.edu.cn
Mesoporous graphic C3N4 photocatalyst was synthesized by using a new cross-linked bimodal
mesoporous SBA-15 as a hard template and cyanamide as the sources for C and N. This mesoporous
g-C3N4 material replicates the periodic mesochannels of the hard template, and has specific surface
area much higher than bulk-g-C3N4 and g-C3N4 prepared using conventional SBA-15 template.
Moreover, this mesoporous g-C3N4 exhibits good photocatalytic performance in the degradation of
methyl orange, and displays its potential in environmental protection.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-07
Hierarchical Mesoporous MFI Zeolites by Steam-Assisted Crystallization
and Applications in Catalysis
J. Zhou1,2, Z. C. Liu1, H. X. Gao1, Y. D. Wang1, Z. K. Xie1, Y. Tang2
1 Shanghai Research Institute of Petrochemical Technology, Sinopec, Shanghai, China
lotuslzc@yahoo.com
2Dep. of Chemistry, Fudan University, Shanghai, China
By employing conventional block copolymers as mesoposity scaffolds, a direct synthetic route of
mesoporous MFI zeolites has been developed with the assistance of post-steaming treatment. It was
found that the resultant materials possess well defined hierarchical micro-/mesoporous structure, large
surface area and high hydrothermal stability. More importantly, such hierarchical micro/mesostructure demonstrated the enhanced catalytic activity for probe reactions involving bulky
molecules, such as cracking of triisopropylbenzene and selective oxidation of trimethylphenol, due to
the increased external surface, and the greatly shortened diffusion length in microporous networks.
P-1.3-08
Organosilanes affecting the structure and formation of mesostructured cellular foams
K. Stawicka1, I. Sobczak1, M. Trejda1, B. Sulikowski2, M. Ziolek1
1A. Mickiewicz University, Faculty of Chemistry, Poznan, Poland, ziolek@amu.edu.pl
2J. Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Krakow, Poland
In this work we dwell on the role of modifying agents, i.e. APTMS and MPTMS (3-aminopropyl- and
3-mercaptopropyltrimethoxysilane) in the formation of pure silica and metallosilicate (Nb) MCF
phases, avoiding simultaneously their contamination with the SBA-15 phase. The synthesis of
mesostructural cellular foams with the reduced amount of HCl was performed to minimize residual
chloride ions content in the final material. MPTMS and APTMS modification of MCF in the direct
synthesis route enhanced the efficiency of formation of pure spherical MCF phases. Addition of Nb
modified the morphology of the material and its role resembled the effect exerted by NH4F.
Modification of MCFs with organosilanes opens up new possibilities in engineering and
manufacturing of pure mesostructural cellular foams needed for catalytic purposes.
P-1.3-09
As-synthesized CTA-MCM-41 modified with methacrylate polymers: characterization and
catalytic evaluation
J. A. Araújo, D. Cardoso
Catalysis Laboratory, Chemical Engineering Department, Federal University of São Carlos, 13565905-São Carlos, Brazil www.labcat.org, dilson@ufscar.br
A clean alternative fuel is increasingly demanded nowadays and among many possible sources,
biodiesel fuel attracts attention as a promising alternative to conventional diesel fuels. The production
is mainly based on the homogeneous route. However, there are efforts to obtain biodiesel by the
heterogeneous route, which offers substantial advantages, including easy separation from the reaction
medium and the ability to reuse the catalyst. In this work, MCM-41 was synthesized using the
emulsion polymerization technique in order to obtain a material that was catalytically more stable.
Small angle X-ray scattering (SAXS) was used to characterize the solids and the dispersions
containing monomer. The SAXS curves confirmed the presence of monomers in the interior of the
micelles, as well as in the channels of the CTA-MCM-41. The presence of the polymeric phase
inhibited leaching of the CTA cation, and therefore promoted catalytic stability.
1.3. Mesoporous materials and hierarchical porous structures
170
P-1.3-10
Desilication of MFI Zeolites under Hydrothermal Condition
Guang Zeng1, 2, Congbiao Chen1, Debao Li1, ∗, Bo Hou 1, Yuhan Sun1, 3, ∗
1 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, Taiyuan, Shanxi 030001, PR China
2 Graduate University of Chinese Academy of Science, Beijing 100039, PR China
3 Low Carbon Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of
Sciences, Shanghai 201203, PR China, yhsun@sxicc.ac.cn
Due to TPA+ cations providing a protective layer on the surface of small mesopores, the initially
existed mesopores of the parent zeolite and sample treated in TPAOH are well preserved and new
mesopores are developed by repeated TPAOH treatment. Hence, it offers us opportunities to precisely
tailor the amount of mesopores. Additionally, the mesopore size can be controlled by varying the time
and temperature of TPAOH treatment. It is therefore concluded that precise design and preparation of
hierarchical zeolites with well preserved micropores can be achieved by adjusting the amount and size
of mesopores through varying the time, temperature and repeated times of TPAOH treatment.
P-1.3-11
Structural and Diffusion Characterizations of Mesostructured
Composite Zeolites BFZ
Jiajun Zheng, Meng Pan, Qiu Zhang, Yan Wang, and Ruifeng Li*
Research Centre of Energy Chemical & Catalytic Technology, Taiyuan University of Technology,
Taiyuan 030024, China, Corresponding author: E-mail: rfli@tyut.edu.cn
A core-shell composite zeolites possessing Beta zeolite cores and Y zeolite polycrystalline shells
(denoted as BFZ) was synthesized by a two-step hydrothermal crystallization procedure. The assynthesized samples were characterized by XRD, N2 adsorption–desorption, SEM, HRTEM, EDS and
Intelligent Gravimetric Analyzer (IGA). A hierarchical pore system resulted from interparticle spaces
in the shell and intracrystalline mesopores in the core was created in the composite, a more than 2
orders of magnitude gas transport improvement was therefore achieved in the composite as compared
with the corresponding physical mixture.
Keywords: Core-shell; Composite zeolites; Hierarchical pores
P-1.3-12
Synthesis of Novel Micro-mesoporous Beta-MCM-48 and Catalytic Performance in FCC
gasoline Hydro-upgrading Process
Aijun Duan*, Huadong Wu, Zhen Zhao*, Guiyuan Jiang, Jian Liu, Yuechang Wei
1 State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing, China,
duanaijun@cup.edu.cn; zhenzhao@cup.edu.cn
A novel micro-mesoporous composite Beta-MCM-48 was synthesized through in-situ self-assembly
method from Beta seed microemulsion in this research. The synthesis conditions of crystallization
time, crystallization temperature, SiO2/Al2O3 and the silica sources were investaged and optimized
systematically. Beta-MCM-48 combined the advantages of mesoporous MCM-48 in porosity and
microporous Beta in acidity. CoMoNi/Al2O3-BM48 catalysts supported on Beta-MCM-48(BM48)
and γ-Al2O3 composites showed good selective hydrogenation, olefin preservation and aromatization
activies. When the crystallization time of Beta precursor was 12 h, SiO2/Al2O3 was 100, WCTAB/WBeta
was 0.1011, the sulfur content in product of FCC hydro-upgrading process was 7.86 mg·L-1 and the
RON loss was only 1.65 units.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-13
Mesoporous HZn-ZSM-5 for methanol to aromatics
M.H. Qiu1, Z.Y. Liu1*, L. Xia1, X. Liu1, L. Wu1, H.J. Zhu1, Y.H. Sun1,2*
1 Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, PR China,
liuziyu@sari.ac.cn
2 State Key Laboratory of Coal Conversion, Shanxi Institute of Coal Chemistry, Chinese Academy of
Sciences, Taiyuan, Shanxi 030001, PR China, sunyh@sari.ac.cn
Mesoporous HZn-ZSM-5 was prepared by incorporating Zn atoms in HZSM-5 framework followed
by an alkali-treatment process. On which methanol was converted completely at 400oC, WHSV=2.5
h-1 and 1 atm during methanol to aromatics (MTA) process. The yield of aromatics increased from
41.39% for conventional HZSM-5 to 55.30% for the mesoporous HZn-ZSM-5, giving a higher space
time yield of aromatics. The high BET specific surface area of 551 m2/g, high pore volume of 0.51
cm3/g and suitable acid sites for mesoporous HZn-ZSM-5 may be responsible for the improved MTA
results.
P-1.3-14
Incorporation of Catalytic and Luminescent Activity in Mesoporous Silica
Via Sol-Gel Coordination Chemistry
N. Linares1, M. Rico1, A. Sepulveda2, E. Serrano1, E. Lalinde2, J. Berenguer2, J. Garcia-Martinez1
1Molecular Nanotechnology Lab., Dep. of Inorganic Chemistry, University of Alicante,
Alicante, Spain, E-mail: j.garcia@ua.es URL: www.nanomol.es
2Departamento de Química- Centro de Investigación en Síntesis Química,
Universidad de La Rioja, E-26006, Logroño, Spain
Sol-gel coordination chemistry is a novel synthetic approach, based on the hydrolysis and cocondensation of metal alkoxides linked to metal complexes, to prepare hybrid materials with
controlled mesoporosity. This method yields mesoporous silica with chemical functionality integrated
in its structure. The main advantages of this technique are excellent dispersion, low leaching and
enhanced stability of the coordination complex, which is protected by the silica framework. Using this
strategy, we have prepared a wide range of silica-based hybrid materials including luminescent solids
and heterogeneous catalysts. The incorporation of Pd(II) and Cu(I) complexes in mesoporous silica is
herein described, as examples of novel materials with catalytic and luminescent properties in their
framework.
P-1.3-15
Facile Large-Scale Synthesis of Monodisperse Mesoporous Silica Nanospheres
with Tunable Pore Structure
Kun Zhang*,1, Lang-Lang Xu1, Hai-Hong Wu*,1, Bélen Albela2, Laurent Bonneviot*,2, Peng Wu1
1Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal Uni-versity, Shanghai, China, kzhang@chem.ecnu.edu.cn
2 Laboratoire de Chimie , UMR-CNRS 5182, École Normale Supérieure de Lyon, Université de Lyon,
Lyon, France, laurent.bonneviot@ens-lyon.fr
MSNs with particle sizes below 200 nm was synthesized using cetyltrimethylammonium as
templating surfactant and small organic amines (SOAs) as the mineralizing agent. Isolation of pure
and re-dispersible monodispersed MSNs with either stellate (ST) or raspberry-like (RB) channel
morphologies was obtained for the first time. Tosylate counterions favored ST and bromide RB
morphologies at ultralow SOA concentrations. Both anions yielded worm-like (WO) morphology at
high SOA concentrations. A three step formation mechanism based on self-assembly and ion
competition at the electrical palisade of micelles is proposed. Facile recovery and re-dispersion using
specific SOAs allowed a high yield production at the kilogram scale.
1.3. Mesoporous materials and hierarchical porous structures
172
P-1.3-16
Study on synthesis and cracking properties of hydrothermally disordered mesoporous
silica-alumina material
J. Y. Zheng, Y. B. Luo, X. H. Mu, X. T. Shu
State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC), Beijing,
China,zhengjy.ripp@sinopec.com
A disordered mesoporous silica-alumina material with pseudo-boehmite structures was successfully
prepared through co-gel and aging process by using industrial inorganic materials. It was investigated
in detail by XRD、BET、MPM、SEM、TEM、XPS、FT-IR、NH3-TPD and ACE. The results
reveal that the material has large surface areas and pore volumes, and the average pore size is in the
range of 7~13 nm. This material is formed by many spherical particles aggregated together and its
micrography looks like uniform wrinkles. It has both Lewis acid and Brönst acid centres as well as
relatively high total acid content. The material possesses high hydrothermal stabilities and shows very
high cracking activities in the conversion of crude oil.
P-1.3-17
Synthesis of mesoporous basic zeolites for upgrading biofuels
V. Callejo1, J.M. Gómez, M.D. Romero.
1Chemical Engineering Department. Faculty of Chemistry. Complutense University of Madrid.
28040, Madrid, Spain. Fax: 913944114. Mail: victoriacallejo@quim.ucm.es
Zeolites are crystalline, hydrated aluminosilicates having microporous, regular structures. Much of
the success of zeolites in chemistry and chemical engineering can be attributed to the presence of the
well-defined micropores, which are responsible for the well-known molecular sieve effect. However,
in numerous cases, the sole presence of micropores also imposes significant limitations on the range
of reactions that are efficiently catalyzed by zeolite catalysts. Thus, several strategies have been
pursued to increase the accessibility of the active sites in zeolite catalysts, and various aspects of these
efforts have been reviewed and highlighted during the last years.
The mesoporous zeolites X may have more potential catalysis application in deoxygenation of larger
methyl esters than methyl octanoate because of their easier accessibility to active sites.
The purpose of this work is to investigate the synthesis of basic mesoporous zeolites in the presence
of anionic surfactant (SDBS-sodium-dodecylbenzene sulfonate) and to check the influence of the
amount of SDBS and to test their basics properties through the deoxygenation of methyl octanoate.
P-1.3-18
Switchable Wettability in a Bulk Material: Synthesis and Function of an Azobenzene Grafted
Silica Material
L. Gräfenstein1, M. Ried2, I. Köhl2, R. Herges2 and W. Bensch1
1Dep. of Inorganic Chemistry, University of Kiel, Germany, lgraefenstein@ac.uni-kiel.de
2Dep. of Organic Chemistry, University of Kiel, Germany
Ordered mesoporous silicas are of great scientific interest. The functionality of such silica materials
can be greatly enhanced by grafting switchable organic molecules on the pore wall surface. The
switching should lead to changes of the surface properties like hydrophilicity. In order to explore
whether the switchable hydrophilicity/hydrophobicity is pronounced enough, release experiments
were carried out with either toluene or tetrahydrofurane. These experiments delivered promising
results. The release of toluene from the trans material was significantly higher than the release from
the material in cis-configuration. An opposite behavior is observed for the release of tetrahydrofurane:
the amount released from the trans-configurated material was lower than that from the cis material.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-19
Desilicated mesoporous zeolites for methane dehydroaromatization
Selene Hernández Morejudo1, Christian Kjølseth2 and Stian Svelle1
1University of Oslo, Department of Chemistry, InGAP, Sem Sælandsvei 26, NO-0371 Oslo, Norwa,
s.h.morejudo@smn.no
2Protia AS, Gaustadalleen 21, NO-0349 Oslo, Norway
Desilicated mesoporous H-ZSM-5 zeolites have been prepared by alkali treatment with 0.1 or 0.2 M
NaOH solution. As a consequence of the desilication procedure, the Si/Al ratio of the materials
decreases. The formation of mesopores in the materials has been also confirmed by N2 adsorption
measurements. Mo/H-ZSM-5 (3wt% Mo) catalysts derived from the alkali treatments show higher
catalytic performance in the methane dehydroaromatization (MDA) when compared with the
untreated catalyst. The presence of mesopores in the zeolite seems to delay the deactivation of the
catalyst and prolonger the lifetime of the catalyst, improving the catalyst effectiveness in the MDA
reaction.
P-1.3-20
One-pot synthesis of mesoporous MCM-22 for benzene alkylation
C.H.L. Tempelman, N.G.R. de Caluwé, B. Mezari, E.J.M. Hensen
Department of Chemical Engineering, Eindhoven University of Technology, Eindhoven, The
Netherlands, c.h.l.tempelman@tue.nl
MCM-22 is currently commercially applied in the alkylation of benzene towards ethylbenzene (EB).
Delaminating MCM-22 to form ITQ-2 has proven an effective method to improve the selectivity
towards mono-substituted products. The procedure to obtain ITQ-2 is a time consuming post
synthesis procedure. In this study we discuss a one-pot synthesis procedure, involving an amphiphilic
organosilane, to obtain partially delaminated MCM-22 having some structural resemblance to ITQ-2.
Crystal thickness has been reduced significantly. Additionally, partial delamination introduces a
significant mesopore volume, not present in the conventional MCM-22. Mechanical stability of
delaminated MCM-22 is improved by the introduction of silica pillars.
P-1.3-21
Synthesis of micro/mesoporous materials by assembling of sol-precursors ZSM-5
in the structure of the mesoporous molecular sieve
R.Yu. Barakov, N.D. Scherban, P.S. Yaremov, V.M. Solomakha, V.G. Ilyin
L. V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine,
Prospekt Nauky, 31, Kyiv 03028, Ukraine. E-mail: barakovchem07@rambler.ru
Micromesoporous materials ZSM-5/MCM-41 were obtained by assembling of sol-precursors of
zeolites with MFI topology in mesostructural materials in the presence of micellar template
cetyltrimethylammonium bromide. The synthesis procedure involved two steps: first the X-ray
amorphous sol-precursors were obtained by a short-term hydrothermal treatment (12 – 24 h) of the
initial reaction mixture for zeolite at 160 °С and then assembled into a mesostructure at 100 °С for 72
h. These materials possess mesostructure and contain secondary building units of zeolite in the framework
which determines the acidic properties of MMM.
1.3. Mesoporous materials and hierarchical porous structures
174
P-1.3-22
Improved SSZ-13 zeolite catalysts for the methanol-to-olefins reaction
X. Zhu, L. Wu, E.J.M. Hensen*
Inorganic Materials Chemistry group, Eindhoven University of Technology, P.O. Box 513, 5600 MB,
Eindhoven, The Netherlands
e.j.m.hensen@tue.nl
SSZ-13 is recognized as a potential catalyst for the methanol-to-olefins (MTO) process due to high
light olefins selectivity. A hurdle hindering commercial application is rapid catalyst deactivation due
to coke deposition. To improve catalyst lifetime, mesoporosity was introduced by using a
diquaternary ammonium-type surfactant as a secondary template. This approach was combined with
synthesis of SSZ-13 in a fluoride medium, because it is known to decrease the silanol defect density.
It is shown that this combination leads to defect-free highly mesoporous SSZ-13 catalyst with the
highest MTO lifetime reported till to date.
P-1.3-23
Surfactant silica vesicles used as templates to obtain macro-mesoporous silicas or biphasic
mesoporous carbons
C.F. Santa1, S. Casale2, M. Jaber2, J.L.Guth3, L. Sierra1
1Materials science Group, Universidad de Antioauia, Medellín, Colombia, ligia.sierra@gmail.com
2 Laboratoire de Réactivité de Surface, UPMC, CNRS UMR 7197, Paris, France
3 Institut de Science des Matériaux de Mulhouse, IS2M-LRC CNRS 7228, Mulhouse, France
Using DLS and confocal microscopy, we show that a mixture of triblock copolymer surfactant with
long hydrophilic chains (PEO140PPO39PEO140) and TEOS self-assembles in alkaline medium into
micelles and vesicles. This dual template system was used to obtain large meso-macroporous silicas.
Also, adding resol monomers to the same system allowed us to prepare biphasic mesoporous carbonsilica hybrids, which can be etched with diluted HF or calcined to obtain biphasic mesoporous
carbons or meso-macroporous silicas, respectively. The materials were analyzed by N2 sorption and
TEM.
P-1.3-24
Facile synthesis of nano-crystallite orientated self-assembled ZSM-5 catalyst and
its LDPE cracking properties
Hongbin Zhang, Yahong Zhang and Yi Tang*
Department of Chemistry, Fudan University, Shanghai, China, 11110220046@fudan.edu.cn
Nano-crystallite orientated self-assembled zeolite ZSM-5 catalyst (denoted as NS-Z5) has been
facilely synthesized within 2 h at TPABr/SiO2 = 0.1 with the aid of seeds in a salt-rich gel system.
The NS-Z5 particle is composed of orientated assembled high-crystalline nanosized MFI crystallite
and possess very large/rough external surface and abundant particle stacking mesopores. Moreover,
this catalyst exhibits prominent performance for LDPE cracking reaction for synchronously
maintaining large amount and high strength of accessible acid sites which benefit from the
introduction of seeds. Therefore, the facile preparation and special structure may open new
possibilities for scaling-up production and catalytic application on large molecule conversion.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-25
Template assisted synthesis of mesoporous ZrO2 for application in catalysis
E.V. Golubina, N.E. Kavalerskaya, E.S.Lokteva
Dep. of Chemistry, Moscow State University, Moscow, Russia, golubina@kge.msu.ru
Ni and Pd catalysts were produced by template synthesis of mesoporous ZrO2 using organic
molecules (CTAB, ethylenediamine or polyethylene glycol) with subsequent impregnation with
corresponding nitrates. Catalytic tests in hydrodechlorination of chlorobenzene in gas phase and
1,3,5-trichlorobenzene in liquid phase demonstrated significant improvement of catalytic performance
in comparison with the use of microporous ZrO2 as a carrier. The influence of pore structure on
catalytic performance is discussed.
P-1.3-26
Comparative study of the porous structure of the products of the direct synthesis
miсromesoporous materials ZSM-11/MCM-41 and their mixtures
P.S. Yaremov, V.L. Struzhko, V.G. Ilyin
L.V.Pysarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine
Prosp. Nauky, 31, 03028 Kyiv, Ukraine. E-mail: yaremovp@ukr.net
A comparative analysis of the adsorption properties of the MMM samples obtained by direct template
synthesis, individual ZSM-11 and MCM-41, as well as their synthetic mixtures (composites) is
carried out. Obtained results shows some distinctive signs – features of the porous structure and
distribution of surface adsorption sites in mesopores, in particular increasing acidity, pK surface
hydroxyl groups of MMM, compared to the corresponding composites. This, seems to suggest the
possibility of using of similar adsorption analysis in combination with other methods of investigation
to diagnose the state of substance (material), in particular signing of hybridity.
P-1.3-27
Supported mesoporous and hierarchical porous Pd-TiO2 coatings with concomitant control
of particle size and pore structure
E. Ortel1, S. Sokolov2, C. Zielke3, I. Lauermann3, S. Selve1, K. Weh1, B. Paul1, J. Polte1,
R. Kraehnert1*
1 TU Berlin, Germany, erik.ortel@tu-berlin.de
2 LIKAT at the University of Rostock, Germany
3 Helmholtz-Zentrum Berlin, Germany
We present a new approach to the preparation of supported catalysts that permits the controlled
coassembly of preformed colloidal nanoparticles, pore templates, and an oxide precursor. The
synthesis is enabled by using Ti(IV) bis(ammonium lactato) dihydroxide as an unconventional oxide
precursor. The presented approach provides a modular strategy for the precise control of the catalysts
nanostructure. This is illustrated for the synthesis of mesoporous and hierarchically porous Pd/TiO2
catalysts prepared from Pd nanoparticles. The catalysts show high activity and selectivity in the gasphase hydrogenation of butadiene.
1.3. Mesoporous materials and hierarchical porous structures
176
P-1.3-28
Stabilizing Self-Assembled Alumina Mesophases
L. López Pérez,1 S. Perdriau,2 G. ten Brink,3 B.J. Kooi,3 H.J. Heeres1 and I. Melián-Cabrera1
1 Chemical Reaction Engineering (ITM), University of Groningen, Nijenborgh 4, 9747 AG
Groningen, The Netherlands. E: i.v.melian.cabrera@rug.nl
2 Stratingh Institute of Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The
Netherlands.
3 Zernike Institute for Advanced Materials and Materials Innovation Institute M2i, University of
Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
The crystallization of soft templated mesoporous aluminas obtained by the evaporation-induced selfassembly (EISA) with (S0H+)(XI) matching of a Al alkoxide derived gel has been investigated. The
solvent remarkably influences the stability of EISA alumina mesophases. The controlled hydrolysis in
sec-BuOH is most likely responsible for the adequate assembly of low-polymerized Al species onto
the surfactant; this appears to be an important factor to provide thermal stability. As a result, a
mesoscopic wormhole -Al2O3 having 300 m2/g (BET surface area), 0.450 cm3/g (pore volume) and
an increased acidic site density was obtained.
P-1.3-29
Catalytic Oxidation of N-heterocycles over Mesoporous TS-1
Jacob Oskar Abildstroem, Jerrik Mielby and Soeren Kegnaes
Department of Chemistry, Technical University of Denmark, Kgs. Lyngby, Denmark,
s072209@student.dtu.dk
Mesoporous TS-1 prepared by carbon-templating is significantly more active than conventional TS-1
for the oxidation of N-heterocycles with aqueous hydrogen peroxide. The increased catalytic activity
is caused by the introduction of mesopores that helps to overcome configurational diffusion
limitations within the microporous catalyst. Utilisation of mesoporous TS-1 for oxidation of Nheterocycles represents a new, more active and environmentally friendly method to synthesise Noxides.
P-1.3-30
The influence of preparation conditions on the formation micromesoporous materials
on the basis of MCM-41 and zeolite MEL
V. L. Struzhko, P. S. Yaremov, E. V. Senchylo, V. M. Solomakha, V. G. Ilyin
L.V.Pysarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine
Prosp. Nauky, 31, 03028 Kyiv, Ukraine. E-mail: vira_struzhko@ukr.net
By direct hydrothermal crystallization were obtained micromesoporous materials (MMM) based on
MCM-41 and zeolite MEL using two templates: molecular TBAJ and micellar TMABr. With the use
of the complex physical and chemical methods of research shows that the synthesized samples are
composition ZSM-11 – MСM-41 MMM with certain degree hybridness. It appears that the
development of MMM hybridness perhaps by use primary foods zeolite structure formation as initial
and subject to condition of zeolitization mainly of mezopore surface.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-31
Ion exchange as a technique of mesopore formation in low-silica zeolite X
A.B. Ayupov1, A.A. Leonova1,2, V.B. Fenelonov1, M.S. Melgunov1
1Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia, artem@catalysis.ru
2Novosibirsk State University, Novosibirsk, Russia
Na+ and NH4+ ion exchanged low-silica zeolite X (LSX) have been prepared and studied by means of
XRD analysis and N2/77K adsorption. NH4+-LSX after evacuation at 200°C has mesopores with
maximum of their pore size distribution at 4-5 nm according to BJH adsorption analysis. The possible
effect of hydrolysis of Si-O(H)-Al bridge bonds at 200°С and further dealumination of zeolite
framework is discussed. Mesopore formation in LSX under mild conditions gives perspective to
control pore size distribution in this adsorbent.
P-1.3-32
Direct synthesis of hierarchical porous SAPO-34-H nano-rod through the double-template
approach
Shang Jiang1, Runwei Wang*1, Zongtao Zhang1, Shilun Qiu1, Hongri Suo1
1 State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130012, China, jiangshang11@mails.jlu.edu.cn.
Formation of mesopores within zeolite crystals and preparation of nano-zeolites are two very
important factors in improving the activity and lifetime of the catalyst. Herein, hierarchical porous
SAPO-34-H nano-rod with a bimodal pore system is the first successfully synthesized by adding an
amphiphilic organosilane surfactant (STSAC) to conventional synthesis mixtures. The XRD spectra
exhibits wide-range patterns and a broad peak at low 2θ range, which are characteristic of the
corresponding SAPO-34 structure with high phase purity and the presence of the disordered
mesopores, respectively. The SEM reveals that the crystals are almost rod-like with diameters of 50–
200 nm and lengths of 1.5 um. For the application as the catalyst for methanol to olefins (MTO)
reaction, we believe that this material could perform better catalytic properties than that of
conventional SAPO-34.
P-1.3-33
Synthesis of hollow mesoporous silica spheres by treatment of core-shell structured mesoporous
spheres with alkaline solutions
M. Okamoto, H. Tsukada, S. Fukasawa
Dep. of Applied Chemistry, Tokyo Institute of Technology, Tokyo, Japan, mokamoto@apc.titech.ac.jp
Hollow mesoporous spheres were synthesized by treatment of core-shell structured spheres with
radial mesopores (core: mesoporous silica, shell: propyl group-grafted mesoporous silica) with
aqueous ammonia in the presence of the surfactant. Since propyl groups of the shell and the surfactant
adsorbed on the mesopore walls of the shell protected mesopore walls against aqueous ammonia, only
mesoporous silica core was dissolved to form hollow structure.
1.3. Mesoporous materials and hierarchical porous structures
178
P-1.3-34
Synthesis and Catalysis of Core-Shell Structured Microporous Titanosilicate and Mesoporous
Materials
Le Xu, Hong-gen Peng, Haihong Wu, Kun Zhang, Peng Wu
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,
East China Normal University, Shanghai 200062, China, hhwu@chem.ecnu.edu.cn
We report the synthesis and novel catalytic properties of core-shell structured hybrid materials with
microporous titanoslicate as core while mesosilica or mesocarbon as shell. TS-1@mesosilica ,
prepared by coating TS-1 zeolite crystals with mesosilica with the assistance of either
cethyltrimethylammonium bromide or P123 triblock copolymer, proves to be a good support for
dispersing and stabilized Au nanoparticles (NPs), giving rise to active and selective catalysts for gasphase epoxidation of propylene with H2 and O2 to propylene oxide (PO). On the other hand, TS1@mesocarbon prepared from TS-1@mesosilica via hard-templating replica technique turned to be
useful catalyst for liquid-phase synthesis of PO after supporting Pd NPs. Through assembling fibrous
silica KCC-1 onto TS-1 crystals and further supporting the Rh(OH)x species, a tandem catalyst for
one-pot synthesis of amides is achieved. Moreover, the mesosilica shell zeolite exhibits protecting
effects for the Ti-MWW core from desilication when employed in continuous ammoximation of
cyclohexanone with H2O2 and NH3.
P-1.3-35
Controlled mesoporosity in ZSM-5 by desilication : Effect of surfactant and quaternary amine
additives
Yun-Jo Lee, Ki-Won Jun, Kyoung-Su Ha, Geun Jae Kwak and Hae-Gu Park
Research Center for Green Catalysis, Korea Research Institute of Chemical Technology, P. O. BOX
107, Yuseong, Daejon, 305-600, South Korea, E-mail: yjlee@krict.re.kr
Effect of surfactant and quaternary amine additives in the creation of mesoporosity in commercial
ZSM-5 zeolite has been performed by desilication in alkaline solution. Triton X-100 as a surfactant
was effective to produce dual small mesopores and high surface area by lowering the surface tension
of the solution. Ink bottle type mesopores with big hysteresis on N2 desorption isotherm were
produced in presence of quaternary amines, especially tetraethylammonium (TEA) and
tetrapropylammonium (TPA) ion, where they interact with zeolite surface and protect the surface
from alkaline solution, finally making inner crystal empty by dissolving inside unprotected layer.
P-1.3-36
Nanoporous magnetic silicate matrices
Pshenko О. А.*, Antropova Т. V.,
Institute of Silicate Chemistry of Russian Academy of Sciences, Saint-Petersburg,
*Zubanova_OA@mail.ru
In present work the new vitreous silicate nanoporous matrices (with pore diameters ≤ 10 nm),
containing a crystalline phase of magnetite, are synthesized by chemical etching of the two-phase
ferriferous alkali borosilicate glasses in water solutions of mineral acids. The chemical kinetics of
etching process as well as the composition and structure of the resulted matrices are investigated.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-37
Structural and dynamics properties of confined water in MCM-41 samples
(Ø = 40Å; 25Å and 19Å).
J.P. Coulomb1*, N. Floquet1, and G. André2.
1 CINAM – CNRS, Campus de Luminy, CASE 913, 13288 Marseille Cedex 09, France.
*coulomb@cinam.univ-mrs.fr
2 Laboratoire Léon Brillouin, C.E.A. Saclay, France.
We have investigated the structural and dynamics properties of confined water phases in MCM-41
samples of different mesopore diameters ( Ø = 40 Å, 25 Å and 19 Å ) both by neutron diffraction ( by
using deuterated water D2O ) and neutron scattering ( by using ultra pure water H2O). By neutron
diffraction we have measured the molecular range order Lcoh., which characterize the confined water
phase in MCM-41 host materials, versus temperature. When decreasing the temperature, we observe a
sharp increases of Lcoh. ( it is the signature of the confined water solidification T3t ). In addition, by
incoherent quasi-elastic neutron scattering we have measured the translation mobility of the water
molecule Dt. We observe that Dt vanishes and that Lcoh. increases in the same narrow temperature
range which define the confined water solidification phenomenon. Such a solidification temperature
is strongly displaced toward the low temperature side for confined water phase in MCM-41 samples :
T3t = 236 K , 220 K and 216 K when the MCM-41 mesopore diameter decreases from 40 Å , 25 Å to
19 Å.
P-1.3-38
Generation of mesopores in ZSM-5 and its effect on catalytic properties
Quanyi Wang, Yingxu Wei, Jinzhe Li, Shutao Xu, Jingrun Chen, Yue Qi, Shuanghe Meng, Fuxiang
Chang, Baolian Su, Zhongmin Liu*
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, 457 Zhongshan Road, Dalian 116023, PR China
* Corresponding Author: liuzm@dicp.ac.cn Tel: 86-411-84379335; Fax: 86-411-84691570
In the present work, two kinds of MFI-based micro-meso composite porous catalysts were
hydrothermally synthesized successfully by the utilization of different soft templates. These catalysts
were well characterized by multi-type techniques. At the same time, their catalytic performances in
the 1,3,5-tri-isopropylbenzene (TiPB) cracking and methanol conversion were studied. Combined
studies in the physichemical character and catalytic properties investigation were employed to shed
light on the function of template in the synthesis of meso-micro composite ZSM-5.
P-1.3-39
Amine Templating Synthesis of Mesoporous Mo-M (M = Ce or Zr) Mixed Oxides
Nabil Al-Yassir 1,*, Abdouelilah Hachimi2, Mohammed Al-Yami1, Mohammed Al-Rasheedi1
1Center of Research Excellence in Petroleum Refining and Petrochemicals, 2 Center of Research
Excellence in NanoTechniology, Research Institute, King Fahd University of Petroleum and
Minerals, Dhahran 31261, Saudi Arabia.nalyassir@kfupm.edu.sa (* Corresponding autor)
Mesoporous Mo-Zr (Mo/Zr = 0.20 – 4.50) and Mo-Ce (Mo/Ce = 0.5) mixed oxides have been
synthesized by amine templating hydrothermal method using cetyltrimethylammonium bromide and
triethylammonium chloride. Crystallization temperature (100 – 175 °C) and time (24 – 72h) had little
effects on the crystalline phases. However, pH, presence of amine, and ratio of Mo/M (M = Ce or Zr)
showed significant influence on the formation of crystalline phases. Mo-Zr oxides of different ratios
showed the presence of different crystalline phases (ZrO2 (monoclinic and tetrahedral), MoO3 and
MoZr), whereas Mo-Ce phase was dominant for Mo-Ce mixed oxides. Mo-Ce mixed oxide displayed
better stabilization of Mo species, as compared to Mo-Zr oxides.
1.3. Mesoporous materials and hierarchical porous structures
180
P-1.3-40
Hierarchically Porous Single Crystal-like Mesoporous Silica and Zeolite by Mesomorphous
Polyelectrolyte-Surfactant Complexes as Dynamic Template
Chengxiang Shi, Hui Zhao, Jinyu Liu, Na Li, Jingui Wang, Tiehong Chen
Institute of New Catalytic Materials Science, Key Laboratory of Advanced Energy Materials
Chemistry (MOE), College of Chemistry, Nankai University, Tianjin 300071, P.R. China, chenth@
nankai.edu.cn
We report the fabrication of single crystal-like mesoporous silica SBA-1 particles with secondary
nanopores by using mesomorphous polyelectrolyte-surfactant complex as dynamical template. The
hierarchically structured silica synthesized by our method possessed single crystalline mesoporous
architecture with both the highly ordered 3-D cubic Pm3n meospores (SBA-1) and continuous
secondary nanopores (20~50 nm) in each crystal-like particle after removing the organic templates by
calcination. Interestingly and importantly, the presence of large amount of secondary nanopores did
not disturb the long-range order of mesostructure of each particle, which would possess both the
functions of crystal-like regularity and high diffusion efficiency of hierarchical pores. The formation
mechanism was discussed. Hierarchically structured zeolites were also successfully synthesized based
on the use of the polyelectrolyte-surfactant complexes as a template.
P-1.3-41
Properties of MCM-41 and SBA-15 mesoporous silicas
modified by ionic liquid
M. I. Onishchenko, I. A. Tyablikov, A. V. Yatsenko, E. E. Knyazeva, and B. V. Romanovsky
Dep. of Chemistry, Moscow State University, Moscow, Russia, mionishchenko@rambler.ru
One of the key steps in preparing the catalytic materials based on supported ionic liquids (ILs) is the
interaction between a functionalized IL and anchor OH groups on the support surface. Main goal of
the present study was the covalent immobilization of imidazolium-based IL on the surface of MCM41 and SBA-15 mesoporous silica supports. Some noticeable changes in the texture and morphology
of MCM-41 and SBA-15 support materials were resulted from the immobilization of IL. The pore
size of support used was shown to be the main factor governing the features of catalytic materials
prepared via IL immobilization.
P-1.3-42
Synthesis of IM-5 Zeolite Hollow Spheres
Weiya Yang1, Fengxiang Ling1, Lei Wang2, Zhiqi Shen1 , Shaojun Wang1
1 Fushun Research Institute of Petroleum and Petrochemicals, Fushun, Liaoning, China
yangweiya.fshy@sinopec.com
2 Department of Chemistry, Fudan University, Shanghai, China
Zeolites IM-5 hollow spheres were synthesized with 1,5-bis(methylpyrrolidinium)pentane as a
structure-directing agent in CTAB emulsion system. The obtained IM-5 hollow pheres displayed a
size of 2-6 μm. And its walls were composed of nano-sized IM-5 crystal particles. It was verified that
crystallization time and the concentration of CTAB strongly affected the formation process of hollow
spheres. The optimal prepared conditions are temperature of 443 K, crystallization time of 10 days,
and CTAB concentration of 1.39 mol/L. The formation mechanism of zeolite hollow spheres was
attributed to micelles in reaction system and charges between the surfactant and precursor particles of
IM-5.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-43
Mesoporous mordenites of different textures prepared by desilication and recrystallization: a
comparative characterization by N2 adsorption and electron tomography techniques
C. Bertrand-Drira1, G. Melinte2, O. Ersen2, D. Minoux3, A. Finiels1, F. Fajula1, C. Gerardin1
1ICGM/MACS, Montpellier, France, chloe.bertrand-drira@enscm.fr
2IPCMS, Strasbourg, France
3Total Research & Technology, Feluy, Belgium
The refining industry has now to treat heavier crude oil feedstocks. One of the major issues is the
development of new catalysts, combining micropores and mesopores, to enhance accessibility of large
molecules. Mesoporous mordenites were prepared by desilication and recrystallization. Desilication
leads to a large mesopore size distribution from 6 to 60 nm and recrystallization to a bimodal
distribution, with a narrow population around 4 nm and a broad one from 6 to 60 nm. In both cases
strong acid sites are maintained while extra weak acid sites are created only after desilication.
P-1.3-44
Highly ordered TiO2 nanotube arrays: factors affecting their morphology
А.N. Morozov, A.I. Mikhaylichenko
D.Mendeleyev University of Chemical Technology of Russia, Moscow, Russia, smallevil.666@mail.ru
In this work, we present a modified method to fabrication titanium oxide films, by potentiostatic
anodization of titanium. The structure of these films is a densely packed arrays of TiO2 nanotubes,
oriented strictly parallel to each other. We experimentally investigated the effects of the fluoride
concentrations, anodization temperatures and applied potentials on the formation and dimensions of
the titania nanotubes. According to the scanning electron microscopy the samples have open porosity,
with the internal pore diameter increasing linearly with the voltage at which the oxidation was carried
out and varied from 35 to 95 nm, for 20 to 60 V potentials respectively. The heights of these tubes
range from 2 to 80 μm. Due to the dense packing and the parallel arrangement of the nanotubes
structures their mechanical strength and absorption of light have improved. All the above advantages
make this structure very promising for various applications.
P-1.3-45
Synthesis of hierarchically porous MFI zeolites via controlled steam crystallization in the
mesoporogen-free system and minimum presence of zeolite structure-directing agent
R. R. Mukti1, M. Rilyanti1, M. Ogura2, H. Nur3, Ismunandar1
1Division of Inorganic and Physical Chemistry, Institut Teknologi Bandung, Jl. Ganesha no. 10,
Bandung, Indonesia, rino@chem.itb.ac.id
2Institute of Industrial Science. Department of Materials and Environmental Science, The University
of Tokyo, Komaba 4-6-1, Meguro-ku, Tokyo 153-8505, Japan
3 Ibnu Sina Institute for Fundamental Science Studies, Faculty of Science, 8130 UTM,
Johor Bahru, Malaysia
Hierarchically porous zeolites have drawn much attention since the sole presence of zeolite micropore
causes restriction to a molecular transport. In the absence of such mesoporogen, we have successfully
obtained mesoporous MFI zeolite via controlled hydrothermal steam crystallization implementing
amount of structure-directing agent that is much lower than typical recipe.
1.3. Mesoporous materials and hierarchical porous structures
182
P-1.3-46
Synthesis of regular hexagonal nut-like SBA-15 without additives
Juan Wang1, Huali Zhao1, Huijing Zhou1, Yuping Liu1
1Research Center for Analytical,College of chemistry, Nankai University, Tianjin 300071,China,
liuypnk@nankai.edu.cn
Morphology control of SBA-15 has attracted more attention due to its great importance in the
practical applications. In this paper, a simple route to regular hexagonal nut-like SBA-15 was
provided under the condition of additive-free by adjusting the amount of water and static time. With
the increase of amount of water, morphology of the obtained SBA-15 changed from particles to
aggregated egg sausages. When x=175, the prepared SBA-15 exhibited regular and uniform
hexagonal nut-like morphology which somewhat resembles steel hexagonal nuts in life. The
hexagonal nut-like particles are connected into a chain by end-to-end. The unusual morphology of
SBA-15 may be attributed to the aggregate behavior of the micelles of block copolymer affected by
long-time static condition and change of the amount of water.
P-1.3-47
Hierarchical TS-1 zeolite for the oxidation of bulky molecules
A. Silvestre-Albero1, A. Grau-Atienza2, E. Serrano-Torregrosa2, J. García-Martínez2 and
J. Silvestre-Albero1
1Laboratorio de Materiales Avanzados, Departamento de Química Inorgánica-Instituto Univesitario
de Materiales, Universidad de Alicante, Alicante, Spain, joaquin.silvestre@ua.es
2Laboratorio de Nanotecnología Molecular, Departamento de Química Inorgánica, Universidad de
Alicante, Alicante, Spain.
TS-1 zeolite has been widely used as catalyst in oxidation reactions. Unfortunately, the microporous
nature of the zeolite limits its catalytic application to small organic molecules. Herein we show that
desilication of TS-1 with NaOH promotes the formation of large mesopores. Catalytic studies in the
oxidation of organic molecules with different molecular dimensions, i.e. cyclohexene and 1-tertbutyl-1-cyclohexene, shows that desililated TS-1 exhibits a large improvement, ca. 400%, in the
catalytic activity for bulky molecules compared to the original TS-1, whereas the catalytic activity for
small molecules remains unchanged.
P-1.3-48
Calorimetric study on acidic properties of hierarchical MFI zeolites obtained from
protozeolitic units
Claudia Mónica López-León1; Héctor Armendáriz-Herrera 2; Ma. De Lourdes Guzmán-Castillo2;
José J. Fripiat 2; María-Guadalupe Cárdenas-Galindo1, and Brent E. Handy1*
1 CIEP/Facultad de Ciencias Químicas, Universidad Autónoma de San Luis Potosí. Av. Dr. Manuel
Nava #6, Zona Universitaria, San Luis Potosí, S. L.P, CP 78210, (México).
2 Instituto Mexicano del Petróleo, Eje central Lázaro Cárdenas #152, Col. San Bartolo Atepehuacan,
Delg. Gustavo A Madero, México, D. F. CP 07730, (México)
lopezleon_85@hotmail.com; handy@uaslp.mx; +52 444 826-2440 ext. 525
Acid properties of hierarchical MFI zeolites obtained by seed silanization and depolymerized
organogel zeolite were obtained using NH3 adsorption microcalorimetry, and FTIR spectroscopy of
alkylpyridine adsorption. These properties have been associated to structural parameters such as Al
content, and pore size distribution. Mesoporosity and microporosity were evident; Si/Al decreased as
a result of synthesis. The location and strength of acid sites are discussed in relation to pore structure.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-49
Synthesis of Zeolitic and non-Zeolitic Support of Random and Ordered Mesoporosity for
Nanosized Mo-M (M = Ce or Zr) Mixed Oxides
Nabil Al-Yassir*, Mohammed Al-Yami, Mohammed Al-Rasheedi
Center of Research Excellence in Petroleum Refining and Petrochemicals, Research Institute, King
Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia. nalyassir@kfupm.edu.sa
(* Corresponding autor)
Mesoporous Beta and ordered silica-alumina have been synthesized as a catalyst support for
nanosized Mo-Zr or Ce mixed oxides. Mesoporous Beta of hierarchical pore topology with random or
ordered mesoporosity was obtained by desilication, surfactant mediated hydrolysis and overgrowth of
ordered silica. Ordered silica-alumina was synthesized via two-step hydrothermal surfactant mediated
hydrolysis of amorphous silica-alumina (ASA). It was observed that the formation of structured pore
topology for Beta zeolite depends on the treatment method. These methods showed strong
dependence on the desilication solution, pH, and amount of surfactant. Surfactant hydrolysis of ASA
using tetramethylammonium hydroxide displayed better properties than NaOH.
P-1.3-50
Synthesis of Mesoporous Zeolite ZSM-58
T. Biemelt, C. Selzer, F. Schmidt, S. Kaskel
Dept. of Inorg. Chemistry, Dresden University of Technology, Dresden, Germany,
tim.biemelt@chemie.tu-dresden.de
ZSM-58 is a zeolite crystallizing in Deca-Dodecasil 3R (DDR) structure. The accessibility of the
pores’ entrances is due to dimensions of 4.4 × 3.6 Å restricted to small molecules like methanol or
carbon dioxide. This results in diffusion limitations and fast coking, causing poor catalyst lifetimes.
To overcome these problems, a hierarchical system with DDR-structure and additional meso- or
macro porosity is of great interest.
By applying several NaOH-as well as NaOH/CTAB-solutions, ZSM-58 was successfully desilicated,
resulting in materials which exhibit either meso- or macropores besides a retained micropore system.
The influences of the composition of the desilication solution and the initial Si/Al-ratios on the
properties of the resulting desilicated ZSM-58 samples were investigated.
P-1.3-51
Design of hierarchical porous aluminas by using one-pot synthesis
and different calcination temperatures
A. R. Passos1, L. Martins1, S. H. Pulcinelli1, C. V. Santilli1
1. Instituto de Química, UNESP - Univ Estadual Paulista, Prof. Francisco Degni 55, 14800-900
Araraquara-SP, Brazil
Significant interest has been directed toward the synthesis of hierarchical structured porous materials,
which are defined as materials that contain a multilevel structure consisting of interconnected pores
on different length scales. Hierarchical porous materials, consisting of mesopores and macropores, are
of considerable interest because they are expected to combine the benefits of each pore size regime.
In the present study we analyze the effect of the firing temperature on the hierarchical structure of the
multimodal porous alumina. Here, both the size and the quantity of macropores and mesopores
families, produced from emulsion and surfactant dual-templating, were tuned in a controlled way by
the firing temperature. Beyond over the control of the macroscopic and mesoscopic pores family, an
integrative sol-gel route allows the synthesis of aluminas with relatively high surface area, narrow
pore size distribution and good macropores connectivity at high temperatures.
1.3. Mesoporous materials and hierarchical porous structures
184
P-1.3-52
Hierarchic zeolites: the accessibility of acid sites
followed by quantitative IR studies of pivalonitrile adsorption
K. Góra-Marek, K. Sadowska, J. Datka
Jagiellonian University, Faculty of Chemistry, Krakow, Poland, gorak@chemia.uj.edu.pl
The new method of IR studies of accessibility of acid sites of Brønsted, Lewis type, and transition
metal cations with hindered pivalonitrile as probe molecules was elaborated. The accessibility factor
(AF) being ratio of concentration of sites interacting with pivalonitrile and pyridine was calculated. In
the series of the hierarchic zeolites ZSM-5 of Si/Al = 31.6 and 177 desilicated in NaOH and
NaOH/tetrabutylamonium hydroxide the AF values correlated well with the values of mesopore
surface determined. In extensively desilicated highly siliceous zeolites all acid sites were accessible to
bulky molecules. The explanation of this fact can be the migration of pivalonitrile inside micropore
The accessibility of Lewis acid sites was better than of Brønsted ones, what is related to the formation
of the Lewis sites by dehydroxylation of the Si-OH-Al groups formed by reinsertion of Al extracted
from zeolite (together with Si) during mesopores formation.
P-1.3-53
Synthesis of hierarchical SAPO-31 molecular sieves
Rui Zhang1, Wei Wu1*, O.V. Kikhtyanin2, Linfei Xiao1, Aijuan Zhao1, Huimin Wu1, A.V. Toktarev2
and G.V. Echevsky2
1 Key Laboratory of Environmentally-friendly Chemical Technology, College of Heilongjiang
Province; Sino-Russian Joint Laboratory of Catalysis, School of Chemistry and Material Sciences,
Heilongjiang University, Harbin 150080, Heilongjiang, China, wuwei@hlju.edu.cn;
2 Boreskov Institute of Catalysis, SB RAS, Novosibirsk 630090, Russia
SAPO-31 molecular sieve loaded with platinum or palladium is known to be very effective in
selective hydroisomerization of n-paraffins. In this paper, hierarchical SAPO-31 molecular sieve was
successfully synthesized by using di-n-butylamine to maintain the microporosity and using a
additional soft template with a silicon containing head group of 3-(trimethoxysilyl)propyl
hexadecyldimethylammonium chloride for the generation of mesopores. It permits to control the
mesopore proportion of hierarchical SAPO-31 molecular sieves by altering the content of TPHAC in
the initial gel composition.
P-1.3-54
Synthesis of cubic Ia3d mesoporous silica AMS-6 with the aid of acetate
S.X. Deng, W.C. He, X.L. Zhang, J.G. Wang, H.J. Zhou, T.H. Chen
Institute of New Catalytic Materials Science, Key Laboratory of Advanced Energy Materials
Chemistry (MOE), College of Chemistry, Nankai University, Tianjin 300071, P.R. China, chenth@
nankai.edu.cn
Mesoporous silica with three-dimensional (3D) bicontinuous cubic Ia3d pore structure and fascinating
caterpillar-like morphology was successfully synthesized by using N-lauroylsarcosine sodium (SarNa) as the template and 3-amionpropyltrimethoxysilane (APS) as the co-structure-directing agent
(CSDA) in the presence of a proper amount of acetate. In order to lead to a better understanding of the
influence of sodium acetate, different species of salts were also employed. It is obvious that
CH3COOK was also able to induce the formation of the cubic Ia3d mesostructure. However, other
species of salts (not including acetate) have the ability of inducing the fascinating morphology, but
fail to induce the cubic structure.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.3-55
Influence of temperature on the synthesis of SBA-3 nanostructured catalytic material
M. V. Ponte, M. L. Martínez, J. Cussa, O.A Anunziata, A R. Beltramone.
NANOTEC (Centro de Investigación en Nanociencia y Nanotecnología) Universidad Tecnológica
Nacional-Facultad Regional Córdoba, Córdoba, Argentina
abeltramone@scdt.frc.utn.edu.ar
Mesoporous silica SBA-3 was synthesized by using cationic surfactant cetyltrimethylammonium
bromide (CTAB). The varying of the synthesis temperature was studied.
The results of the X Ray Diffraction analysis show mesoporous materials where uniform mesopore
structure were obtained. We can observe that the temperature optimal was at 30 ºC. The
diffractograms show the formation of a higher ordered structure at 30ºC, and as the temperature
moves away from this value, a less ordered structure is obtained. The lattice parameter was calculated
by XRD, the value a0 at 30 ºC is 3.7 nm.
P-1.3-56
Synthesis of mesoporous ZSM-12 using a soft-template - Acid activity in the cyclohexane
cracking
Kele T. G. Carvalho¹, Ernesto A. Urquieta-Gonzalez¹
1Department of Chemical Engineering, Federal University of São Carlos, C. Postal 676, CEP 13565905 - São Carlos (SP) Brazil, urquieta@ufscar.br
Zeolites are crystalline microporous materials which have become extremely successful as catalysts
for the oil refining, petrochemistry and organic synthesis. The major drawback of zeolites is that their
micropores or cavities impose diffusional limitations. Recently, the creation of mesopores in zeolites
to increase the accessibility to the internal active sites has been the subject of many studies. The
objective of this work was to produce mesoporous ZSM-12 by direct synthesis using an amphiphilic
organosilane as mesopore-generating agent. The zeolites were characterized by XRD, N2
physissorption, SEM, EDX, and NH3-TPD and evaluated as acid catalysts in the cyclohexane
cracking. Intracrystalline mesopores were effectively generated during the synthesis of ZSM-12 using
the organosilane TPOAC. Mesoporous ZSM-12 with higher crystallinity were obtained using a
TPOAC/SiO2 molar ratio of about 0.03 and synthesis time of 11 or 16.5 h. In comparison with the
conventional ZSM-12, those zeolites containing mesopores were slightly more active at the beginning
of the reaction and catalytically more stable.
P-1.3-57
Remarkable enhancement of catalytic performance in the benzylation of aromatics with benzyl
alcohol over hierarchical mordenite
K. Leng, Y. Wang, Y. Sun*
School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin, China,
yysun@hit.edu.cn
The hierarchical mordenite obtained by acid-base-acid treatment (HM-ABA) exhibited excellent
catalytic activity in the benzylation of benzene with benzyl alcohol. The apparent reaction rate
constant for HM-ABA is 15 times as that for parent mordenite (HM) and twice as acid-leaching
mordenite (HM-A) and base-leaching mordenite (HM-AB). The enhanced catalytic performance for
HM-ABA could be attributed to more accessible acid sites and rich mesoporosity in HM-ABA.
Additionally, the catalytic performance on HM-ABA has been evaluated in other Fridel-Crafts
alkylations such as the benzylation of mesitylene with benzyl alcohol.
1.3. Mesoporous materials and hierarchical porous structures
186
P-1.3-58
CoZr/Mesoporous Zeolite Hβ Hybrid Catalyst for Efficient Synthesis
of C5-18 Paraffins from Syngas
Xing Huang1,2, Bo Hou2, Jungang Wang2, Debao Li2, Litao Jia2, Yuhan Sun2,3
1Key Laboratory of Renewable Energy and Gas Hydrate, Guangzhou Institute of Energy Conversion,
Chinese Academy of Sciences, Guangzhou 510640, P.R. China
2State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, Taiyuan 030001, Shanxi, P.R. China
3Low Carbon Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of
Sciences, Shanghai, 201203, P.R. China, yhsun@sxicc.ac.cn
CoZr/Hβ hybrid catalyst was prepared by a hydrothermal synthesis method, where mesoporous
zeolite Hβ was enwrapped onto the common Co-ZrO2 Fischer–Tropsch synthesis (FTS) catalyst. The
catalyst was characterized by BET, XRD, 27Al NMR, SEM, TEM, H2-TPR and NH3-TPD techniques.
CoZr/Hβ catalyst exhibited low reducibility due to the strong interaction between cobalt and the
support. As a result, it showed low FTS activity. However, quite high selectivity (74.3%) towards C5–
18 hydrocarbons was obtained even at a relatively low reaction temperature (503 K).
P-1.3-59
Hierarchical SAPO-11: synthesis, characterization and catalytic behavior in long chain
n-alkane hydroisomerization
R. Bértoloa, A. Fernandesa*, M. F. Ribeiroa, J. M. Silvaa,b, A. Martinsb,
aIBB, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, P-1049-001
Lisboa, Portugal
bADEQ and CIEQB, Instituto Superior de Engenharia de Lisboa - ISEL, R. Cons. Emídio Navarro
1959-007, Lisboa, Portugal,
* auguste.fernandes@ist.utl.pt
Hierarchical SAPO-11 materials were prepared by creation of a secondary mesopore system, using
two commercial carbon matrixes from Merck and Norit, with or without stirring. Structural and
textural properties of the samples were evaluated by XRD, SEM and N2 adsorption. All samples
showed XRD patterns typical of AEL phase. The presence of micropores and mesopores (average
size 150 Å) were detected for carbon templated samples. SEM images showed the presence of
cavities formed as a consequence of carbon combustion. The catalytic properties of the materials
(0.5wt.% Pt) were studied in the hydroisomerization of n-C10. All carbon prepared samples showed
high selectivities in monobranched isomers in spite of low conversions. Preliminary results suggest
possible interaction between the carbon surface groups and the synthesis gel, leading to different
distribution of the active sites in SAPO-11.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.4-01
Flexibility of ZIF-8 structure studied by 129Xe NMR
Marie-Anne Springuel-Huet, Andrei Nossov, Flavien Guenneau, Antoine Gédéon
UPMC, Univ. Paris 06, LCMCP, F-75005, Paris, France, marie-anne.springuel-huet@upmc.fr
The zeolitic imidazolate framework ZIF-8 has attracted much attention due to its remarkable thermal
and chemical stability. This structure was supposed to be rigid, but subsequent studies have shown
that ZIF-8 can easily adsorb molecules much larger than the window size thus revealing some degree
of flexibility of the framework Here we report the results of variable-temperature 129Xe NMR studies
of xenon adsorbed in ZIF-8 using a continuous flow of hyperpolarized xenon. At low temperatures,
129Xe NMR experiments as well as the adsorption isotherms show an abrupt increase of the chemical
shift (ca. 100 ppm within 2-3 K) and the amount of adsorbed xenon (up to ca. 8 Xe atoms per cavity),
respectively. These observations indicate that a change in the framework occurs.
P-1.4-02
Synthesis and characterization of Zeolite/Fe3O4 nanocomposite material and investigation
catalytic reaction of it
Mojgan Zendehdel*a, Safura Molla Mohammad Zamani
Department of Chemistry, College of Science, Arak University, Arak; Iran, mZendehdel@araku.ac.ir, mojganzendehdel@yahoo.com
In this paper, Fe3O4/NaY Zeolite nanocomposite with different molar ratio was synthesized and their
catalytic activity in esterification reaction was studied to determine the best molar ratio.
In the next step, the best molar ratio of Fe3O4/NaY Zeolite nanocomposite was used to prepare
Fe3O4/NaYZeolite/MCM-41 composite and then characterized by using FT-IR, XRD, TGA, SEM and
VSM techniques.
In esterification reaction, the effect of the amount of catalyst, reaction time, reaction temperature and
reusability of catalyst were investigated, and the Zeolite +16.6% Fe3O4composite showed the best
result. The catalyst can be easily separated from reaction with magnet and it can also be used for
several times.
1-S. P. Gubin, "Magnetic Nanoparticles", Wiley, (2009)
2- M. Zendehdel, A. Mobinikhaledi, H. Alikhani, N. Jafari, J. Chin. Chem. Soc, 57(4A), 2, (2010).
P-1.4-03
The Secret of the Maya Blue. A Story of Microporous Solid
E. Lima1, A. Guzmán2, M. Vera3, J.-L. Rivera1, J. Fraissard4
1Inst. Investigaciones en Materiales, Univ. Nac. Autónoma, México D. F.,
2Instituto Politécnico Nacional - ESIQIE, Zacatenco, 07738 México D.F., Mexico
3Universidad Autónoma Metropolitana, Iztapalapa, CP 09340, México D.F., Mexico
4Université Pierre et Marie Curie and ESPCI, LPEM, 75231 Paris Cedex 05, France
E-mail: lima@iim.unam.mx
The famous pre-Columbian Maya Blue pigment, a mixture of palygorskite and indigo, has been the
subject of much research without explaining the preparation and the extreme stability of this hybrid
organic/inorganic pigment. Our results have shown that indoxyl desorbed from Añil plant (Indigofera
Suffructicosa) is adsorbed on palygorskite and diffuses easily into the micropores where it is slowly
oxidized by atmospheric oxygen and UV radiations to provide indigo.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
188
P-1.4-04
Fluorinated Hydrotalcites: A New Family of Layered Double Hydroxides
Enrique Lima1, María de Jesús Martínez-Ortiz2, Jorge L. Flores-Moreno3
1Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito
exterior s/n, Cd. Universitaria, Coyoacán, 04510, México D. F., Mexico.
2 Instituto Politécnico Nacional-ESIQIE-DIQI. UPALM, Edif. 7 P. B., Zacatenco. México, D.F,
07738, Mexico, mjmartinez@ipn.mx.
3Universidad Autónoma Metropolitana-Azcapotzalco, Área de Química de Materiales, Av. San Pablo
No. 180, 02200 México D. F., Mexico.
Hydrotalcite-like compounds were synthesized by coprecipitation method at constant-pH. Aluminum
was introduced in the form of an octahedral aluminum fluorine complex during the synthesis. The
control of pH during the synthesis ensured that aluminum fluorine did not decompose to tetrahedral
species but remained in the octahedral (AlF6)3‑ form to be incorporated into brucite-like sheets.
Physicochemical, thermal, and spectroscopic characterizations showed significant modifications by
fluorine introduction regarding structural, textural, and adsorption properties. Fluorinated
hydrotalcites memory effect differed from that commonly observed in fluorine-free hydrotalcites.
Nitromethane and NH3 adsorption showed that the basicity of hydrotalcite was greatly modified by
the fluorine loading.
P-1.4-05
In Situ Generated Metal Nanoparticles on Porous Copper Chlorophosphate Frameworks
for Catalytic Aerobic Oxidations
C. S. Hinde1, R. Leithall1, T.S.A. Hor2, R. Raja1
1School of Chemistry, University of Southampton, UK, SO17 1BJ, C.Hinde@soton.ac.uk
2Institute of Materials Research and Engineering (IMRE), A*STAR, Singapore, 117602
A synthetic approach for novel generation of metal nanoparticles in situ from noble metal chloride
filled, 1D porous chlorophosphate framework materials is presented. Complex anions are supported in
the pores of the framework by inclusion of MClx (M= Au, Pt, Pd) in the precursor gel, with assynthesised materials calcined to generate nanoparticles on the material surface. These materials are
active catalysts in the oxidation of benzyl alcohol using molecular oxygen, with each metal providing
unique catalytic profiles and superior selectivity for benzaldehyde. Further application in aerobic
oxidation catalysis by activation of C-H bonds is explored.
P-1.4-06
Layered lanthanide 1,3,5-benzenetriphosphonates pillared with organic cationic species
Takahiro Araki, Atsushi Kondo, Kazuyuki Maeda
Dept. of Applied Chemistry, Tokyo University of Agriculture and Technology, Tokyo, Japan, kmaeda@cc.tuat.ac.jp
Pillared layer-type lanthanide 1,3,5-benzenetriphosphonates (LBP) were prepared with 4,4′-bipyridyl
(bpy) and 1,4-diazabicyclo[2,2,2]octane (dbo) as organic pillars. Isomorphous compounds LBP-bpyLn and LBP-dbo-Ln (Ln = Ce, Pr, and Nd) were obtained. According to powder X-ray crystal
structure solution these organic pillars do not exist as coordinating ligands but as cationic species.
Especially LBP-dbo has ordered micropores adsorbing N2, CO2, and H2 gas.
17 IZC, 2013. POSTER COMMUNICATIONS
189
P-1.4-07
Synthesis of Metal-Free Highly Nitrogen-Doped Carbon Porous Materials for Oxygen
Reduction Reaction in DMFC
Chin-Te Hung1, Ningya Yu2, Yu-Siang Kao1,3, Tuan-Chi Liu3, Shang-Bin Liu1,4,*
1 Inst. of Atomic & Molecular Sci., Academia Sinica, Taipei 10617, Taiwan, sbliu@sinica.edu.tw
2 Key Lab of Sustainable Resources Processing & Advanced Materials of Hunan Province, Hunan
Normal Univ., Changsha 410081, China
3 Dept. of Chemical Eng., National Taiwan Univ. of Sci. & Tech., Taipei 10607, Taiwan
4 Dept. of Chemistry, National Taiwan Normal Univ., Taipei 11677, Taiwan
A facile method to fabricate highly nitrogen-doped carbon porous materials (CPMs) by microwaveassisted self-assembly is reported. The metal-free N-CPMs exhibit good electrocatalytic activity
involving a typical 4-electron transfer pathway, durability, and excellent resistance towards methanol
cross-over during oxygen reduction reaction (ORR) surpassing Pt/XC-72. Further DFT calculations
showed that quarternary-N species tend to donate electrons to high-lying LUMO, hence are
responsible for the good ORR activity observed.
P-1.4-08
Selective olefin formation from butanol-2 on mesopores iron-phosphates LISICON and
NASICON catalysts
A.I. Pylinina, I.I. Mikhalenko
Peoples’ Friendship University of Russia, Russia, pylinina@list.ru, imikhalenko@mail.ru
Catalytic and adsorption properties of complex iron-phosphates LiFe2(PO4)3 and Na1+xZr2-xFex(PO4)3
known as LISICON and NASICON-type materials respectively with Fe2+ in the anionic part of the
phosphate before and after plasma chemical treatment in glow discharge of hydrogen are studied.
It was shown that a new type of catalysts from NASICON and LISICON-family is perspective in
selective alcohol transformation to desired products. Full conversion of butanol-2 to olefin can be
achieved by use of NASICON and LISICON plasma chemical pre-treatment in H2 medium as well as
the use of absorbed form of alcohol.
P-1.4-09
Impact of group VI metals on Ni/MgO for catalytic growth of CNTs by ethylene chemical vapor
deposition
A. E. Awadallah
Process Development Division, Egyptian Petroleum Research Institute, Cairo, Egypt, E-mail:
ahmedelsayed_epri@yahoo.com.
The present work aims to attain a correlation between the periodicity and catalytic growth activity of
carbon nanotubes (CNTs). Accordingly, the influence of adding group VI metals on Ni/MgO was
studied for synthesis of CNT by ethylene chemical vapor deposition. The materials were
characterized by XRD, SEM, TEM, TGA, Raman spectroscopy and BET measurements. The data
showed that the addition of group VI metals enhanced both dispersion and stabilization of Ni particles
on MgO solid support. XRD data of used catalysts revealed that, the intensity of graphite peak
increase gradually with increasing the atomic weight of group VI metals up to Mo, beyond which the
activity slightly decreases when using the W metal as a promoter. The Ni-Mo/MgO catalyst displayed
higher growth activity compared to Ni-Cr and Ni-W containing catalysts. TEM images illustrated that
the accumulated carbon over all catalysts are multi-walled carbon nanotubes in nature.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
190
P-1.4-10
COK-16: a tunable MOF with cation exchange properties
Sneha R. Bajpe1, Eric Breynaert1, Ana Martin-Calvo2, Danilo Mustafa1, Sofia Calero2, Christine E.
A. Kirschhock1 and Johan A. Martens1
1Center for Surface Science and Catalysis, University of Leuven, Belgium-3001.
Sneha.Bajperohita@biw.kuleuven.be
2Department of Physical, Chemical, and Natural Systems, University Pablo de Olavide, Seville,
Spain.
The HKUST-1 type hybrid metal organic framework (MOF) previously reported as
HPW@Cu3(BTC)2⋅3H2O (HPW=Keggin-type [PW12O40]3- polyoxometalate (POM), BTC=1,3,5benzenetricarboxylicacid) was tuned to allow exploiting its intrinsic cation exchange properties.
Occupation of the Keggin-type polyoxometalate [PW12O40]3- in every alternate pore of the framework
leads to limited pore accessibility. By reducing the fraction of encapsulated Keggin ions this hybrid
MOF (COK-16) becomes a fully functional cation exchanger. Cu2+ cations compensating the charge
of the [PW12O40]3- in the as-synthesized material can be exchanged with cations such as Na+ and Eu3+.
When exchanged with Eu3+, the material emits bright red color under UV light, suggesting that this
material could also prove to be an intriguing candidate for luminescence based applications.
P-1.4-11
Preparation of magnetic ZIF-based core-shell structure and its potential application
in a microreactor
Tong Zhang, Xinjuan Yan, Haiou Liu, Xiongfu Zhang*
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of
Technology, Dalian, China, xfzhang@dlut.edu.cn
Magnetic metal-organic frameworks (MOFs)-based core-shell structure, as a new kind of material,
began to attract attention with the aim of finding meaning applications in catalysis and pharmaceutical
chemistry. In this study, we initially prepared a novel magnetic zeolitic imidazolate framework8(ZIF-8)-based core-shell structure using two different strategies, electrostatic attraction method and
ZnO-induced growth method. Both of the two means are facile and mild which provide new
methodologies for the designing and synthesizing of magnetic MOF-based core structure.
Furthermore, the potential application of the magnetic core-shell structure in microfluidic devices is
presented.
P-1.4-12
Enhanced luminescent performance of hybrid mesoporous silicas via grafting by 1,8-naphthalic
anhydride and then modification with Europium
F. Wang, J.P. Wang, S.Y. Bai, and J.H. Sun
Department of Chemistry and Chemical Engineering, College of Environmental and Energy
Engineering, Beijing University of Technology, Beijing 100124, P. R. China. E-mail:
jhsun@bjut.edu.cn
Bimodal mesoporous silicas (BMMs), with well-defined mesopore channel and controlled structures,
were proved to be a good carrier for drug delivery. However, how to track the sustained/controlled
drug delivery performance would be difficult. Our preliminary results showed that the strategy of
fluorescent tracer play an important role but with unsatisfactory fluorescence intensity. Herein, the
luminescent hybrid BMMs were prepared successfully via grafting by 1,8-naphthalic anhydride and
then modified with Europium. Meanwhile, the structure and properties were characterized in detail
and gave the results that the effects of Eu amount on the structure characteristic and luminescent
properties were remarkable. The detailed characterization and deeper discussion are in progress.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.4-13
Versatile and Scalable Cooperative Template-Directed Coating Method to Construct Uniform
Microporous Carbon Shell for Multifunctional Core-shell Nanocomposites
Buyuan Guan, Xue Wang, Yu Xiao, Yunling Liu and Qisheng Huo
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun, China, huoqisheng@jlu.edu.cn
A very simple cooperative template-directed coating method are developed for the preparation of
core-shell, hollow, and yolk-shell microporous carbon nanocomposites. Particularly, the surfactant
used in the coating procedure improves the core dispersion in the reaction media and serves as the
soft template for mesostructured resorcinol-formaldehyde resin formation. The core diameter and the
shell thickness of the nanocomposites can be precisely tailored. Grams of polymer and carbon
nanocomposites can be easily prepared in a one-pot reaction. The Au@carbon yolk-shell catalyst
favors the reduction of more hydrophobic nitrobenzene than hydrophilic 4-nitrophenol, which makes
this type of catalyst promising nanomaterials as selective catalysts for hydrophobic reactants.
P-1.4-14
Construction of Two 3D Copper-Based Coordination Polymers With
Multifunctional Ligand, PmBC
Jiahuan Luo, Jing Wang, Peng Tian, Yunling Liu, Lirong Zhang*
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun 130012, P. R. China, zlr@jlu.edu.cn
Coordination polymers as an emerging class of functional solid state materials, has bourgeoned in the
last decade due to their unique hybrid character, exceptional tunable porosity and potential logical
assembly from molecular building blocks. The potential applications of coordination polymers are
being realized in areas such as gas adsorption and separation, catalysis, non-linear optics, and drug
release. Our group has explored a series of N-heterocyclic carboxylic acids based ligand such as 4,5imidazoledicarboxylic acid, 1,2,3-triazole-4,5-dicarboxylic acid and 2-positon of the imidazole ring
with diverse substituent groups such as methyl, ethyl or pyridyl. Here, we design and synthesize a
new type of 4-(Pyrimidin-5-yl)benzoic acid (PmBC) as multifunctional ligand, and construct two
compounds with 3D framework. Both compounds were characterized by elemental analysis, IR
spectroscopy and single-crystal X-ray diffraction.
P-1.4-15
Construction of Two 3D Metal-Organic Frameworks Based on 1,2,3-Triazole-4,5-dicarboxylate
Ligand
Tingting Zhao, Dongmei Wang, Huoqi Sheng, Yunling Liu*
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun 130012, P. R. China. yunling@jlu.edu.cn
Two novel metal-organic frameworks (MOFs) |(H3O)1.5(H2O)3|[Cd2K0.5(C4N3O4)2(H2O)] (1),
|(H3O)(H2O)|[Cu4(C4N3O4)3(H2O)3] (2), were solvothermally synthesized using 1,2,3-triazole-4,5dicarboxylic acid (H3tzdc). In compound 1, the ligand coordinated to cadmium atoms to generate a
tetranuclear cluster that leads to a 5-connected bnn network with two distinct channels along the
[001] and [010] directions. In compound 2, the ligand, which serves as a T-shaped linker coordinated
to copper atoms to form a unique metalloporphyrin-like plane, resulting in a pto network. In addition,
Gas adsorption was investigated for compound 1.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
192
P-1.4-16
Synthesis and Applications of Nitrogen-containing Ordered Mesoporous Carbons
Jinming Xu, Xiaochen Zhao, Aiqin Wang and Tao Zhang*
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, China, xujm@dicp.ac.cn
A new two-step method is developed to synthesize ordered mesoporous polymer and ordered
mesoporous carbon. In this regard, resorcinol and formaldehyde were employed as the source of
polymer and carbon, while the self-assembly process were accomplished rapidly by using a low
amount of base and acid catalysts at room temperature, subsequently. Via the same strategy, Ncontaining ordered mesoporous polymers and carbons were also fabricated by adding dicyandiamide
to the synthetic solution. The stability of obtained mesoporous carbon is extremely high. After the
activation by CO2, the carbon materials maintained well ordered mesostructure, the BET surface area
enlarged to 2660 m2/g, and total pore volume increased to 2.01 cm3/g. Besides, in the catalytic
dehydrochlorination of 1,2-dichloroethane into vinyl chloride reaction, the N-containing ordered
mesoporous carbon exhibited excellent activity, selectivity and stability.
P-1.4-17
Growing a porous γ-AlO(OH) layer of tunable thickness
on MIL-53(Al) particles
I. Bezverkhyy1, G. Ortiz2, G. Chaplais2, C. Marichal-Westrich2, J.-.P. Bellat1
1Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR6303 CNRS – Université de Bourgogne,
Dijon, France, igor.bezverkhyy@u-bourgogne.fr
2 Institut de Science des Matériaux de Mulhouse, LRC CNRS 7228, Mulhouse, France
We report a new method allowing to obtain a porous γ-AlO(OH) layer on the surface of MIL-53(Al)
particles. The method is based on a partial hydrolysis of MIL-53(Al) during reflux in water at 100°C
which is shown to proceed in the following way:
Al(OH)bdc + xH2O → (1-x)Al(OH)bdc + xH2bdc + xγ-AlO(OH)
After reaction the molecules of 1,4-benzenedicarboxylic acid (H2bdc) are intercalated into the pores
of MIL-53(Al). γ-AlO(OH) (boehmite) forms on the surface of MIL-53 particles a porous layer
whose thickness depends on the reflux time. Extraction of the intercalated H2bdc molecules under
mild conditions allows to obtain MIL-53(Al) crystallites coated with a layer of γ-AlO(OH). The OH
groups of such layer can be used as anchoring sites for the material functionalization by grafting.
P-1.4-18
Metal-organic frameworks as strong basic catalysts via post-synthetic deprotonation of
hydroxyl groups
P. Valvekens1, D. Jonckheere, 1 D. De Vos1
1Centre for Surface Chemistry and Catalysis, Department of Microbial and Molecular Systems,
University of Leuven, Leuven, Belgium, pieterjan.valvekens@biw.kuleuven.be
This work introduces a new approach towards metal-organic frameworks (MOFs) as basic catalysts.
Rather than introducing N-functionalized ligands as weak basic sites, as is often reported in literature,
the weak acidic hydroxyl functions in MOFs are converted into strong basic sites within the
framework via a post-synthetic deprotonation procedure using a strong homogeneous base. This
procedure was performed on a selection of hydroxyl bearing MOFs. The extent of deprotonation in
these materials was evaluated using FTIR and NMR. The applicability and reusability of these basic
catalysts was explored for Michael additions, Tishchenko condensations and alkyne isomerization
reactions.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.4-19
Fast Synthesis of MOFs Using Nanosized Zeolite Crystal Seeds
Suyan Liu1, Ying Zhang2, Yan Meng2, Fei Gao2
1Department of Applied Chemistry,
2Department of Materials Science and Engineering, China University of Petroleum (Beijing),
Changping District, Beijing102249, China Y.Zhang@cup.edu.cn
We report a seed growth method using zeolite MOR, ZSM-5 and Y crystal seeds for the rapid
hydrothermal synthesis of MOFs. Common microsized zeolites without surface modification are
added to MOFs hydrothermal synthesis systems and in-situ break into nanosized zeolite seeds.
Nanosized zeolite seeds can offer enormous surface areas to nucleate MOFs and the in-situ generation
way can avoid aggregation and separation troubles relevant to nanosized zeolite production.
Typically, only about 1.3 wt% microsized MOR crystals relative to the metal and ligand precursors
for MIL-101 formation, can shorten the crystallization complete time by 75% compared to the
conventional MIL-101 crystallization without adding zeolites. The methodology is an important step
toward the MOF industrial production and may shed light on the preparation of MOFs and zeolits
composite materials.
P-1.4-20
Cu Schiffbase Functionalized Periodic Mesoporous Organosilica: A Highly Stable
Heterogeneous Catalyst
X.F. Shi1, X.H. Hu1, B.B. Fan1, W.B. Fan2, R.F. Li1
1Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan,P.R. China,
fanbinbin@tyut.edu.cn
2State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, China
A new approach for the preparation of metal complex functionalized periodic mesoporous
organosilica is presented. The approach involves that cloromethylation of -C6H4- in the framework of
PMOs into active –C4H3CH2Cl-, followed by grafting CuSaldien (N, N′-bis(salicylidene)diethylenetriamine) via reacting -C4H3CH2Cl- with Saldien. The obtained samples were
characterized by XRD, N2-adsorption, FTIR, UV-vis, TEM and 13C NMR. Compared with the sample
prepared by immobilizing CuSaldien on SBA-15 modified by 3-chloropropyltriethoxysilane, the
sample prepared by this novel approach exhibited much higher stability in the oxidation of
cyclohexane with H2O2.
P-1.4-21
Highly porous neutral, acid and basic micro- and mesoporous carbon materials: synthesis and
properties
N.D. Scherban, P.S. Yaremov, V.G. Ilyin, S.M. Filonenko
L. V. Pisarzhevsky Institute of Physical Chemistry, National Academy of Sciences of Ukraine,
Prospekt Nauky, 31, Kyiv 03028, Ukraine. E-mail: natalka112@bigmir.net
Micropore volume and adsorption capacity for hydrogen (up to 1,48 wt.%) increase in the conditions
of non-catalytic bulk carbonization of sucrose with increasing the temperature. It was found that
activation with steam at 800 and 850 °C leads to a significant increase of specific surface area of
carbon materials (up to 2290 m2/g) and hydrogen adsorption – up to 1,9 and 2,0 wt.% respectively. Pand N-containing carbon porous materials are characterized with highly developed porous structure
(SBET up to 1500 m2/g), acidic and basic properties respectively and high ion-exchange capacity (up to
5.9(1,5) mmol/g).
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
194
P-1.4-22
Determining the indomethacin loading efficiency
in isostructural MIL-101 frameworks with the solid-state NMR
Tomaž Čendak1, Emanuela Žunkovič1, Tina Ukmar1, Venčeslav Kaučič1, Gregor Mali1,2
1National Institute of Chemistry, Hajdrihova 19, Ljubljana, Slovenia, tomaz.cendak@ki.si
2ENFIST Center of Excellence, Dunajska 156, Ljubljana, Slovenia
In this contribution, we report about the solid-state NMR study of indomethacin molecules adsorbed
in the isostructural MIL-101 frameworks. MIL-101 frameworks with different metal centers (Al, Cr,
Fe) were impregnated with different concentrations of indomethacin. We studied the effects of metal
centers and amino groups on the drug loading ratio. We also showed how relatively simple and quick
NMR measurements can be used as a tool to determine indomethacin loading efficiency.
P-1.4-23
Synthesis and crystal structures of two new microporous
copper rubidium diphosphates
L.V. Shvanskaya, O.V. Yakubovich, V.S. Urusov
Dep. of Geology, Moscow State University, Moscow, Russia, lshvanskaya@mail.ru
Two new copper rubidium diphosphates, Rb2CuP2O7(I) and Rb2Cu3(P2O7)2(II), have been obtained
using solid-state and flux crystallization methods in the system Rb-Cu-P-O at 650o and 750o C,
respectively. Their crystal structures were determined by single-crystal X-ray diffraction: (I) S.G. Cc,
Z = 4, a = 7.0020(10) Å, b = 12.751(3) Å, c = 9.773(2) Å, β = 110.93(3)o, R = 0.035; (II) S.G. P21/c,
Z = 2, a = 7.7119(2) Å, b = 10.5245(5) Å, c = 7.8034(2) Å, β = 103.862(2)o, R = 0.033. Their crystal
structures are based on mixed microporous 3D frameworks built from diphosphate [P2O7] groups and
[CuO5] tetragonal pyramids (for I) and the triplets of highly distorted [CuO6] octahedra sharing edges
(for II). The framework of (I) has a system of intersecting open channels along [001], [101], [110],
and [100] directions. The 3D framework of (II) is denser and characterizes by 1D channels along
[001] direction. The Rb+ ions positioned in the channels show CN8 (I) and CN 10 (II).
P-1.4-24
Anomalous paraffin selectivity of ZIF-7 in the separation of light
olefin/paraffin mixtures
Canan Gücüyener, Johan van den Bergh, Jorge Gascon, Freek Kapteijn
Catalysis Engineering, Chemical Engineering Department, Delft University of Technology,
c.gucuyener@tudelft.nl
ZIF-7 is a member of the MOF family and has a sodalite topology with a six-membered ring pore
opening of 3 Å. Unary adsorption of several hydrocarbons on ZIF-7 shows Type IV isotherms
indicating a ‘gate opening’ mechanism: the specific interaction between the linker and the adsorbent
causes an uptake and release of the hydrocarbons in certain pressure ranges. Preferential adsorption
depends on the polarity, shape and molecular mass of the adsorbent. This behaviour is further
confirmed by olefin/paraffin binary adsorption studies in terms of breakthrough experiments. Through
adsorptive separation, direct production of pure olefin upon adsorption and pure paraffin upon
desorption in ZIF-7 packed columns is possible. In this work a detailed investigation of this step-wise
adsorption and separation of paraffins and olefins is presented together with a rigorous performance
assessment.
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P-1.4-25
Synthesis of porous materials based on a Si-N network in Ionic Liquids
Ana Isabel Saugar1, Joaquín Pérez-Pariente1*
1Institute of Catalysis and Petroleum Chemistry (CSIC), Madrid, Spain, * jperez@icp.csic.es
Silicon-nitrogen network based porous materials have been obtained by a novel method based on the
preparation of silicon diimide gel by the ammonolysis of silicon tetrachloride using an ionic liquid as
solvent followed by a heating process. The resulting materials contain ionic liquid species occluded
inside the framework, which can be removed by heat treatment at 600 ºC under flowing ammonia,
leading to high surface area materials with a mesoporous or microporous structure depending on the
composition of the synthesis gel. Due to their high quantity of strong basic NH sites and the
possibility of tailoring the pore size, these silicon-nitrogen based materials are promising shape
selective basic catalysts.
P-1.4-26
Materials Center – Materials for every Challenge
Ronny Grünker,1 Martin R. Lohe,1 Stefan Kaskel,1
1Dresden University of Technology, Germany, stefan.kaskel@chemie.tu-dresden.de
No matter whether you are interested in porous materials such as silica, carbons, metal-organic
frameworks (MOFs) or MOF precursors (pre-formed metal clusters or linkers), Materials Center can
provide you with appropriate adsorbents. Our experienced researchers can give appropriate guidance
finding suitable materials for challenging applications and solutions to problems of any kind in the
field of “porous materials”. You might choose between various adsorbents from our permanent portfolio, for instance MOF materials differing in metals, linker functionalities, pore sizes, surface areas,
thermal and hydrothermal stabilities. But also materials which are currently not part of our product
list can be synthesized on demand to get the right material for a certain task.
URL: http://www.chm.tu-dresden.de/ac1/materials_center/index_engl.shtml (status 2012/11/30)
P-1.4-27
Kinetic Water Stability of an Isostructural Family of Zinc-based Pillared Metal-Organic
Frameworks
Himanshu Jasuja, Nicholas C. Burtch, You-gui Huang, Yang Cai, and Krista. S. Walton
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive
NW, Atlanta, Georgia 30332, U.S.A, hjasuja3@gatech.edu
In this work, it is shown that by varying the functional groups on the 1,4-benzenedicarboxylic acid
(BDC) linker of DMOF [Zn(BDC)(DABCO)0.5] it is possible to systematically tune the kinetic water
stability of this isostructural family of MOFs in the presence of large amounts of adsorbed water.
Notably, while the parent DMOF structure is unstable, the variation containing the tetramethyl BDC
ligand remains fully stable after the cyclic adsorption of large amounts of water. We show that these
trends are not due to hydrophobicity and that the precise placement of the methyl groups on the BDC
ligand is critically important in determining the water stability of these MOFs. Furthermore, we shed
light on the important distinction between kinetic and thermodynamic stability in these MOFs.
Molecular simulations are also used to provide insight into the structural characteristics governing
these trends in kinetic water stability.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
196
P-1.4-28
Zr and Hf based Metal-Organic Frameworks
Volodymyr Bon,1 Irena Senkovska,1 Volodymyr Senkovskyy,2 Stefan Kaskel1
1Dresden University of Technology, Germany, irena.senkovska@chemie.tu-dresden.de
2Leibniz-Institut für Polymerforschung Dresden, Dresden, Germany
Herein we report novel Zr- and Hf-based topologically different materials DUT-67, DUT-68 and
DUT-69, synthesized by applying a modulated synthesis approach, and the bent 2,5thiophenedicarboxylate (tdc2-) ligand as well as DUT-51 (isoreticular to DUT-67), where
dithieno[3,2-b;2',3'-d]thiophene-2,6-dicarboxylate (dttdc2-) was used as a linker. Nitrogen
physisorption was performed to evaluate the porosity of all synthesized materials. Specific surface
areas calculated from nitrogen adsorption isotherms using BET theory amount to 2335 m2g-1 for
DUT-51(Zr), 1859 m2g-1 for DUT-51(Hf), 1064 m2g-1 for DUT-67(Zr), 810 m2g-1 for DUT-67(Hf),
891 m2g-1 for DUT-68(Zr), 749 for DUT-68(Hf), 560 m2g-1 for DUT-69(Zr) and 450 m2g-1 for DUT69(Hf). All reported materials are hydrolytically stable and show extreme high chemical stability in
the acidic medium.
P-1.4-29
Mesoporous carbon functionalized with Ni nanoparticles
for hydrogen storage
D. Fernand1, P.L. Llewellyn1, V. Hornebecq1
1MADIREL, CNRS UMR 7246, Aix-Marseille University, Marseille, France,
deborah.fernand@etu.univ-amu.fr
H2 is a promising energy carrier. However, some key issues need to be unlocked, such as the
reversibility of the storage. In the case of adsorption of H2 on porous solids, specific interactions need
to be developed between both components, leading to not only high adsorbed amounts of gas but also
to a desorption that is not too costly from an energetic point of view. The idea is thus to associate, in a
same material, a high specific surface area and specific adsorption sites. In this way, organized
mesoporous carbon is first synthesized; it exhibits a high specific surface area (~700 m2/g). Then, Ni
NPs are inserted in the porous matrix. Finally, H2 adsorption properties are studied at 77 K and p < 1
bar with a Tian-Calvet type microcalorimeter coupled with a manometer, allowing to draw the
isotherms and evaluate the adsorption enthalpies as a function of surface coverage.
P-1.4-30
Synthesis and properties of photochromic quartz-like glasses
M.A. Girsova, I.N. Anfimova, T.V. Antropova, O.A. Pshenko
Institute of Silicate Chemistry of Russian Academy of Sciences, Saint-Petersburg, Russia,
antr2@yandex.ru
Photochromic quartz-like glasses (PCQG) are new composite photosensitive materials in which can
be realize the phenomenon of localized plasmon resonance owing to formation of the metal particles
in a dielectric matrix by UV irradiation.
Relevance of the work is due to the prospect of PCQGs for creation of the plasmon waveguides. The
PCQG plates are synthesized by impregnation of the nano porous glasses by photosensitive
component. The spectroscopic studies of the PCQGs, containing AgCl phase have been performed.
The plasmon resonance peaks of silver are revealed on a surface and in the volume of PCQG plates
when they were exposed to UV laser radiation.
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P-1.4-31
N-containing heterocyclic carboxylate−CaFe layered double hydroxide nanocomposites −
synthesis, characterisation and some catalytic reactions
M. Sipiczki1, Á. Kukovecz2,3, Z. Kónya2,4, P. Sipos1, I. Pálinkó5
1Department of Inorganic and Analytical Chemistry, University of Szeged, Szeged, Hungary
2Department of Applied and Environmental Chemistry, University of Szeged, Szeged, Hungary
3MTA-SZTE "Lendület" Porous Nanocomposites Research Group, Szeged, Hungary
4Reaction Kinetics and Surface Chemistry Research Group of the Hungarian Academy of Sciences,
Szeged, Hungary
5Department of Organic Chemistry, University of Szeged, Szeged, Hungary, palinko@chem.uszeged.hu
In this contribution, results of our work concerning the immobilisation of L-prolinate, DLpipecolinate, indol-2-carboxylate, dihydroindole-2-carboxylate or the anions of nipecotic and
isonipecotic acids are communicated together with full-scale characterisation (XRD, TEM, SEM,
EDX, thermogravimetry, FT-IR, UV-Vis, the ICP method and molecular modelling) and application
of some as organocatalysts in cross aldol dimerisation−condensation.
The intercalation was successful in each case and some of the nanocomposites were proved to be
active in the test reaction.
P-1.4-32
Synthesis and characterization of Zn-tartarate MOF
Ana Palčić1, Matjaž Mazaj2, Emanuela Žunkovič2, Josip Bronić1.
1Ruđer Bošković Institute, Bijenička 54, 10000 Zagreb, Croatia, bronic@irb.hr
2National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia
Conventional hydrothermal synthesis of the starting clear solution mixture, having following molar
composition: 1.0 Zn(NO3)2 × 2.0 C4H4O6 × 206.0 H2O, was made at 120 °C. After 72 h of heating
and slow cooling, relatively large (up to 250 m), elongated, transparent, polycentric crystals were
obtained. Characterizations of the crystals were done using several methods such as: elemental
analysis (AAS), FTIR spectroscopy, electron microscopy (SEM), thermal analysis (TG, DTG), N2
absorption/desorption, and structure analysis (PXRD). The results have shown that new phase
consists of monoclinic crystals (alpha = gamma = 90.000°, beta = 90.916°) with following unit cell
parameters: a = 11.76 Å, b = 9.034 Å and c = 5.076 Å.
P-1.4-33
Synthesis, Characterization, and CO2 Adsorption Properties of Chromium-based MOFGraphene Oxide Composite
Zhou Xin, Xia Qibin, and Li Zhong
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou,
China, cezhli@scut.edu.cn
Adsorption separation by porous adsorbents is a cost-effective and energy-saving way to collect trace
CO2 at ambient condition. We combined the uniqueness of MIL-101 and graphene sheets, and
synthesized the composite of MIL-101 and graphene oxide, GO@MIL-101. This composite was
characterized by using nitrogen sorption, XRD, FT-IR and SEM. The adsorption isotherms of CO2 on
this GO@MIL-101 were measured by gravimetric method. It is interesting that despite the decline of
its surface area, the CO2 isotherms on GO@MIL-101 was higher than that on MIL-101. The CO2
adsorption capacity of GO@MIL-101 is up to 22.4mmol/g at 25bar, 298K, which is higher than that
of GO@MIL-101, 20.9mmol/g.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
198
P-1.4-34
Enhancement of the mechanical resistance of Metal Organic Frameworks by functionalization:
A subtle combination of X-ray diffraction and molecular simulations
P.G. Yot 1, Y. Ke 1, F. Salles 1, P. Horcajada 2, T. Devic 2, C. Serre 2, G. Férey 2, G. Maurin 1.
1 ICGM, University Montpellier 2, France, pascal.yot@um2.fr
2 ILV, University of Versailles St-Quentin, France
The impact of the applied mechanical pressure (<3 GPa) upon of a series of MOFs, MIL-47(V), MIL125(Ti), MIL-125(Ti)_NH2, UiO-66(Zr) and UiO-66(Zr)_NH2 was explored by combining x-ray
powder diffraction and force field based molecular simulations. The influence of topologies (1D or
3D arrangements of micropores), crystal density of these porous solids and presence/absence of
grafted functions the organic linkers were evidenced. MIL-47 exhibits a spectacular reversible
pressure induced structural transition at 125 MPa under compression with a unit cell variation of 40%
and a large hysteresis (70 MPa). At the difference, MIL-125 and UiO-66 only show a tiny volume
change (2%) in the pressure range with an expansion of the pressure domain of stability and a higher
compressibility for the NH2 versions.
P-1.4-35
Controlled defect introduction during synthesis as a novel tool to improve the catalytic activity
of Zr-MOF UiO-66
Frederik Vermoortele1, Bart Bueken1, Ben Van de Voorde1, Alexandre Vimont2, Dirk De Vos1
1Centre of Surface chemistry and catalysis, KULeuven, Leuven, Belgium,
frederik.vermoortele@biw.kuleuven.be
2Laboratoire Catalyse et Spectrochimie, UMR CNRS 6506 – ENSICAEN, Caen, France
In this study we show that the addition of a large amount of a volatile monocarboxylic acid during the
synthesis, is not only beneficial for the crystallinity of the material, but also enhances the catalytic
activity of the MOF. These monocarboxylates are incorporated inside the crystals and create extra
open Lewis acid sites upon mild thermal pretreatment, particularly if the corresponding acids are
highly volatile, like trifluoroacetic acid. This results in a much increased activity, without
compromising framework stability. The incorporation of trifluoroacetic acid is proven by F-MASNMR and FT-IR. The addition of HCl as crystallizing agent even further increases the incorporation
of the monocarboxylates, creating even more active catalysts.
P-1.4-36
Crystal Structures, Sorption Properties and Photochemistry of a Versatile Series of Aluminium
MOFs
H. Reinsch,1 M. A. van der Veen,2 F. Hinterholzinger,3 T. Bein,3 D. De Vos,2 N. Stock1
1Institute of Inorganic Chemistry, Christian-Albrechts-University, Kiel, Germany, hreinsch@ac.unikiel.de
2Centre for Surface Chemistry and Catalysis, University of Leuven, Belgium
3Department of Chemistry and Center for NanoScience, Ludwig-Maximilians-University, Munich,
Germany
The synthesis, crystal structures and sorption properties of a series of seven different MOFs based on
chains of cis-connected corner-sharing AlO6-polyhedra and isophthalic acid (H2BDC) or a
functionalized derivative of this linker molecule (H2BDC-X) with the common formula
[Al(OH)(BDC-X)] denoted as CAU-10-X are reported. Moreover, the properties of six compounds
based on mixtures of linker molecules were investigated. The humidity-dependent phase-change
behavior of CAU-10-CH3 was studied in detail. Furthermore the photochemical generation of stable
radicals employing CAU-10-NO2 and several alcohols was investigated.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.4-37
Synthesis and characterization of Mixed ligand Zr-MOFs.
Sachin Chavan1; Stian Svelle1, Silvia Bordiga2 and Karl Petter Lillerud1
1Department of Chemistry, University of Oslo, P.O. Box 1033, N-0315 Oslo, Norway,
Sachin.chavan@kjemi.uio.no
2 Department of Chemistry IFM & NIS Centre of Excellence, University of Torino, Via Quarello 11,
I-10125 Torino, Italy
An amine functionalized zirconium metal-organic framework (UiO-66-NH2) is considered a material
of importance due to its performance in CO2 adsorption, base catalysis, and photo-catalysis.
However, to its detriment, UiO-66-NH2 is thermally less stable than unmodified UiO-66. A mixed
ligand (terephthalic acid, BDC and aminoterephthalic acid, ABDC) approach has been employed in
order to improve the thermal stability of the framework while maintaining the reactive –NH2 sites.
Presented herein are the results of the synthesis, characterisation, and CO2 adsorption measurments
obtained on the mixed ligand zirconium MOFs of the UiO-66 topology. For the first time, Uv-Visible
spectroscopy has been applied in the quantification of the amino terephthalate ligand in the mixed
ligand MOFs.
P-1.4-38
EPR study of the mobility of nitroxide radicals confined in MIL-53(Al) nanochannel system
1Alena Nishchenko, 1Matvey Fedin, 2Alexander Stepanov, 2Daniil Kolokolov, 2Anton Gabrienko ,
3Sergey Gromilov, 4Inna Shundrina, 4Elena Bagryanskaya
1International Tomography Center, Institutskaya 3a, 630090, Novosibirsk, Russia,
arlenushka@gmail.com
2Boreskov Institute of Catalysis, SB RAS, Ac. Lavrentieva ave. 5, Novosibirsk 630090, Russia
3Nikolaev Institute of Inorganic Chemistry, SB RAS, Ac. Lavrentieva ave. 3, Novosibirsk 630090,
Russia
4N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Ac. Lavrentieva ave. 9,
630090, Novosibirsk, Russia
Structure of the dehydrated aluminum form of the metal-organic framework compound MIL-53
shows a temperature driven phase transition with pronounced structural hysteresis large-pore (LP) and
narrow-pore (NP) crystalline states with cell volume of 1427.5(5) A3 and 863.9 A3 in its high- and
low-temperature form, respectively. In this work, we present first studies on TEMPO radicals
adsorbed in MIL-53(Al). CW EPR for samples with 1/1000 ratio of TEMPO demonstrated a
temperature driven phase transition with pronounced structural hysteresis. “Breathing” properties of
MIL-53 with large amount of radical (1/10 and 1/1 per unit cells of MIL-53) are suppressed.
P-1.4-39
Mg- and Ca-based metal-organic frameworks: from design to application
M. Mazaj, T. Birsa Čelič,. M. Rangus, G. Mali, N. Zabukovec Logar, V. Kaučič
National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia, matjaz.mazaj@ki.si
Metal-organic frameworks (MOFs) can be developed by rational design. This however requires
proper knowledge of interaction behaviour between metal cations and functional groups of organic
linkers in different synthetic conditions. In this contribution we focused on the case studies of the
design, structural dynamic investigations and application opportunities of Mg- and Ca-based MOFs.
Firstly, the influence of solvent composition on the framework dimensionality will be presented for
magnesium trimesate system. Investigation on framework dynamics upon heating will be shown for
the case of new calcium-terephthalate. Finally, degradation studies of Mg- and Ca-based MOFs with
biocompatible aliphatic ligands for potential bio-applications will be discussed.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
200
P-1.4-40
A combined computational and experimental FTIR study of CH4 and CO2 adsorption on
Porous Aromatic Framework (PAF) materials
G . Gatti1, M . Errahali1, L. Canti1, L. Tei1, M . Cossi1, L . Marchese1
1Dipartimento di scienze e Innovazione tecnologica (DISIT), Centro interdisciplinare Nano-SiSTeMI,
Università del Piemonte Orientale “A. Avogadro”, via T. Michel 11, I-15121, Alessandria, Italy,
giorgio.gatti@mfn.unipmn.it
Porous aromatic frameworks (PAF) are a new class of materials with diamond-like structure and rigid
phenyl rings. They are characterized by exceptionally high surface area, thermal and hydrothermal
stability and are suitable for gas storage of H2, CH4 and CO2. A PAF-type sample was synthesized
and characterized by a multidisciplinary physico-chemical approach. Particular attention was devoted
to the FTIR study of the interaction of the PAF structure with CO2 and CH4 and the results compared
with DFT calculations.
P-1.4-41
Chemical and thermal switch in copper-based MOF materials
B. Gil1, B. Marszalek1, R.E. Morriss2
1Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland,
gil@chemia.uj.edu.pl
2University of St Andrews, St Andrews, Fife, KY16 9ST, Scotland, United Kingdom
MOFs are hybrid organic-inorganic materials consisting of metal cations and organic linkers. Upon
heating or adsorption of guest molecules they undergo specific structural changes. For this work CuMOFs are chosen to underline the role of organic linker in construction of flexible networks.
STAM-1 and HKUST-1 are constructed from the same copper inorganic block and trimellitic acid
linker. Solvent and different proportions of reagents direct synthesis into different pathways, causing
formation of double channel system for STAM-1.
CuSIP-3 and CuSIP-3-Py are isoreticular MOFs based on the 5-sulfoisophthalic acid linker where
breathing effect causes break of hydrogen bonds and drastic rearrangement of the structure. Pyridinebased sample is more hydrophobic and shows superior thermal resistance.
P-1.4-42
Controlling hydrothermal stability of Zn-MOF materials
T. Birsa Čelič1, M. Mazaj1, M. Rangus1, T. Čendak1, G. Mali1 and N. Zabukovec Logar1,2
1National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia, natasa.zabukovec@ki.si
2Centre of Excellence Low Carbon Technologies, Hajdrihova 19, 1000 Ljubljana, Slovenia
Zinc carboxylates show some very interesting sorption and fluorescence properties; however, their
exploitation is limited due to their sensitivity to water. Exposure to water or humid air usually causes
amorphization, phase transformations or desolvation of the structure. Here we report on the structural
investigation of hydrothermally stable Zn-trimesate structure. Its structural changes are completely
reversible upon hydration/dehydration processes and the structure withstands 40 cycle-hydrothermal
stability tests. The possible reasons for this kind of behavior are discusses and compared with known
structures, including the ligand to metal connectivities, chain-type SBUs and hydrogen-bonding
scheme.
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P-1.4-43
Alternate Layered Nanostructures using Click Reaction of Organic-modified Metal Oxides
Dai Mochizuki, Kozue Kumagai, Funinao Kishimoto, Masato Maitani and Yuji Wada
Department of Applied Chemistry, Tokyo Institute of Technology, Japan, daim@apc.titech.ac.jp
The nanoconjugations of 2 metal-oxides are expected to enhance and innovate their functionalities
and properties. One of the best candidates for nanoconjugation is a photocatalyst consisting of
titanium and tungsten oxide. Nanoconjugations precisely arranged on a nanometer scale are crucial
for improved function and the development of new properties. To realize the new methodology of
alternating nanoconjugation, we focused on click chemistry. Click chemistry is a reaction used to
easily form stable connections between specific functional groups. The present study proposes a new
methodology to realize alternating multilayer powders using a thiol-ene reaction. Two kinds of metaloxide species were each modified with alkene and alkylthiol groups, and dispersed into organic
solvent to exfoliate the layers. A radical initiator was added to induce a thiol-ene reaction, then the
powder of hundreds of layers of alternate stacks were synthesized in 1 step.
P-1.4-44
Dual Template-Directed Synthesis of Hierarchically Zeolitic Imidazolate Framework-8 (ZIF-8)
in an Aqueous System with Enhanced Porosity
Y.N. Wu, B.Z. Wu, F.T. Li
College of Environmental Science and Engineering, State Key Laboratory of Pollution Control and
Resource Reuse, Tongji University, Shanghai, China, 51@tongji.edu.cn
The development of hierarchically porous metal-organic frameworks is a great challenge. Here, we
report the synthesis of hierarchically zeolitic imidazolate framework-8 (ZIF-8) with both micro- and
mesopore using cetyl-trimethylammonium bromide (CTAB) and amino acid as dual templates. It is
demonstrated how the dual templates play a cooperative role on the formation of hierarchical porous
structure in the ZIF-8 nanospheres. When the surfactant or amino acid was applied individually, no
hierarchical structure can be obtained. Moreover, due to the additives of amino acid, the porosity
(surface area and pore volume) of our ZIF-8 was enhanced over several times, which can be
compared favourably with those previous reported ZIF-8 via solvent-thermal synthesis strategies.
P-1.4-45
Stability of CPO-27 materials upon activation and rehydration
Mojca Rangus, Benjamin Barth, Martin Hartmann
Erlangen Catalysis Resource Center, Friedrich-Alexander Universität Erlangen-Nürnberg, 91058
Erlangen, Germany, Mojca.Rangus@ecrc.uni-erlangen.de
In this work we discuss the influence of activation and rehydration on the structure and porosity CPO27 with different metals. In order to study structural changes of CPO-27-Mg upon rehydration, the
activated sample was exposed to a controlled flow of water vapor while the X-ray diffractograms
were recorded in-situ. The changes in CPO-27-Mg diffraction peak intensities indicate a structural
transformation. The specific surface area ABET of CPO-27-Mg also decreased dramatically when the
sample was rehydrated. Hydration of CPO-27 materials also leads to considerable differences in the
13C solid-state NMR spectra. They confirm the structural transformations in the hydrated CPO-27-Mg
sample but also indicate that the structure does not completely collapse. The obtained results for
CPO-27-Mg were compared to the measurements on activated and rehydrated CPO-27-Ni which is
more hydrothermally stable and shows only a minor decrease in BET surface area upon hydration.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
202
P-1.4-46
A novel (3,3,6)-connected luminescent metal-organic framework for sensing of nitroaromatic
explosives
Libo Sun, Xiaowei Song, Zhiqiang Liang,* Jihong Yu, Ruren Xu
State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun,
130012, P. R. China, liangzq@jlu.edu.cn
A novel metal-organic framework [Cd3(CPEIP)2(DMF)3]·DMF (1) based on a neutral non-oxo
triangular [Cd3(COO)6] secondary building unit (SBU), was synthesized under solvethermal condition
by using a rigid unsymmetrical tricarboxylate ligand 5-((4-carboxyphenyl)ethynyl)isophthalic acid
(H3CPEIP). Such a structure exhibits a rare (3,3,6)-connected 3-D framework. The incorparation of
CPEIP3+ into 1 gives rise to the high luminescence in solid state. So the micrometer-sized compound
1 (1') dispersed in ethanol was used for the detection of aromatic explosives. The result shows that 1'
could be efficiently quenched by piric acid (PA).
P-1.4-47
Pillar-Layer Assembly of Four Novel Cd-based Metal-Organic Frameworks with Structural
Varieties Derived from the Replacement of Organic Linkers
Fang Wang,1 Xuemin Jing,2 Bing Zheng,1 Guanghua Li,1 Guang Zeng,1 Qisheng Huo,1 and
Yunling Liu*,1
1State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun 130012, P. R. China. yunling@jlu.edu.cn
2Faculty of Chemistry and Material Science, Langfang Teachers College, Langfang 065000, P. R.
China
Four three-dimensional (3D) Cd-based metal-organic frameworks (MOFs) have been rationally
designed and systematically synthesized by using organic linker H2pyip and Cd(NO3)2·4H2O under
solvothermal condition. Compound 1 possesses 3,6-connected rtl network, and compounds 2-4
exhibit 3,5-connected interpenetrate hms network constructed by 2-fold layers and bridging coligands
pillars (Diox, pz and bpy), respectively. In compound 2-4, Diox, pz and bpy as pillars extend the
distance between two layers from 7.34 Å to 11.36 Å, and the different conformation and length
among the coligands have influenced on the angle between the bridging ligands and the layers.
Additionally, four compounds exhibit strong luminescent emissions in the solid state at room
temperature and the latter three compounds exhibit robust architectures as evidenced by their
permanent porosity and high thermal stability.
P-1.4-48
Evaluation of CTA-MCM-41 modified with polyacrylates for use in catalytic transesterification
F. T. Cruz, D. Cardoso
Catalysis Laboratory, Chemical Engineering Department, Federal University of São Carlos, 13565905-São Carlos, Brazil www.labcat.org, dilson@ufscar.br
The molecular sieve CTA-MCM-41 possesses basic sites due to the presence of siloxy anions (≡SiO-)
associated with the CTA cations. A problem is that the catalyst loses part of its activity during the
course of successive usage for the transesterification of monoesters. The challenge of this work was to
stabilize the catalytic activity of CTA-MCM-41 employing the method of polymerization after the
synthesis. The SAXS technique provided confirmation of the increased diameter of the channels, with
a shift of the scattering vector (q) to smaller values. In terms of catalytic stability, poly(octyl
acrylate)-MCM-41 was the most stable of the materials investigated. This suggested that the polymers
formed provided the best interaction within the micelles, with the greater stability probably being due
to the partial blocking of leaching of the CTA cations.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.4-49
Nanocrystalline M-MOF-74 (M= Mg, Mn, Co, Ni, Zn) prepared at room temperature
Manuel Díaz-García1, Manuel Sánchez-Sánchez1, Álvaro Mayoral2, Isabel Díaz1
1Instituto de Catálisis y Petroleoquímica, CSIC, Madrid, Spain, idiaz@icp.csic.es
2Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Zaragoza, Spain.
Amongst MOF materials, Me-MOF-74/CPO-27-Me possess exceptional properties including the
presence of unsaturated and exposed metal centers. In order to take advantage of these properties for
some applications such as heterogeneous catalysis, it is almost compulsory to drastically reduce their
crystal size until the nano-scale range.
We have prepared different M-MOF-74 at room temperature. The resultant materials are indeed of
MOF-74 topology and nanocrystalline nature. To prove that, XRD identification is not enough as the
crystals forming the samples are too small to diffract, so a series of advanced characterization
techniques have been used. One of the conclusive proofs was given by STEM images of
unprecedented high-resolution.
P-1.4-50
Effect of Solvent Reduction on the Synthesis of the Highly Robust Zr-BDC (UiO-66) MOF
Himanshu Jasuja, Deonte Fletcher, and Krista. S. Walton
School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Drive
NW, Atlanta, Georgia 30332, U.S.A, hjasuja3@gatech.edu
Despite numerous desirable attributes of MOFs, their commercialization requires them to be
synthesized on much larger scales. Solvothermal technique is the most frequently used method for
MOF synthesis. However, this method suffers from the use of large amounts of solvents and hence, it
cannot address prominent cost and environmental concerns. In this work, we have studied the effect
of solvent reduction on the solvothermal synthesis of the highly robust UiO-66 MOF. We have
synthesized UiO-66 with increasing reactant amounts in fixed solvent volume, i.e., with increasing
reactant concentrations, and studied the quality and yield of the product. Quality is assessed using
powder XRD and BET analysis of N2 adsorption isotherms. We observe that the yield of UiO-66
increases with the reactant concentrations.We have refined UiO-66 synthesis methods such that we
are now able to produce more than 60 times the yield obtained from the original synthesis report
using the same solvent volume.
P-1.4-51
Non-classic Crystal Growth of Some Selected MOFs
H. F. Greer1, C. M. Zheng1,2, Y. H. Liu1, R. E. Morris1, W. Z. Zhou1
1EaStCHEM, School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, United
Kingdom, wzhou@st-andrews.ac.uk
2Dep. of Materials Science and Engineering, School of Aerospace Science and Engineering, National
University of Defense Technology, Changsha, Hunan 410073, China
Some MOFs materials, such as MOF-5, HKUST-1, have been synthesized using the same methods as
reported in the literature. Intermediate specimens were collected at several reaction times.
Investigations of the early stage specimens, mainly using XRD, SEM and TEM, revealed a nonclassic crystal growth route. It has been found that when aggregation of precursor molecules or
nanocrystallites dominates the early stage of crystal growth, the most active site of growth is the
surface of aggregates, leading to a reversed crystal growth route. Many novel morphologies of the
particles can be identified.
1.4. Hybrid and composite materials (MOF, POM, ZIF, Porous carbons, etc)
204
P-1.4-52
Phase transformations in the system of two iron carboxylates
T. Birsa Čelič1, M. Rangus1, V. Kaučič1,2, N. Zabukovec Logar1,2
1National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia, tadeja.birsa@ki.si
2Centre of Excellence Low Carbon Technologies, Hajdrihova 19, 1000 Ljubljana, Slovenia
Metal organic framework (MOF) materials are promising for a variety of applications due to their
high surface areas, porosity and tuneable structures. On-demand design of MOFs cannot be
accomplished without understanding the formation and crystallisation processes and the roles that the
individual parameters have in the synthesis. Till now several parameters have been considered in the
thermodynamic and kinetic control in the formation of MOFs but still the formation is far from being
fully understood.
We investigated the crystallization of MIL-45(Fe) material by using two different synthetic
approaches and the phase transformations in the system of two iron carboxylates MIL-45(Fe) and
MIL-100(Fe). The insight into formation mechanisms revealed that the acetone as aprotic solvent
influences the rate of the solvation process of the reagents and the formation of intermediate phases
but it is also a trigger site for reduction of iron at higher temperatures. However, obtained results
suggest that MIL-45(Fe) is a metastable phase that eventually evolves into the thermodynamically
more stable MIL-100(Fe) structure.
P-1.4-53
The study of I2 guest molecule binding ability in different organic solution
of PAF-1 and JUC-Z2
Cuiying Pei1, Teng Ben2, Shilun Qiu1
1 State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun (China), sqiu@jlu.edu.cn
2 Department of Chemistry, Jilin University, Changchun, China
The crisis at Japan's Fukushima Dai-Ichi nuclear energy center remind us that nuclear waste
management is the key of the application of clean, safe, and responsible nuclear energy. The
radionuclide 129I and 131I, as they both produced from nuclear fuel reprocessing and inadvertent
environmental releasing, are the main components of waste streams. Several projects aimed at capture
I2 have been undertaken, such as wet scrubbing, silver-containing zeolites and ZIF-8. However, in
each of these cases there are several technical challenges to be over come. We believe these can be
addressed by employing porous aromatic frameworks (PAFs) with high surface areas and
physicochemical stability as storage media. PAF-1[1] with dia topology, ultrahigh surface area (SBET =
5600 m2 g-1), and the electron-rich polytriphenylamine JUC-Z2[2] with hcb topology are two typical
PAFs. Here we studied the I2 guest molecule binding ability in different organic solution of PAF-1
and JUC-Z2. The formation constant (Kf), the number of binding sites (mol) per g of the host
([BS]0/ω) for guest molecules and Gibbs free energy (ΔG) were estimated. The selective I2 binding
ability in different solvents (indicated in Kf) was listed in order of n-hexane >chloroform > methanol.
It is evident that the host has a stronger adsorption with the guests in nonpolar solvents, which can be
used to systematic study the interaction between I2 molecule and host.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.5-01
Synthesis and characterization of nanocomposite Ge-MFI alumina membranes for CO2/N2
separation from wet flue gases
C-H. Nicolas,1 M. Pera-Titus,1
1Eco-Efficient Products and Processes Laboratory (E2P2L), UMI 3464 CNRS/Rhodia, Shanghai,
China, marc.pera-titus-ext@ap.rhodia.com
Ge-MFI membranes with nanocomposite architecture have been prepared on α-alumina tubes by
pore-plugging hydrothermal synthesis at 443 K for 89 h using a precursor clear solution with molar
composition 1 SiO2 : 0.45 TPAOH : 27.8 H2O : x GeO2 (x=0-0.02). Ge incorporation to the MFI
framework increases the hydrophobic behaviour. The synthesized membranes present optimal
permeation properties and partial CO2/Air separation even in the presence of huge amounts of water
in the feed stream. The best material consists of a Ge-MFI-alumina membrane with a Si/Ge ratio
about 10, offering a steady-state CO2 permeance as high as 0.4 µmol.m-2.s-1.Pa-1 at 373 K in the
presence of 10% water concentration in the feed.
P-1.5-02
Oriented Zeolite Membranes: Preparation, Characterization and Special Wettability
Jiancheng Di, 2 Xiaofang Wang,2 Kangjian Tang,*,1,2 Yangdong Wang,1 and Weimin Yang
1Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China.
tangkj.sshy@sinopec.com
2State key laboratory inorganic synthesis and preparative chemistry, College of Chenistry, Jilin
University, Changchun 130012, China
Oriented zeolite membranes, MFI (Silicate-1) and AFI (AlPO4-5) were prepared on flat substrates.
Through adjusting the reaction conditions, MFI, and AFI membranes with different surface patterns
and orientations were synthesized as well. The surface patterns and structures of asprepared
membranes were investigated with FE-SEM, XRD and wetting investigation. The MFI and AFI
membranes with various patterns show orient- dependant wetting abilities. Interestingly, the well
oriented AFI membrane shows superamphiphilicity and with the surface modification of low energy
species, the AFI membrane possess both superhydrophobicity and superoleophicity, which offers a
promoting separation strategy on oil and water.
P-1.5-03
Oriented Heterostructured Surface Mounted Metal-Organic Frameworks:
[Cu3btc2]@[Cu2(ndc)2(dabco)]
Min Tu1, Roland A. Fischer1
1Chair of Inorganic Chemistry II, Ruhr-University Bochum, Bochum, Germany, min.tu@rub.de
Deposition of MOFs (Metal-Organic Frameworks) on top of substrates to form films or membranes
offers great potential for application in gas/liquid separation, chemical sensors and non-linear optical
devices. Surface mounted metal-organic frameworks (SURMOFs) fabricated by step-by-step liquid
phase epitaxy (LPE) method are highly crystalline, homogeneous, and the crystallite orientation can
be controlled. Growth of one MOF layer on top of the surface of another one to give heterostructured
MOFs have attracted much interest due to the fact that the porous properties of MOFs can be
modified by functionalization of the outer surface. Here we present the fabrication of a SURMOF of
[Cu3btc2] (HKUST-1; btc = 1,3,5-benzenetricarboxylae,) on top of preoriented SURMOF
[Cu2ndc2dabco] (ndc: 1, 4-naphtalene dicarboxylate, dabco: 1, 4-diazabicyclo (2.2.2) octane) which is
grown on pyridy-terminated SAMs on Au substrates by LPE.
1.5. Zeolite and MOF membranes and films
206
P-1.5-04
Improved performance of supported zeolite and MOF membranes by chemical support
modification for seeding-free syntheses
J. Caro1, A. Huang2
1Institute of Physical Chemistry, Leibniz University Hannover, Hannover, Germany
juergen.caro@uni-hannover.de
2A.Huang, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences,
Ningbo, China
Despite much progress in the development of MOF and zeolite molecular sieve membranes, their
performance is still not sufficient for an industrial application. By simple chemical modifications of
the macro porous ceramic supports, the growth of the zeolite or MOF layer on the support can be
facilitated. By doing so, the use of seeds turned out to be dispensable.
There are two main mechanisms that facilitate the growth of MOF and zeolite layers on supports if
their surfaces are modified by suitable chemical treatment:
• Since the macromolecular zeolite and MOF precursors in the synthesis solution are
negatively charged, a positive or at least neutral surface charge (zeta potential) facilitates nucleation
and gel formation on the surface.
• Short chain hydrocarbons turned out as suitable linker molecules with one end covalently
bound to the support and with the other end anchored to the molecular sieve zeolite or MOF layer.
P-1.5-05
Synthesis and surface modification of silicalite membranes
N.A. Kosinov, E.J.M. Hensen
Inorganic Materials Chemistry group, Eindhoven University of Technology, n.a.kosinov@tue.nl
In the present work we investigated the synthesis and surface silylation of silicalite membranes.
Silicalite-1 (MFI) and, for the first time, silicalite-2 (MEL) films were prepared on hollow fiber αalumina supports by hydrothermal secondary growth. These membranes were silylated in order to
improve hydrophobicity and alter the pore morphology of the film. It was found that the
hydrophobically modified membranes exhibit improved selectivity for recovery of ethanol from its
aqueous solution. The beneficial hydrophobic properties are preserved after high-temperature
treatment (500°C) which is very advantageous because calcination is the conventional way to
reactivate zeolite membranes.
P-1.5-06
Zeolite hybrid films for space decontamination
N. Lauridant1, T.J. Daou1, G. Arnold2, H. Nouali1, J. Patarin1, D. Faye3
1 Univ de Haute Alsace (UHA), CNRS, Équipe Matériaux à Porosité Contrôlée (MPC), Institut de
Science des Matériaux de Mulhouse (IS2M) LRC 7228, 68093 Mulhouse, France, jean.daou@uha.fr
2 Univ de Haute Alsace (UHA), Equipe Propriétés Physiques et Mécaniques des Revêtements
(PPMR), Laboratoire Physique et Mécanique Textile (LPMT), EA 4365, F-68093 Mulhouse, France.
3 Service Laboratoires et Expertise, Centre National d’Etudes Spatiales (CNES), 31401 Toulouse
cedex 9, France
In low earth orbit, global performances of satellites can be affected by contamination of critical
surfaces due to the outgassing of organic pollutants. If zeolitic materials are selective in size and
shape and display various relevant properties depending on their nature or chemical composition, the
combination of different zeolites might be a wise solution to enhance the sorption and corrosion
properties. As a consequence, two-layered films of different zeolites were developed on aluminum
substrates, one of the major constituents of the satellite structure.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.5-07
Synthesis of ion-exchanged SAPO-34 zeolite membrane
Yanfeng Zhang1, Meng Li1, Dongyan Zheng1, Yuhan Sun1.
1Low-carbon conversion center, Shanghai Advanced Research Institute, Shanghai, China,
A simple one step method of preparing ion-exchanged SAPO-34 membrane by combining template
removal and ion-exchange into one step was developed. As prepared SAPO-34 membrane (template
not removed) was soaked in salt solution and then calcined to remove template. The melting point of
deposited salt is lower than calcinations temperature, so ion-exchange should occur during
calcinations process. Na, K and Li-SAPO-34 membranes were prepared with this method. Compared
with un-exchanged SAPO-34 membranes, the obtained ion-exchanged SAPO-34 membranes have
30~60% higher CO2/CH4 selectivity, which is the result of increased basicity and reduced pore size
from ion-exchange. The combination of template removal and ion-exchange simplifies membrane
synthesis and lowers the cost.
P-1.5-08
Sulfur stabilized sodalite for membrane applications
Christiane Günther, Hannes Richter, Ingolf Voigt
Fraunhofer Institute for Ceramic Technologies and Systems, Michael-Faraday-Str. 1, 07629
Hermsdorf, christiane.guenther@ikts.fraunhofer.de
The industrial separation of hydrogen from steam reforming and water gas shift reaction as well as
water separation from Fischer-Tropsch synthesis shifts the chemical equilibrium into the direction of
the products. Membrane materials for these separations have to be thermal and hydrothermal stable.
The standard hydroxy-sodalite (H-SOD) and NaA are both not stable at high pressure. Hence the
sodalite was modified with sulfur. This so called S-SOD was tested for stability and investigated with
X-ray diffraction, EDX, IR and RAMAN spectroscopy. S-SOD is stable under low pressure (with and
without water) until 800°C and under high pressure (10 bar - 57 bar, 25 % - 30 % H2O) until 270°C.
The structure of S-SOD is assumed to be a combination of the H-SOD and the ultramarine structure.
The further clarification of the structure of S-SOD is the focus of the ongoing work.
P-1.5-09
Zeolite membranes on full zeolite bodies
Hannes Richter, Gundula Fischer, Ingolf Voigt
Fraunhofer Institute for Ceramic Technologies and Systems, Michael-Faraday-Str. 1, 07629
Hermsdorf
Hannes.richter@ikts.fraunhofer.de
Zeolite membranes are usually prepared as a thin layer on top of a porous ceramic or metallic
substrate. Thermal mismatch and chemical reactions between support and zeolite layer cause cracks
in membrane layers and deviations in the chemical composition of the zeolites respectively. Full
zeolite supports may prevent these problems. Zeolite tubes, hollow fibres and honeycombs were
produced, coated with zeolite membranes and tested. MFI- and NaA-membranes were successfully
prepared on top of full zeolite substrates of different geometries. The full zeolite tubes may give the
opportunity to prepare ultra-thin defect free zeolite membranes. Beside this zeolite substrates are less
expensive than conventional supports made of Al2O3. New geometries allow the installation of huge
membrane areas in limited volumes.
1.5. Zeolite and MOF membranes and films
208
P-1.5-10
Sod-ZMOF/Matrimid Mixed Matrix Membranes for CO2/CH4 Separation
A. Kılıç, Ç. Atalay-Oral, A. Sirkecioğlu, Ş.B. Tantekin-Ersolmaz, M.G. Ahunbay*
Department of Chemical Engineering, Istanbul Technical University, Istanbul, Turkey,
ahunbaym@itu.edu.tr
Zeolite-like metal organic frameworks (ZMOFs) have anionic frameworks unlike other MOFs and
ZIFs which typically have neutral framework. The charge-compensating extra-framework cations in
ZMOFs improves their gas separation performances. In this study, sod-ZMOF crystals were
synthesized and polymer/ZMOF mixed matrix membranes (MMMs) were prepared for CO2/CH4
separation. Matrimid® 5218 was used as the polymer phase. Pure gas permeability measurements of
CH4 and CO2 showed that permeabilities increased with the amount of ZMOF loading. With 10 wt %
ZMOF loading, single gas permeabilities increased approximately 40% with respect to neat polymer
membrane. Although ideal CO2/CH4 selectivity did not change significantly in the MMMs, selectivity
in mixed gas conditions (50% CO2 / 50% CH4) increased with the addition of ZMOF particles due to
competitive adsorption.
P-1.5-11
ZIF-8 mixed matrix membranes for natural gas and exhaust gas purification
L. M. Diestel1, X. Liu2, F. Steinbach1, Y. Li2, W. Yang2, J. Caro1
1 Physikalische Chemie und Elektrochemie, Leibniz Universität Hannover, Hannover, Germany,
lisa.diestel@pci.uni-hannover.de
2 Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, China
In our experiments we compared the separation behaviour of pure PolyMethylPhenylSiloxane, pure
ZIF-8 and PMPS-ZIF-8 Mixed Matrix Membranes. We found that the MMM separates CO2 from N2
and CH4 as effective as the PMPS and ZIF-8 membrane but with much higher gas fluxes. So, we
observed that for CO2/N2 and CO2/CH4 the PMPS and the ZIF-8 membrane had Separations Factors
of 12 and 9 or 9 and 5 respectively. The fluxes through the membranes were low. The MMM had SFs
of 10 and 7 but much higher gas fluxes.
P-1.5-12
Zeolite MFI membranes on inexpensive supports for pervaporation
Zhengbao Wang1*, Yong Peng1, Zhiying Zhan1, Yushan Yan1, 2
1Department of Chemical and Biological Engineering, and MOE Engineering Research Center of
Membrane and Water Treatment Technology, Zhejiang University, Hangzhou, Zhejiang 310027, PR
China.
2Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware
19716, USA.* zbwang@zju.edu.cn
Zeolite membranes showed good performance in PV separation of organic/water solution. However,
their price is very high. Inexpensive alumina tubes with defects and hollow fibers were used as the
supports in this study. Zeolite MFI membranes with high PV performance can be obtained on the
outer surface of alumina hollow fibers and tubes with large defect pores by using a novel seeding
method of wetting-rubbing. The TPAOH content, the alkalinity of the synthesis solution and the
synthesis time have great effects on PV performance of zeolite MFI membranes.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.5-13
Hexane isomers separation through tubular silicalite-1 membrane
M. Matsukata1,2, T. Kaneko1, M. Sakai1
1Department of Applied Chemistry, Waseda University, Tokyo, Japan, saka.moto@asagi.waseda.jp
2Advanced Research Institute for Science and Engineering, Waseda University, Tokyo, Japan
Silicalite-1 membrane was prepared on a porous tubular alumina support by a secondary-growth
method. The seeded support was hydrothermally grown at 443 K for 24 h. Vapor phase permeation
properties through silicalite-1 membrane for hexane isomers (n-hexane, 2-methylpentane, 2,2dimethylbutane) were investigated. Molecular sieving effect was clearly observed in the permeation
results. Permeation tests were performed at 373 -653 K. The permeances of n-hexane and 2methylpentane in the unary systems were strongly affected by diffusion below 573 K and by
adsorption above 573 K. These permeances in the binary systems were smaller than those in the unary
systems because of the effect of competitive adsorption. Such an inhibition effect attenuated with
increasing temperature. In contrast, 2,2-dimethylbutane permeance was one order of magnitude
smaller than those of other two kinds of isomers, since 2,2-dimethylbutane pass through the
boundaries of zeolite crystals.
P-1.5-14
Effect of Na+ Cation on the Water/Acetic acid Separation
through Mordenite Membrane
M. Matsukata1, 2, Y. Imanishi1, M. Narashima1
1Department of Applied Chemistry, Waseda University, Tokyo, Japan, yuhei31@fuji.waseda.jp
2Advanced Research Institute for Science and Engineering, Waseda University, Tokyo, Japan
Vapor phase separation properties of Na- and H-mordenite membrane for water/acetic acid (AcOH)
mixture were investigated. Mordenite membranes were synthesized by a seed-assisted crystallization
method on the outer surface of porous -alumina tubular support. Vapor permeation tests of
mordenite membrane for water/AcOH were carried out 398 K. Na-mordenite membrane exhibited
excellent water selectivity. Acetic adid was hardly permeated through Na-mordenite membrane and
its permeation was below the detection limit. On the contrary, in the case of H-mordenite membrane,
both water and AcOH were hardly permeated. Strong interaction between water and Na+ locating in
the narrow channels of mordenite plays an essential role for the appearance of high selectivity to
water permeation. In the case of H-mordenite membrane, AcOH would strongly adsorb in such
narrow 8-membered channels and blocked water adsorption and permeation.
P-1.5-15
SBS/Aminated SBA-15 Mixed Matrix Membranes For Gas Separation
Maria Giovanna Buonomenna1, Giovanni Golemme1, Cristina Maria Tone2, Maria Penelope De
Santo2, Federica Ciuchi2, Enrico Perrotta3
1Department of Chemical Engineering and Materials, University of Calabria; and INSTM
Consortium; Italy; ggolemme@unical.it
2IPCF-CNR UOS Cosenza, c/o Physics Department, University of Calabria, Italy
3Department of Ecology, University of Calabria, Italy
Discoid SiO2/ZrO2 SBA-15 (800 nm) grafted with 3-aminopropyl tails was used in variable amounts
(0-10 wt%) to prepare new membranes in a poly(styrene-b-butadiene-b-styrene) matrix with high
ideal selectivity (CH4/N2 = 7.3; CO2/N2 = 53) and permeability (CO2 = 173 Barrer), which make them
ideal candidates for the post-combustion capture of carbon dioxide and for the exploitation of natural
gas with high N2 content.
The work leading to these results has received funding from the EC’s FP7/2007-2013, GA no. NMP3SL-2009-228631, project DoubleNanoMem.
1.5. Zeolite and MOF membranes and films
210
P-1.5-16
Elucidating the kinetics of pentene cracking on H-ZSM-5 by combining theory with experiment
J. Van der Mynsbrugge1, S. Schallmoser2, M. Waroquier1, J.A. Lercher2,3,
V. Van Speybroeck1
1 Ghent University, Center for Molecular Modeling, Ghent, Belgium
2 TU München, Department Chemistry, Garching, Germany
3Pacific Northwest National Laboratory, Institute for Integrated Catalysis, Richland (WA), USA
jeroen.vandermynsbrugge@ugent.be
Zeolite-catalyzed cracking of alkenes is important in many chemical processes, e.g. in FCC cracking,
in which H-ZSM-5 is often added to increase yields of ethene and propene. This study focuses on
cracking of 1-pentene as a model reaction. Chemical kinetics for monomolecular cracking are
assessed experimentally at typical operating temperatures. Static and dynamic ab initio simulations
are combined to identify key intermediates and determine feasible reaction paths. Corresponding free
energy profiles and kinetic parameters are correlated with experimental data.
P-1.5-17
Zeolite Films: A New Synthetic Approach
Davinder S. Bhachu1, Andrew J. Smith1, Ivan P. Parkin1, Andrew J. Dent2 and Gopinathan Sankar1
1Department of Chemistry, University College London, 20 Gordon Street London, WC1H 0AJ, United
Kingdom, d.bhachu@ucl.ac.uk
2Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, United
Kingdom
A new strategy is reported using chemical vapor deposition, to deposit an amorphous film on a
substrate, followed by conversion to a zeolite using hydrothermal methods. This is demonstrated by
converting a dense, amorphous silicon dioxide film into silicalite-1 and a titanium doped silicon
dioxide film into titanium silicalite-1 (TS-1). TS-1 films were then analyzed by X-ray Absorption
Spectroscopy (XAS) at Diamond Light Source in order to determine the local stricture of the titanium
species. It was found that Ti is incorporated with tetrahedral coordination at the CVD stage and this
coordination is retained upon conversion into TS-1.
P-1.5-18
Self-templated Synthesis of Porous Coordination Polymer thin Films based on Metal Oxides
K. Khaletskaya1, H. Parala1 and R. A. Fischer1
1Department of Inorganic Chemistry II, Ruhr University Bochum, Bochum, Germany,
kira.khaletskaya@rub.de
Thin porous PCP films supported on solid substrates are a well-studied and promising area. However,
the secure attachment of PCP crystals to the substrate surface requires suitable functionalization in
form of self-assembled monolayers (SAMs). By contrast, the synthesis strategy of PCP thin films
based on metal oxides nanostructures may be a rational solution, as substrates coated with metal oxide
layers provide metal ions which initiate the growth of PCP crystals directly in close proximity to the
substrate without any surface modifications. Accordingly, immobilized amorphous aluminum and
zinc oxide phases were subsequently converted into crystalline and dense [Al(OH)(1,4-ndc)]n and
Zn(MeIM)2 (ZIF-8) PCP films.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-1.5-19
Cascade pervaporation through polymer and zeolite membranes
for biobutanol recovery
D.A. Fedosov1, A.V. Smirnov1, E.E. Knyazeva1, I.L. Borisov2, V.V. Volkov2, I.I. Ivanova1
1Dep. of Chemistry, Moscow State University, Moscow, Russia, dfedosov@phys.chem.msu.ru
2A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia
Concentration of alcohols in fermentation is a critical step in terms of energy consumption for biofuel
technologies. Two-stage cascade separation using polymer (PTMSP/PDMSM) and NaA zeolite
membranes was developed to produce dry butanol from fermentation broth. Application of this
approach allowed to increase the content of butanol from 1 to 97.4 wt% and to reduce the content of
water to 0.2 wt.%. NaA zeolite membrane provides for efficient dehydration of biobutanol in the
presence of fermentation by-products including acetic and butyric acids.
P-1.5-20
Ionothermal Synthesis of Aluminophosphate Molecular Sieve Membranes through Substrate
Surface Conversion
Xiaolei Li1, 2, Keda Li1, 2, Zhijian Tian1, Renshun Xu1, Huaijun Ma1, and Bingchun Wang1
1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, 457 Zhongshan Road, Dalian, China, tianz@dicp.ac.cn
2Universityl of Chinese Academy of Sciences, Beijing, China
Ionothermal synthesis is a promising method for the preparation of aluminophosphate molecular sieve
membranes under ambient pressure. Molecular sieve membranes of types AEL, AFI, CHA,and LTA
were prepared on δ-alumina substrates. The most significant feature of this method is that the porous
alumina substrate acts as both support and Al source. Different types of membra-nes can be
synthesized by adjusting the kind of ionic liquids and organic amines. The CHA me-mrane was taken
as an example to investigate the permeability. The ideal separation factors for H2 from CO2, N2, O2,
and C3H8, are 4.8, 4.1, 5.0, and 21 respectively, which are higher than the corresponding Knudsen
value, suggest that the CHA membrane is gaspermeable.
P-1.5-21
The preparation of the integrated metal-organic framework membranes on ceramic support
under mild conditions
V.I. Isaeva1, M.I. Barkova1, M.M. Ermilova2, E.A. Mironova2, A.V. Kucherov1, L.M. Kustov1
1N.D..Zelinskii Institute of Organic Chemistry RAS, Moscow, Russia, sharf@ioc.ac.ru
2A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia
Our study aimed at the development of the preparation procedures for the integrated MOF (metalorganic framework) membranes by crystallization on ceramic support. The important task was
producing the continuous MOF layer on the support surface. Phenylenetricarboxylate coppercontaining framework MOF-199 ([Cu3(BTC)2] and zeolitic imidazolate framework ZIF-8 (Zn(mIm)2)
were selected as representative membrane materials. Two concepts were used: a) modifying the
ceramic surface; b) providing the covalent interaction between MOF and support surface. The
developed preparation procedures allowed us to achieve a non-defective coating the ceramic surface.
The MOF-199 membrane showed high separation selectivity with respect to CH4. ZIF-8 membrane
demonstrated high level of the gas permeability and selectivity in gas mixture separation including
Не/СО2 и Не/N2 gas pairs.
1.5. Zeolite and MOF membranes and films
212
P-1.5-22
Electrospinning technology applied in the synthesis of Zeolite and MOF membranes
L. Fan, Z. Kang, M. Xue, S. Qiu
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry,
Dep. of Chemistry, Jilin University, Changchun, China, xueming@jlu.edu.cn
Electrospinning is the most efficient means for manufacturing fibers. The introduction of this
technique into synthesis of supported porous membranes opens bright prospects of realizing practical
applications. This novel strategy has wide suitable range for various substrates with the possibility of
large-area processing. We successfully synthesized several kinds of porous materials into high quality
membranes on different substrates by this method, such as zeolite NaA and pure-silica-zeolite Beta
membrane on porous Al2O3 tube, zeolite NaY membrane on stainless steel net and a zeolitic
imidazolate framework-8 membrane on porous silica disc.
P-1.5-23
Pure silica LTA zeolite membranes on porous alumina supports
M. Palomino1, H. Ono1,2, S. Valencia1, A. Corma1
1Instituto de Tecnología Química, UPV-CSIC, Universidad Politécnica de Valencia, Avda. de los
Naranjos s/n, 46022, Valencia, Spain, miparo@upv.es
2JX Nippon Oil & Energy Corporation, 8 Chidoricho, Naka-ku, Yokohama 231-0815, Japan
Pure silica LTA zeolite (ITQ-29) membranes are expected to be suitable for ethanol separation from
an aqueous solution by pervaporation, due to its hydrophobic character. Germanium promotes the
formation of ITQ-29, but the resulting zeolite is not stable to moisture after calcination, while pure
silica LTA is highly stable.
Within this work, the effect of several variables on the membrane quality have been systematically
studied, such as seeding procedure, size of the seed crystals, duration of the secondary growth, water
content in the synthesis gel, and synthesis temperature, among others.
Under given conditions, defect-free, stable upon calcination, pure silica LTA membranes were
prepared on porous alumina supports. To our knowledge, Ge- and Al-free LTA membranes have
never been reported in the literature.
P-1.5-24
Electrochemical Synthesis of cobalt containing Metal-Organic frameworks
S. K. Vankova1, M. Cataldo Hernandez1, M. Thalluri1, N. Russo1, G. Saracco1
1Dep. of Applied Science and Technology, Polytechnic University of Turin, Turin, Italy,
svetoslava.vankova@polito.it
Nowadays, metal-organic frameworks (MOF’s) have enjoyed tremendous popularity do to the large
flexibility in the preparation, the possibility to apply rational design, the large surface area and pore
volume and the high metal content. The major studies have dealt with the synthesis of new structures,
and most applications have focused on gas adsorption/separation and storage, catalysis and the
manufacturing of luminescent sensors. Many of the mentioned applications require MOF deposition
on various surfaces. However, the development of more facile and generally applicable method of
growing crystalline MOF’s on surfaces remains an open challenge. Considering the high cost of
hydrothermal preparation it is important to research new synthesis methods. This study intend to
produce cobalt containing MOF’s outside the autoclave. In view of the good results obtained using
electrodeposition method in the synthesis of Cu and Zn containing MOF’s, the electrochemical
synthesis could be an attractive alternative. Different parameters were analyzed in order to obtained
good crystalline film and low energy consumption.
17 IZC, 2013. POSTER COMMUNICATIONS
213
P-1.5-25
Preparation of b-oriented HZSM-5 multilayer on stainless steel tube
with remarkably enhanced catalytic performances
Meiling Ji, Guozhu Liu1, Li Wang, Xiangwen Zhang
School of Chemical Engineering and Technology, Tianjin University, Tianjin, China, jiml@hotmail.com
1 Corresponding authors: (Tel: 022-27892340, Email: gliu@tju.edu.cn)
b-Oriented MFI membranes have attracted much attention in various areas including catalytic
process. A facile and efficient strategy of introducing a TiO2 interlayer for preparation of b-oriented
HZSM-5 bi-layers, which showed improved activity in catalytic cracking of n-dodecane, was
proposed here. n-Dodecane conversion increased with reduction in TiO2 thickness. The b-oriented
HZSM-5 bi-layer with ultra-thin TiO2 interlayer, prepared via a surface sol gel process, showed a
higher activity than that prepared by depositing method. It is expected that b-oriented HZSM-5
multilayer can be prepared by the same method and find potential use in many important areas.
P-1.5-26
Separation of CH4/CO2 binary mixtures using micro- and nano-sized ZIF-8 membranes
J. Cookney1, K. Lecoanet1, P. Hrabanek2, V. Fila1
1Institute of Chemical Technology Prague, 16628 Prague, Czech Republic,
Joanna.Cookney@vscht.cz
2J. Heyrovsky Institute of Physical Chemistry of the ASCR, 18223 Prague, Czech Republic
This paper demonstrates the potential for separation of CH4/CO2 gas mixtures by utilisation of zeolitic
imidazolate framework 8 (ZIF-8) membranes. ZIF-8 membranes were prepared via synthesis routes
that employ methanol solutions saturated either with (i) 2-methylimidazole or (ii) zinc chloride;
followed by in-situ solvothermal synthesis. The developed methods were further improved by (i)
varying the molar ratios of the compounds forming the synthesis solution, and (ii) replacing sodium
formate modulating ligand with n-butylamine. Fabricated micro (~ 8 μm) and nano-sized (~ 60 nm)
membranes were employed for separation of CH4/CO2 gas streams under various process conditions,
subsequently enabling the identification of the optimum operating parameters and process limitations.
P-1.5-27
Size and Drying Effects on Preparation of Nafion/ZSM-5 Composite Membranes
for DMFC Application
Wei-Jen Chou, Soofin Cheng*
Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
*chem1031@ntu.edu.tw
Nafion/ZSM-5 composite membranes were prepared by solution cast method in mixing ZSM-5
particles with DE520 Nafion® dispersed in DMAc. ZSM-5 particles varied from 84 to 887 nm in
diameter was prepared by incresing the water/TEOS molar ratios from 10 to 100 in the synthesis gel.
The composite membrane prepared with as-made zeolite in wet showed lower methanol permeability
and higher proton conductivity than the composite prepared with dried or calcined zeolite samples.
The composite membrane with 20 wt% as-made ZSM-5 of 141 nm size gave the lowest methanol
permeability of 1.8x10-6 cm2s-1, proton conductivity of 3.32x10-2 Scm-1 at 90oC and 90% humidity.
The selectivity was almost twice better than Nafion®117 and three times better than recast Nafion
membrane.
1.5. Zeolite and MOF membranes and films
214
P-1.5-28
Amine-Functionalized MIL-53 Metal-Organic Framework and Aminosilanes Grafted
FAU/EMT zeolite In Polyimide Mixed Matrix Membranes for CO2/CH4 Separation
Xiao Yuan Chen, Vinh-Thang Hoang, Omid Ghaffari Nik, Denis Rodrigue, Serge Kaliaguine,
Department of Chemical Engineering, Laval University,mQuebec City, Canada G1V 0A6.
xiao-yuan.chen.1@.ulaval.ca
Flexible crystalline metal organic framework (MOF) nano-size particles (Al-MIL-53) and 6FDAODA polyimides were used to produce mixed matrix membranes (MMM). FAU/EMT intergrowth
zeolites were grafted with 3-aminopropyltriethoxysilane (APTES), 3aminopropylmethyldiethoxysilane (APMDES), and 3-aminopropyldimethylethoxysilane (APDMES)
containing respectively trihydrolyzable ethoxy groups (3E), di-hydrolyzable ethoxy groups (2E), and
monohydrolyzable ethoxy group (1E) in isopropanol (IPA) polarity solvents. These were used as the
inorganic phase in preparing mixed matrix membranes with 6FDA-ODA polyimide cross-linked by
APTMDS (Bis(3-aminopropyl)-tetramethyldisiloxane) as the organic phase. The amine-grafted
zeolites and MOF were characterized using BET and SEM, and the adsorption capacity for CO2 of
the samples was also measured. MMMs were characterized by TGA, FTIR, DMA and SEM. The gas
transport properties of MMMs for pure gas and blends of CO2 and CH4 were investigated at 35 and
150 psi pressure. The MMMs of MOF/PI display excellent CO2/CH4 separation properties even
without any compatibilization (amine grafting).Their results showed that the ideal selectivity and
separation factor of these MMMs were found to increase with increasing MOF loading. Furthermore,
these materials have improved CO2/CH4 separation factor with increasing pressure, in contrast to
traditional polymer membranes. For the performance of MMMs from zeolite/PI at 25 wt.% zeolite are
excellent for CO2/CH4 separation. A detailed study of the relation between MMM’s membrane
properties and their morphology as affected by their interactions with the amine grafted by inorganic
phase and the cross-linking agent is reported.
P-1.5-29
Fabrication of new mixed matrix membranes based on poly-etherimide and
metal organic frameworks
M. Galizia1, N. Gargiulo2, D. Caputo1, P. Musto3, G. Mensitieri1
1Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università
Federico II, Napoli, Italy, domenico.caputo@unina.it
2Centro di Ricerca Interdipartimentale sui Biomateriali, Università Federico II, Napoli, Italy
3Istituto per la Chimica e la Tecnologia dei Polimeri, ICTP-CNR, Pozzuoli, Italy
In this work, new generation mixed matrix membranes (MMMs) based on poly-etherimide (PEI) and
metal organic frameworks (MOFs) have been synthetized and characterized, in view of their possible
application in gas separation field, such as natural gas sweetening and/or air enrichment. MMMs
based on PEI and copper benzene tricarboxylate (Cu-BTC) MOF were prepared via solution casting:
scanning electron microscopy (SEM) micrographs revealed a good dispersion of the filler within the
polymer matrix. Interestingly, a strong increase of permeability was measured in the composite
membrane as compared to the neat PEI, as expected on the basis of the microporous nature of the
filler. Such an increase of permeability is accompanied by a loss of selectivity of about 25%, likely
due to the presence of non-selective voids at the interfaces between polymer and MOF: our next goal
is to introduce a coupling agent, to guarantee a better adhesion between the polymer phase and MOF
particles.
POSTER COMMUNICATIONS
SECTION 2
“Advances in fundamental understanding of
structure and properties”
2.1. Theory and modeling
216
P-2.1-01
Methane, hydrogen and carbon dioxide adsorption in porous aromatic frameworks (PAFs):
a computational study
M. Cossi1 , G. Gatti 1, L. Canti1, M. Errahali1 , L. Tei1 and L. Marchese1
1Dipartimento di Scienze e Innovazione Tecnologica, Centro Interdisciplinare Nanosistemi,
Università del Piemonte Orientale “Amedeo Avogadro”, Viale T. Michel 11, 15121, Alessandria, Italy.
maurizio.cossi@mfn.unipmn.it
The modelling with Grand Canonical Monte Carlo technique of Porous aromatic frameworks (PAFs)
in which a different number of phenyl rings (1-4) spaced two consecutive sp3 carbon atoms is
reported. The ability of these materials to adsorb gases (CH4, CO2 and H2) at different pressures and
different temperatures was theoretically explored. Using Monte Carlo simulations with adapted force
fields the BET surface area of the materials was also predicted. The simulations showed that some
members of the PAF family have an enormous potential especially as CH4, CO2 adsorbents.
P-2.1-02
A theoretical study of hydrocarbon pool mechanism for methanol-to-olefins conversion
in HSAPO-34: Cluster model
Chuan-Ming Wang, Yang-Dong Wang, Zai-Ku Xie
Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai, China,
wangcm.sshy@sinopec.com
Methanol-to-olefins (MTO) conversion catalyzed by zeolites or zeotype materials has attracted much
attention as light olefins such as ethene and propene can be produced from coal, natural gas or
biomass through this reaction. However, the detailed reaction mechanism is still unclear. The effect of
catalyst structures on activity and selectivity remains to be elucidated based on the proposed reaction
mechanism. By using density functional theory calculations, we systematically investigated the side
chain hydrocarbon pool mechanism for the MTO conversion using 48T HSAPO-34 model for
different MBs (hexaMB, TetraMB, and PX) and different acid sites. It was found that the catalytic
activity of HexaMB is not more active than those of TetraMB and PX, consistent with our previous
calculated results using periodic model.
P-2.1-03
Enumeration and interpretation of ABC-6 zeolites via intuitive framework encoding
Yi Li, Jihong Yu, Ruren Xu
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun
130012, China, yili@jlu.edu.cn
The ABC-6 family of zeolites have been widely used as the catalysts for many reactions, which are
built from layers of parallel 6-rings linked by 4-rings. In 1981, Smith and Bennett devised the
symbols s, c, and a, and enumerated 98 simplest ABC-6 structures. Different from this approach, we
adopt an intuitive framework encoding, through which the ABC-6 structures are transformed into
ternary numbers. Using this approach, we have enumerated 84292 ABC-6 structures consisting of
≤16 layers of 6-rings. More significantly, structural information, such as the composite building units
(CBUs) and the size of the largest ring, can be automatically extracted from this encoding by our
computer programs.
17 IZC, 2013. POSTER COMMUNICATIONS
217
P-2.1-04
Methanol carbonylation and oxidative carbonylation over alkaline earth and transition metal
zeolites
Andrei A. Rybakov1*, Alexander V. Larin1, Georgy M. Zhidomirov1,2, Daniel P. Vercauteren3
1Chemistry Department, Lomonosov MSU, Moscow, Russia; rybakovy@gmail.com 2Boreskov
Institute of Catalysis, Novosibirsk, Russia; 3 University of Namur, Namur, Belgium
The scheme of dimethylcarbonate formation in the Ca- and Cu-forms of MOR and FAU zeolites is
discussed at the levels of the isolated cluster approach and using periodic boundary conditions (PBC).
Our interpretation allows confirming the first step of the reaction for carbonate species in zeolites
which requires moderate activation energy 27.89 kcal/mol via the sp2-sp3-sp2 transformation, typical
for carbon chemistry. The studied steps showed a pretty nice coherence between the energies and
geometries calculated with and without PBC. This rare situation proves the possibilities of isolated
cluster approximation for the considered case.
P-2.1-05
Impact of framework topology on CO2/N2 separation properties of zeolite frameworks: A
building-block based approach
Michael Fischer, Robert G. Bell
Department of Chemistry, University College London, London, United Kingdom m.fischer@ucl.ac.uk
The removal of CO2 from flue gases using microporous adsorbents is a current topic of high scientific
interest. This contribution presents results of grand-canonical Monte Carlo simulations of CO2 and
CO2/N2 adsorption in various zeolite frameworks, as well as additional results from density-functional
theory calculations. The aim of this study is a better understanding of the relationship between zeolite
topology and the predicted CO2 adsorption properties. In an initial set of common topologies, an
analysis of simulation snapshots is used to assess which building units are mostly responsible for a
high affinity towards CO2. The concept of natural tilings is then exploited to identify other framework
types that might exhibit promising properties.
P-2.1-06
Modeling of structure, sorption, and transport in zeolite-impregnated membranes for gas
separation
A.J. Petsi, V.N. Burganos
Institute of Chemical Engineering Sciences - Foundation for Research and Technology, Hellas,
Patras, 26504, Greece, vbur@iceht.forth.gr
Zeolites and other ordered microporous materials hold strong promise for improved sorption and
separation performance of membranes. However, the performance of the resulting hybrid membrane
is often found to be inferior to the anticipated one. Among other factors, this is attributed to the poor
adherence of the membrane matrix to the zeolite inclusions. It is believed that the gas molecules
bypass the zeolite inclusions taking advantage of the relatively wide avenues of reduced transport
resistance that are formed at the zeolite-matrix interface. The objective of this work is to elucidate the
underlying transport and sorption phenomena and quantify the relationship between zeolite sorption
properties and overall performance of the membrane. The methodology involves reconstruction of the
zeolite-impregnated material and transport simulations.
2.1. Theory and modeling
218
P-2.1-07
Distribution of Al and Adsorption of NH3 and Pyridine in ZSM-12: A Computational Study
G. Feng1, Y.-Y. Lian1,2, X. Qi1, D. Yang1, J. Liu3,*, D. Kong1,*
1 Shanghai Research Institute of Petrochemical Technology SINOPEC, Shanghai 201208, China,
fengg.sshy@sinopec.com
2 State Key Laboratory of Chemical Engineering, East China University of Science and Technology,
Shanghai 200237, China.
3 National Supercomputing Center in Shenzhen, Shenzhen,518055, China.
The present work investigated the distribution of Al and H/Na atoms in p(1×2×1) ZSM-12 cell, which
contains HO112AlSi55 using density functional theory. The adsorption of NH3 and pyridine in the
ZSM-12 were also investigated. The results indicate that the Al atoms could distribute evenly in the
ZSM-12. NH3 and pyridine interacted with the Na+ slightly in NaZSM-12, while they could form NH4
and NC5H6 species in HZSM-12.
P-2.1-08
Understanding adsorption and diffusion of highly polar vapors on mesoporous MOFs through a
combined experimental and molecular simulation approach
M. F. De Lange1,2, J. J. Gutierrez-Sevillano3, S. Hamad3, J. Gascon1, T.J.H. Vlugt2, S. Calero3, F.
Kapteijn1
1Catalysis Eng., Chem. Eng. Dep., Delft University of Technology, Delft, The Netherlands
2Process & Energy Lab., Delft University of Technology, Delft, The Netherlands
3Dep. of Phys., Chem., & Nat. Systems, University Pablo de Olavide, Seville, Spain
Monte Carlo and Molecular Dynamics simulations were performed to investigate adsorption and
diffusion of H2O and methanol on MOFs MIL-100 and MIL-101. For methanol, fair agreement with
adsorption experiments was obtained. For H2O the used force field highly influences the extent of
agreement. In these materials accurate description of adsorption is strongly determined by adsorbateadsorbate interactions. H2O is more mobile in both structures and diffusion is faster in MIL-101. A
maximum in diffusion is observed for MIL-101 at moderate loadings.
P-2.1-09
Electronic propensity of Cu(II) / Cu(I) sites in zeolites to activate NO: spin- and orbital-resolved
Cu–NO electron transfer
E. Broclawik1, P. Kozyra2, M. Radon2, A. Stępniewski1, J. Datka2
1J. Haber Institute of Catalysis PAS, Krakow, Poland, broclawi@chemia.uj.edu.pl
2Faculty of Chemistry, Jagiellonian University, Krakow, Poland
Notable decline of NO activation by Cu(II) compared to Cu(I) sites in zeolites is explained by spinresolved electron transfers between copper center and NO. Results of charge transfer analysis for
Cu(II)-NO adduct in MFI are compared with Cu(I)-NO and referenced to interaction of NO with free
Cu+. We show that backdonation, strongly activating NO bond by populating antibonding π* orbital,
dominates only for Cu(I) site. For other models, the donation of unpaired electron prevails,
strengthening the N–O bond by depopulating antibonding orbital. IR shows blue-shift of NO
stretching frequency for Cu(II) site and strong red-shift for Cu(I).
17 IZC, 2013. POSTER COMMUNICATIONS
219
P-2.1-10
Atomic structure of Fe- and Ti- substituted thin films of silica on Ru(0001)
F.D. Fischer1, R. Wlodarczyk1, J. Sauer1, X. Yu,2J.A. Boscoboinik2, E. Emmez2, B. Yang2, S.
Shaikhutdinov2, H.-J. Freund2
1Humboldt-Universität zu Berlin, Department of Chemistry, Unter den Linden 6, 10009 Berlin,
Germany, f.fischer@hu-berlin.de
2Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4 - 6, 14195 Berlin, Germany
Density functional theory calculations and surface science methods provide new insights into
ultrathin, well-defined films of substituted silica grown on a Ru(0001) single crystal. The substitution
of Fe- or Ti-atoms for Si does not follow Löwenstein’s rule; instead, the structures can be understood
as silica monolayers grown ontop of a monolayer of metal oxide.
P-2.1-11
Theoretical Study of Effects of Exchangeable Cations on Electronic, Structural Properties of
ETS-10
M. Koç1, D. Toffoli2, H.Toffoli3, B.A. Kurç1,4
1Micro and Nanotechnology Department, Middle East Technical University, Ankara, Turkey,
koc.mehmet@metu.edu.tr
2 Dep. of Chemistry, Middle East Technical University, Ankara, Turkey
3 Dep. of Physics, Middle East Technical University, Ankara, Turkey
4Central Laboratory, Middle East Technical University, Ankara, Turkey
Although there are recent works on different ion-exchange studies in ETS-10 investigating the
structural changes induced into ETS-10 and their potential applications, there is still limited
information about the local distortions occurring in the above mentioned titania chain as a function of
varying concentration and type of exchanged cations. Accordingly, in this current study we have
modeled ETS-10 using DFT to investigate the effect of exchangeable cations on the O-Ti-O chain in
ETS-10 giving clues on its local structure and potential use in such applications. Furthermore,
geometric, electronic and optical properties of ETS-10 are calculated including partial charge
distribution, optimized cation positions, band gap, bond length and angle analysis.
P-2.1-12
Computational Approach of the Inverse Sigma Transformation of Zeolites
Elke Verheyen1, Lennart Joos2, K.Van Havenbergh,E.Breynaert,N.Kasian,E.Gobechiya,
K.Houthoofd,C.Martineau,M.Hinterstein,F.Taulelle,Veronique Van Speybroeck2, Michel
Waroquier2,S.Bals,G.Van Tendeloo,Christine E.A. Kirschhock1 and Johan A. Martens1
1Center for Surface Chemistry and Catalysis, KU Leuven, Belgium
2Center for Molecular Modeling, Ghent University, Belgium, lennart.joos@ugent.be
Inverse sigma transformation of a zeolite framework was for the first time achieved experimentally
[Nat Mater]. Computational chemistry helped to understand the reaction and resolve the structure of
final material. Starting from a UTL type zeolite, a new framework connectivity was obtained by
elimination of germanium and contraction of the zeolite layers. This led to the discovery of the allsilica COK-14 zeolite with intersecting 12- and 10-membered ring channel system and may open
perspectives for the synthesis of many more zeolites.
2.1. Theory and modeling
220
P-2.1-13
Enhancing diffusion selectivities in FER-type structures by molecular traffic control
C. Chmelik1, F. Hibbe1, A. Lauerer1, J. Kärger1, J.M. van Baten2, R. Krishna2, V.R.R. Marthala3, J.
Weitkamp3
1University of Leipzig, Germany, chmelik@physik.uni-leipzig.de
2University of Amsterdam, The Netherlands,
3University of Stuttgart, Germany
We present a study of the diffusivity of small alkanes and alcohols in siliceous ferrierite. A
surprisingly high difference in the diffusivities of methanol and ethanol has been observed. This
difference most likely results from an interplay of two phenomena, which have been recently
discussed as options to manipulate mixture diffusion. The major conclusion can be summarized in
two points: (i) molecular traffic control effects can be facilitated by molecular clustering and (ii) their
combination provides a new option for enhancing diffusion selectivities and, thus, for further
optimizing the use of nanoporous crystalline materials in technical applications.
P-2.1-14
A DFT study on the acidity of SAPO-34 molecular sieves with different Si contents
Yanyan Chen, Zhihong Wei, Junfen Li, Mei Dong, Zhangfeng Qin, Weibin Fan*, Jianguo Wang*
State Key laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences,
Taiyuan, Shanxi 030001, PR China, fanwb@sxicc.ac.cn, iccjgw@sxicc.ac.cn
The effect of Si contents in SAPO-34 molecular sieves on their Brønsted acidity was studied at the
level of periodic density functional theory. The substitution of one Si in the framework shows that the
four possible location of proton around Si is approximately equivalent, whereas the acidic strength on
oxygen atom located in one 4-O, one 6-O, and one 8-O ring is the strongest. With the increase of Si in
the framework, the acidic strength increases synchronously as indicated by adsorption energies of
NH3 and the vibrational frequencies of O-H, which is consistent with the experimental results. In
addition, the adjacent substitution of Si sites improves the acidic strength. However, the formation of
Si islands by two Si atoms is unfavorable with endothermic energy up to 236.4 KJ/mol, whereas
further substitution of Si around Si islands is exothermic.
P-2.1-15
Effect of Electrostatic Properties on VOCs Binding in IRMOFs:
Density Functional Theory Study
Wu Ying1, Wu Yongbiao2, Liu Defei3, Xia Qibin4, Li Zhong5, Xi Hongxia6
1The School of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou, Guangdong 510641, People’s Republic of China, dixonsion@gmail.com
Volatile Organic Compounds (VOCs) have numerous bad effects on environment and mankind.
Metal-Organic Frameworks (MOFs), a new class of porous solid materials are considered to be great
potential candidates to solve the VOCs problems. In attempt to understand the adsorption mechanism
of MOFs, based on the molecular level, the Quantum Chemical Calculation was used to investigate
VOCs adsorption properties of MOFs. Methanol, acetaldehyde and acetone adsorbed in IRMOF-1
were explored using the Density Functional Theory (DFT) method. These VOCs were chosen based
on their electrostatic properties. The adsorption behaviors of them in IRMOF-1 were found to be
similar, they tend to be adsorbed at the corners than organic linkers. Based on the results, an
assumption was proposed to explain the electrostatic interaction mechanism between VOCs and
IRMOFs. In order to enhance the adsorption capacity of organic linkers, NH2 groups were inserted
into organic linker. This insertion was found to have a great influence on organic linker, which made
a distinct change in the binding energies, proving that NH2 insertion was particularly useful to
enhance the adsorption capacity at the organic linker of IRMOFs.
17 IZC, 2013. POSTER COMMUNICATIONS
221
P-2.1-16
Water adsorption in a flexible metal-organic framework (IM19): adsorption-induced structural
transition and hydrothermal stability
V. Haigis1, D. Bousquet1, F.-X. Coudert2, A.H. Fuchs2, R. Vuilleumier1, A. Boutin1
1 École Normale Supérieure, CNRS, UPMC, Paris, France, volker.haigis@ens.fr
2 CNRS & Chimie ParisTech, Paris, France
Understanding the adsorption of water in metal-organic framework (MOF) and particularly in
compliant frameworks is crucial in view of considering a given MOF for a specific industrial process.
The IM-19 MOF is a gallium based MIL-53 type solids that exhibit large amplitude shrinkage and
expansion (so-called "breathing"). A joint experimental and theoretical study has allowed to fully
caracterize the water adsorption in IM-19 from both thermodynamic and structural point of view. A
complete water pressure – temperature phase diagram has been established, revealing specificities of
the system that can be attributed either to metal nature of the material or to water. In order to get
insights on the microscopic behavior and the hydrothermal stability of the system, first-principle
molecular dynamics have been performed to elucidate the degradation mechanism of the material at
the microscopic level.
P-2.1-17
Computational design of a highly gas selective acidic substituted porous Zr terepthalate toward
the synthesis & adsorption characterization
Qingyuan Yang1,2, Dong Wu1,2, Sébastien Vaesen3, Ana Lago4, Florence Ragon4, Thomas Devic4,
Christian Serre4, Guy De Weireld3, Philip Llewellyn5, Chongli Zhong2 and Guillaume Maurin1
1 ICGM UMR CNRS 5253 Université Montpellier 2, France, guillaume.maurin@um2.fr 2 BUCT,
China 3Université de Mons, Belgium ; 4 Université de Versailles-CNRS, France,5 Université AixMarseille - CNRS, Marseille, France
A computational screening effort was deployed to predict the CO2/N2 and H2S/CH4 adsorption
selectivity via GCMC simulations for a wide range of existing and hypothetical functionalized MOF
type materials. This exploration evidenced that a Zr-based MOF, the UiO-66(Zr), grafted by two
carboxylic groups outperforms the selectivities currently reported for the conventional adsorbents.
Such a predicted solid was then successfully synthesized.
P-2.1-18
Evaluation of site occupancy factors in refinements of zeolite-type crystal structures
R.X. Fischer1, W.H. Baur2]
1 Fachbereich Geowissenschaften, Universität Bremen, Germany, rfischer@uni-bremen.de
2 Western Springs, IL 60558, USA
Zeolite-type crystal structures very often contain atom positions which are not fully occupied. These
are typically nonframework cations and sorbants. The occupancy factors are usually determined in
least squares refinements of crystal structures based on X-ray or neutron diffraction data. Especially
in those cases where two atom positions are too close to each other to be simultaneously occupied by
atoms the plausibility of the refinement results has to be evaluated. Here we apply techniques for the
evaluation of site occupancy factors using boolean satisfiability (SAT) optimizations. Comprehensive
testing of the approach was performed using the zeolite data compiled by us in the databank ZeoBase
and published in the Landolt Börnstein series IV/14 on microporous and other framework materials
with zeolite-type structures. ZeoBase contains more than 5,000 entries of crystal structure data of
zeolites. Most of these entries have atoms with statistical occupancies of the nonframework atoms and
species. The SAT approach revealed that many of the published occupancy factors in entries of
zeolites cannot be correct.
2.1. Theory and modeling
222
P-2.1-19
A theoretical study of Cu2O and Cux clusters hosting in MOR dealuminated zeolite
D. Homero Galván1, Joel Antúnez-García1, Vitalii Petranovsky1
1Centro de Nanociencias y nanotecnología at UNAM, Ensenada, Baja California, México,
donald@cnyn.unam.mx
We present a theoretical study of the formation of composites, on terms of periodic density functional
method, as result of hosting cooper and cooper-oxide clusters within the main channel of
dealuminated MOR zeolite. On general terms, our results shows that clusters not embedded in the
walls of main channel, instead they were captured trough electrostatic confinement. However, the
electrostatic confinement is stronger for copper oxide clusters than for pure cooper clusters.
Interestingly, the electrostatic confinement is able to reduce considerably the forbidden energy band
gap. On addition, our results shows that both electrostatic confinement and forbidden energy gap
reduction, is influenced by oxygen atoms interactions.
P-2.1-20
Application of DFT calculations to study the active site on the MCM-41 with T-atoms
substituted
E.O. Castrejón-González1, J.C. Fierro-González1, G. Herrera-Pérez2
1Dep. of Eng. Chem., Inst. Tech. of Celaya, Mexico.
2Dep. of Eng. in Mater., Inst. Tech. Sup. of Irapuato, Mexico.gaherrera@itesi.edu.mx
The MCM-41 may consist only of units (SiO4)-4, this unit can be replaced by other metals of Group
III or IV replacing If the network. The versatility of the MCM materials for applications in catalysis is
attributed to the substitution referred to in order to influence the chemical reactivity, which may be
evaluated using the criteria of surface acidity. In mesoporous materials there is no certainty about
their microstructures therefore proposes a cell design for calculation T8 when one atom is replaced by
another atom as B, Al, Ga or In. To determine the potential energy, geometry optimization, electronic
charge distribution and energy calculation of the frontier orbitals are performed with a level of ab
initio calculations with both the methodology of the Density Functional Theory (DFT).
P-2.1-21
Lithium as a Trojan Horse for Aluminum Incorporation in Zeolites
Lennart Joos1, Leen Van Tendeloo2, K. Lauwers2, Y. Lorgouilloux2, Veronique Van Speybroeck1,
Christine E. A. Kirschhock2 and Johan A. Martens2
1Center for Molecular Modeling, Ghent University, Belgium, lennart.joos@ugent.be
2Center for Surface Chemistry and Catalysis, KU Leuven, Belgium
When high concentrations of Li+ ions are present during zeolite synthesis, KFI and CHA type zeolites
are formed with Si/Al ratios as low as 1.67. These products show excellent perspectives for deep
removal of CO2. All obtained zeolites were fully characterized by complementary techniques
including XRD, SEM, TEM, 27Al and 29Si MAS NMR. Moreover, molecular modeling techniques
explored the initial steps in the zeolite formation and showed that lithium strongly interacts with the
aluminum atoms. This interaction results in a faster Si-Al condensation rate when Li+ is present,
thereby assisting the incorporation of Al in the zeolite framework.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.1-22
Molecular Simulation of Zn+, Cu+2, NH4+ Ion-Exchange on Clinoptilolites
B. Demir1, R. Ekhteiari Salmas2, A. Sirkecioglu1, M. Yurtsever2, M.G. Ahunbay1
1 Department of Chemical Engineering, Istanbul Technical University, Turkey,
2 Department of Chemistry, Istanbul Technical University, Turkey, ahunbaym@itu.edu.tr
Zn+, Cu+2, and NH4+ are the most abundant cations in the domestic, and industrial wastewaters. It is
essential to remove these cations from wastewaters before discharging into surface water,
groundwater or the sea due to the environmental regulations. The commercially available natural
zeolite, Clinoptilolite has high metal cation removal potential from wastewaters. Cation (Na+, K+,
Mg2+, Ca2+) composition of clinoptilolite may vary significantly based on its origin. In this study,
quantum mechanical calculations and molecular dynamics (MD) simulations are used to investigate
principal parameters (concentration of the electrolyte solution, temperature and crystal thickness)
affecting the removal Zn+, Cu+2, and NH4+ cations from model wastewater through ion-exchange
process. The electrostatic charges of the framework atoms at the crystal surface were determined via
DFT calculations. MD simulations are used to simulate the ion exchange between the clinoptilolite
and the electrolyte solutions with different cation concentrations. The changes in the ion release rates
and ion-exchange ratios were analyzed by varying the considered parameters.
P-2.1-23
Molecular simulation by KMC of early stages of zeolites nucleation and study of synthesis
parameters.
M. Ciantar1; C. Nieto-Draghi1, C. Mellot-Draznieks2, P. Sautet3, Thuat T. Trinh3
1IFP Energies nouvelles, 1-4 avenue de Bois-Préau, 92852 Rueil-Malmaison, France,
marine.ciantar@ifpen.fr
2Laboratoire de Chimie des Processus Biologiques, Collège de France, Paris, France
3Laboratoire de Chimie, École normale supérieure de Lyon, Lyon, France
Nucleation is one of the first steps in the process of crystallization of porous materials like zeolites.
Zeolite synthesis depends on reactant concentrations, pH, templates, etc., and the role played by these
variables on the final structure is a real challenge. The first steps of oligomerisation represent a key
factor in the comprehension of the kinetically driven nucleation process. In this context, molecular
simulation techniques represent an useful tool to shed some light in this early steps of the zeolite's
synthesis inaccessible from experiments.
In the present work we provide a kinetic Monte Carlo study of the influence of different synthesis
variables (species concentration, pH and temperature) on the early stages of the oligomerisation
mechanism. We focus our study on the analysis of the topology and nature of the species formed in
the system (rings, tretramers, etc). In this case we have used the SPPARKS parallel kMC simulation
code to explore the time evolution of the concentration of the different species involved in the
reaction using data on kinetic barriers obtained from DFT calculations of silicate species. The specific
influence of template is studied, shedding some lights on templating effects.
2.2. Advanced characterization techniques
224
P-2.2-01
Synthesis of gold catalysts supported on Ce-modified mesoporous zirconia: Effect of Ce/Zr
molar ratio on the dispersion of gold particles
H. Azzi1, L.Aouali-Chérif*1, S. Siffert2,3, ,S.Royer4, A.Aissat2,3, R. Coussin2,3,S. Spronier4,A.
Bengueddach5.
1Laboratoire de Catalyse et Synthèse en Chimie Organique, Université de Tlemcen BP 119, Algérie
2Université Lille Nord de France, F-59000 Lille, France 3ULCO
3UCEIV, F-59140 Dunkerque, France
4LACCO, Université de Poitiers-CNRS, ESIP,40avenue du Recteur Pineau, F_86022 Poitiers cedex,
France
5 Laboratoire de Chimie des Matériaux, Université d’Oran, Algérie
E-mail addresses: *cherif_leila@yahoo.fr, catalyse030781@yahoo.fr
Ce-modified mesoporous zirconia supports were prepared by a templating sol-gel method with a
variation of Ce/Zr molar ratio. 1% of Au was loaded on Ce-modified mesoporous zirconia by
deposition precipitation method. CeZrO2 and Au/CeZrO2 samples were characterized by XRD, N2
adsorption-desorption, H2-TPR, MET and DR/UV-vis,. The results showed that the Ce/Zr molar ratio
had a great influence on the dispersion of gold particles
P-2.2-02
Dehydration dynamics of levyne: evidence for a new zeolite topology
Rossella Arletti1, Simona Quartieri2, Giovanna Vezzalini3, Fernando Cámara1
1Dip. di Scienze della Terra, Univ. di Torino, Torino, Italy, rossella.arletti@unito.it
2Dip. di Fisica e di Scienze della Terra, Univ. di Messina, Messina, Italy
3Dip. di Scienze Chimiche e Geologiche, Univ. di Modena e Reggio Emilia, Modena, Italy
The thermal induced structural modifications of a natural levyne were studied by both time-resolved
synchrotron X-ray powder diffraction between room-T and 800°C, and by conventional-source highT single crystal X-ray diffraction. Above 230°C, a new topology rises, coexisting in a percentage of
about 50% with the original one. The new framework consists of a sequence of a new zeolitic cage
(described as a 20-hedron formed by fourteen 6mR and by six 4mR) and two cancrinite cages along
[0001]. The new topology – reported in the database of the hypothetical zeolite structures as
166_2_293 – belongs to the ABC-6 family and can be described with the sequence ABABABCBC, to
be compared with that of levyne AABCCABBC.
P-2.2-03
Estimation of the real temperature of samples in IR cell using OH frequency of silica
H. Yamazaki1, H. Shima2, E. Yoda3, T. Yokoi1, T. Tatsumi1, J.N. Kondo1
1Chemical Resource Laboratory, Tokyo Institute of Technology, Yokohama, Japan,
yamazaki.h.ah@m.titech.ac.jp
2Science and Technology Research Center, Mitsubishi Chemical Group, Yokohama, Japan
3Dep. of Chemistry and Material Engineering, Ibaraki National College of Technology, Ibaraki,
Japan
In IR cells for studies on catalysts, which are widely used recently, the estimation of the real
temperature sometimes becomes difficult. We report here, the method employed for the calibration of
real temperatures to those measured from outside the cell, and submit the correlation between the real
temperatures and the peak top frequencies of OH stretching vibration of amorphous silica.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.2-04
Structural characterization of fluorenone dye in zeolite L
L. Gigli1, G. Agostini2, R. Arletti3, E. Fois4, C. Lamberti2, G. Tabacchi4, S. Quartieri5, G. Vezzalini1
1 DSCG,UNIMORE, Largo S. Eufemia 19, 41121 Modena , Italy, lara.gigli@unimore.it.
2 NIS, UNITO, Torino, Italy
3 Earth Sciences Dpt., UNITO, Torino, Italy
4 DSAT and INSTM, UNINSUBRIA, Como, Italy
5 Physics and Earth Sciences Dpt., UNIME, Messina, Italy
Zeolite L is a versatile host material for the supramolecular organization of cromophore molecoles.
The inclusion of dyes into the channels may give an hybrid material with unique properties, such as
efficient energy transfer. The dehydrated ZL-fluorenone complex was investigated by synchrotron Xray powder diffraction and Rietveld refinement. 1.7 dye molecules per unit cell are embedded in the
12-ring channel, running parallel to c axis. The strong interaction between dye carbonyl group and the
extraframework potassium cation, predicted by theoretical modeling, is experimentally confirmed by
the short bond distances and explains why dye is not displaced by water molecules when the hybrid is
re-exposed to the air.
P-2.2-05
New phospho-silicate and niobo-phospho-silicate MCF materials modified with MPTMS –
structure, surface and catalytic properties
K. Stawicka, M. Trejda, M. Ziolek
Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 60-780 Poznan, Poland,
tmaciej@amu.edu.pl
Phosphorous (P) and niobium (Nb) sources were introduced into the gel during the synthesis of MCF.
The materials obtained were used as supports for grafting of (3-mercaptopropyl)trimethoxysilane
oxidised by H2O2 to sulphonic groups. The focus in this work is on the deep insight into the textural
parameters of the materials, estimation of the efficiency of P and Nb incorporation into MCFs,
surface acidic properties and activity and selectivity in acetic acid esterification with glycerol. P is
much easier included into the structure of MCF when the source of Nb is present in the synthesis gel.
Nb species present in MCF support participate in anchoring of MP, whereas P species are not
involved in linkage to organosilane. The location of Brønsted acid sites preferentially in the windows
of MP/PMCF-10 material provides a quick esterification resulting in the highest glycerol conversion
(94 %).
2.2. Advanced characterization techniques
226
P-2.2-06
Direct hydrothermal synthesis of monodisperse nickel oxide in SBA-15, and its enhanced
catalytic selectivity
Baowang Lu, Katsuya Kawamoto
Center for material cycles and waste management research, National Institute for Environmental
Studies, 16-2 Onogawa, Tsukuba, Ibaraki 305-8506, Japan; *E-mail: lu.baowang@nies.go.jp, Tel:
(+)81-29-850-2959, Fax: (+)81-29-850-2091,
By small-angle and wide-angle XRD patterns, NiO/SBA-15 was obtained by direct hydrothermal
synthesis method. With NiO amount of 1~3 wt%, NiO particles size was much smaller than the
diameter of nanochannels, NiO particles were almost in nanochannels. With NiO amount of 5~15
wt%, NiO particles size was ≈ 30 nm and larger than the diameter of nanochannels, NiO particles
were also on the outer SBA-15 surface except in nanochannels. As the NiO amount increased to
20~40 wt%, NiO particles size was ≈ 38 nm, NiO particles may aggregated. The nitrogen adsorptiondesorption isotherm was typical type IV isotherm with H1-type hysteresis for SBA-15 The TEM
image had ordered mesoporous structure for typical SBA-15, indicating that NiO particles were
highly dispersed into SBA-15. We also investigated the RWGS reaction using NiO/SBA-15. With
NiO loading of less than 15 wt %, CO selectivity was 100%, regardless of temperature. When NiO
loading exceeded 20 wt %, CO selectivity was 100 % at the temperature of over 600 °C, by contrast,
CO selectivity was not 100 % at the temperature of less than 500 °C. Therefore, CO selectivity was
influenced by NiO dispersion at low temperature.
P-2.2-07
Synthesis of Silica-alumina with Tunable Acidity Investigated by MAS NMR Spectroscopy
Jun Huang1, Yijiao Jiang2, Alfons Baiker3, Michael Huang4
1 Laboratory for Catalysis Engineering, School of Chemical and Biomolecular Engineering, The
University of Sydney, NSW 2006, Australia, Tel: #61 9351 7483; Email: jun.huang@sydney.edu.au
2 ARC Centre of Excellence for Functional Nanomaterials, The Particles and Catalysis Group, The
University of New South Wales, Sydney, 2052 Australia
3 Institute of Chemical and Bioengineering, ETH Zürich, Switzerland
4 Institute of Chemical Technology,University of Stuttgart, Germany
Solid acids facilitate cleaner and much easier reactions and thus have replaced toxic, corrosive, and
unrecyclable liquid mineral acids in many catalytic applications, the most prominent being the
cracking and refining of a billion tons of crude oil into useful chemical components. Amorphous
silica/alumina (SA) is one of the popular solid acids that provide moderate Brønsted acidity, albeit
weaker than that of zeolites. Herein, we show SAs prepared by flame-spray pyrolysis (FSP SAs) and
a tunable Brønsted acidity ranging from moderate to zeolitic acid strength has been observed by
multi-nuclei MAS NMR spectroscopy, thereby allowing their versatile utilization in oil refineries and,
furthermore, as excellent supports for nanoparticles in many hydrogenation and oxidation reactions.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.2-08
Powder Diffraction Analysis of Porous Structures Using the Derivative Difference Method
L.A. Solovyov1, A.G. Anshits1, S.N. Vereshchagin1, G.V. Echevsky2, A.V. Toktarev2
1Institute of Chemistry and Chemical Technology, Krasnoyarsk, Russia, leosol@icct.ru
2Boreskov Institute of Catalysis, Novosibirsk, Russia
Detailed and reliable powder diffraction structure analysis of functional porous materials is, in
general, a challenging task due to a number of issues. The powder patterns of such materials are,
normally, contaminated by various background modulations resulted from amorphous and semicrystalline impurities, inhomogeneous distribution of guest species and other parasitic sources. In
addition, functionality of materials often implies their non-ideality manifested in a complex
microstructure of crystallites, faulting, twinning, intergrowths, etc. In this report, the application of
the Derivative Difference method to the structure analysis of microporous and mesoporous materials
is presented and discussed. As a particular case in point illustrating the advantages of the method, the
structure analysis of a series of ZSM-5 zeolites revealing MFI/MEL intergrowths is described.
P-2.2-09
Evaluation of the behavior of nitrogen and sulphur compounds whith adsorbents in fixed bed to
be used in pre treatment of diesel in hydrotreatments units
Silva, L.S(1), Figueiredo, M.A.G(1)
(1) Industrial and Operations Processes Department, Chemistry Institute, Rio de Janeiro,
Brazil, Masters Degree Program in Chemical Engineering, mgaya@uerj.br
In the present work, we have sought to measure the behavior of fuel contaminants in fixed bed tests
performed in studies for the selection of commercial adsorbents, which the goal is the selective
removal nitrogen, sulfur and aromatic compounds family in diesel feeds during the adsorption process
with a clay as an adsorbent. The diesel feed was pre-treated with solid phase extraction using alumina
separating three different fractions with hexane, chloroform and chloroform plus methanol. The
results of the breakthrough tests showed that the benzothiophene’s and dibenzotiophene’s families,
the adsorbent was saturated quickly, and the nitrogen compound’s families such as: anilines,
quinolones, acridines, indoles and carbazoles presented a better connection with the adsorbent.
P-2.2-10
Exploring diffusion and reaction in nanoporous catalysts
by IR micro-imaging
Tobias Titze1, Christian Chmelik1, Dirk Enke1, Roger Gläser1, Jens Kullmann1, Jörg Kärger1,
Lutz Prager2, Jens Weitkamp3
1University of Leipzig, Germany, titze@physik.uni-leipzig.de
2Leibniz Institute of Surface Modification, Leipzig, Germany,
3University of Stuttgart, Germany
A century after the formulation of the fundamental laws of interdependence between diffusion and
reaction in heterogeneous catalysis, the measurement of the diffusivities under reaction conditions in
the interior of nanoporous catalysts has remained a challenge for the experimentalists. By coating
nanoporous glass membranes, we succeeded in creating a model system which allows the selective insitu observation and recording of transient concentration profiles of the different components
involved in counter-diffusion experiments and catalytic conversion by means of IR micro-imaging.
We are presently performing experiments for demonstrating these potentials by recording the spatial
distribution of the components involved in simple model reactions like the reduction of benzene to
cyclohexane.
2.2. Advanced characterization techniques
228
P-2.2-11
Characterizing the Hydrothermal Stability of Zeolites for
Thermal Energy Storage Applications
F. Fischer1, A. Hauer1, E. Lävemann1
1Bavarian Center for Applied Energy Research (ZAE Bayern), Division 1: Technology for Energy
Systems and Renewable Energy, Garching, Germany, fischer@muc.zae-bayern.de
Thermal energy storages (TES) based on adsorption processes are a promising alternative to
conventional storage devices for specific applications. Hydrophilic zeolites, like type 13X are suitable
adsorbent materials with high water uptake and high temperature lift during the adsorption process.
However the hydrophilicity of these zeolites can decrease with the number of adsorption and
desorption cycles and consequently the energy storage density decreases as well. The degree of
hydrothermal destruction of zeolite can be examined by measuring the loss of water uptake with
increasing number of adsorption and desorption cycles.
An experimental setup has been built wherein four temperatures, four water vapour pressures and
duration of the exposure can be varied independently. Thus 16 different data points are recordable at
once. After defined time spans the water uptake of each sample is externally measured
gravimetrically. The loss of water uptake corresponds to the hydrothermal stability of each sample.
With this experimental setup detailed information of the different influences regarding the
hydrothermal stability of the adsorbent can be achieved.
P-2.2-12
Investigation of distribution and chemical state of Ti species in deactive Hollow TS-1 zeolite
from industrial ammoxidation process
Changjiu Xia, Yanjuan Xiang, Bin Zhu, Aiguo Zheng, Min Lin, Xu Guangtong, Xingtian Shu
State Key Laboratory of Catalytic Materials and Reaction Engineering , Research Institute of
Petroleum Procesing, SINOPEC, Beijing, P. R. CHINA, minlin@tom.com
Hollow TS-1 zeolite is an efficient catalyst for the industrial cyclohexanone ammoxidation by low
concentration H2O2 aqueous solution under mild conditions. However, catalytic performce of this
material is decreasing during long-time alkaline ammoxidation, which is attributed to the effect of
coke deposit, framework Si atoms dissolution and tetrahedral Ti atoms removal. Coke deposit can be
resolved by calcination, and other two processes are irreversible for catalytic activity. In this paper,
XPS spectrum of deactive Hollow TS-1 zeolite indicates the ratio of framework Ti/ nonframework Ti
is greater than the fresh one which means some framework tetrahedal Ti atoms translate into nonframework Ti atoms. From TEM and EFTEM pictures, highly scattered Ti aggregates were found in
the zeolite, which is considered amorphous TiO2 or TiO2-SiO2 oxides.
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P-2.2-13
Investigation of the templates in microporous SAPO STA-7 and MgAPO STA-15 using
polarised synchrotron IR radiation
E. C. Eschenroeder1, A. Turrina1, L. Picone1, G. Cinque2, P. Cox3, R. Howe4, P. A. Wright1
1 School of Chemistry, University of St Andrews, North Haugh, KY16 9ST, UK, ecve@standrews.ac.uk, at75@st-andrews.ac.uk
2 Diamond Light Source, Harwell Science and Innovation Campus, Didcot, OX11 0DE, UK
3 School of Pharmacutics and Microbiology, University of Portsmouth, St. Michael’s Building, White
Swan Road, Portsmouth, UK PO1 2D, UK
4 Department of Chemistry, University of Aberdeen, Meston Building, King’s College, Aberdeen
AB24 3UE, UK
High-intensity synchrotron IR micro-spectroscopy is used to gain detailed insights into the templating
and calcination process for microporous materials. In combination with polarisation the orientation of
templates with respect to crystallographic axis is observable. In-situ monitoring of the template
decomposition is accessible using a Linkam cell set-up. In this study the concept was successfully
applied to single-crystals of SAPO STA-7 and MgAPO STA-15. Linking these experimental results
to computational methods enables models for the orientation and geometry of the templates within the
channels and cages to be developed.
P-2.2-14
Local order in zeolites from 14N NMR
Eddy Dib and Bruno Alonso
ICGM-MACS, UMR 5253 CNRS-ENSCM-UM2-UM1, Institut Charles Gerhardt de Montpellier, 8
rue de l’Ecole normale, 34296 Montpellier cedex 5, France. Eddy.Dib@enscm.fr
Owing to the quadrupolar interaction, 14N nucleus (I = 1, 99.6 % abund.) is a highly sensitive NMR
probe for the investigation of the local charge distribution and dynamics. We investigate these
potentialities for the 14N solid-state NMR characterization of as-synthesized mesoporous materials
and zeolites where tetraalkylammonium cations are used as structure directing agents.
We are currently working on MFI-type zeolites obtained through different synthetic conditions (OHvs. F- routes) and possessing different chemical compositions (Si/Al ratio). After syntheses or posttreatments, 14N solid state NMR investigation allows us to correlate the quadrupolar parameters to the
local structure of the organic and/or inorganic species. The 29Si and 13C NMR parameters are
investigated also to emphasize the structural-spectroscopic 14N correlations.
In this communication, we will present our NMR approach, the resulting 14N quadrupolar parameters,
and their correlation to the local structural properties of the as-synthesized MFI-type zeolites (charge
distributions, defects).
2.2. Advanced characterization techniques
230
P-2.2-15
Nonlinear optical spectroscopy reveals the external surface and phase transitions of metalorganic frameworks
Monique A. van der Veen,1,2 Helge Reinsch,3 Karen Markey,1 Ivo Stassen,1 Thierry Verbiest,1
Mischa Bonn,2 Norbert Stock,3 Ellen H.G. Backus,2 Dirk E. De Vos1
1 University of Leuven, KU Leuven, Belgium, monique.vanderveen@biw.kuleuven.be
2 Max-Planck Institute for Polymer Research, Mainz, Germany
3 Christian-Albrechts Universität zu Kiel
Second-order nonlinear optical effects have the powerful property that they are only allowed when
symmetry is broken, i.e. at interfaces and for non-centrosymmetric materials. The result is 1) that they
can selectively study interfaces present between centrosymmetric media, and 2) that they are
extremely sensitive to symmetry properties of non-centrosymmetric crystals. The external surface of
metal organic frameworks (MOFs) plays a critical role in many applications as it is the first barrier for
entering molecules. It would be highly desirable to directly obtain chemical information from the
surface. Such information can be obtained using sum frequency generation (SFG), a surface specific
vibrational spectroscopy technique. We use SFG to study the external surface of ZIF-8. Furthermore,
the extreme sensitivity of nonlinear optics to symmetry is used to determine with second-harmonic
generation microscopy the vapour pressure modulated phase transitions of the aluminium metalorganic framework CAU-10 family.
P-2.2-16
Characterization of Zeolites via Isomerization and Disproportionation of
1,3-Dimethylbenzene, 1,3-Diethylbenzene and 1,3-Diisopropylbenzene as Catalytic Test
Reactions
C.Y. Chen1, R. Bermejo-Deval1,2, S.I. Zones1, S.A. Elomari1 and D. Xie1
1Chevron Energy Technology Co., Richmond, California 94802, USA, cychen@chevron.com
2California Institute of Technology, Pasadena, California 91125, USA
Isomerization and disproportionation of 1,3-diethylbenzene is established as a new test reaction for
characterizing the effective pore structures of zeolites, complementary to those of 1,3dimethylbenzene and 1,3-diisopropylbenzene as feeds. Isomerization of 1,3-diethylbenzene is favored
over its disproportionation when the pore sizes of zeolites decrease, with 1,4-diethylbenzene being
favored over 1,2-diethylbenzene. The results from the test reactions with these three feeds over a
broad spectrum of zeolite structures are compared and discussed.
P-2.2-17
A Synergic Exploration of the Rotational Dynamics of MOFs upon Drug Encapsulation by
Combining Dielectric Relaxation Spectroscopy & Molecular Simulations
S. Devautour-Vinot1, G. Maurin1, D. Cunha2, P. Horcajada2 and C. Serre2
1 Institut Charles Gerhardt, UMR CNRS 5253 UM2, ENSCM, UM1, Place E. Bataillon, Montpellier,
France, sabine.devautour-vinot@um2.fr
2 Institut Lavoisier, UMR CNRS 8180, 45 Avenue des états Unis, Université de Versailles SaintQuentin, Versailles cedex, France
Metal Organic Frameworks (MOFs) appear as valuable candidates for various applications related to
their sorption abilities. The optimization of their performances requires a control of the parameters
that govern the adsorption process, including the confined species/MOF interactions and the synergic
dynamics of the host framework. In this context, Dielectric relaxation spectroscopy is coupled with
molecular simulations to correlate the flexibility of a series of functionalized UiO-66(Zr) MOF
frameworks with the strength of the host/drug guest interactions, which is also of interest for the
implication of MOFs as nano-carriers in the biomedical domain.
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P-2.2-18
Influence of the nitric acid treatment on framework composition and acidity of BEA zeolite:
MQ MAS NMR and FTIR studies
R. Baran1, 2, Y. Millot2, T. Onfroy2, J.-M. Krafft2, T. Grzybek1, S. Dzwigaj2
1AGH University of Science and Technology, Faculty of Energy and Fuels, Al. A. Mickiewicza 30, 30059 Krakow, Poland, rafalbaran@onet.eu
2Laboratoire de Reactivite de Surface UMR 7197, CNRS, UPMC, Site d’Ivry – Le Raphaël, 3, rue
Galilée, Ivry-sur-Seine, France
Dealuminated BEA zeolites were prepared by treatment of HAlBEA(17) zeolite with concentrated
nitric acid (13 mol L-1) for 0.08, 0.16, 0.5, 2 and 4 h. The kinetics of dealumination of HAlBEA(17)
zeolite was investigated by chemical analysis, XRD, FTIR and NMR. Two periods can be
distinguished in the removal of Al atoms from this zeolite. The initial period (up to 0.08 h) during
which the dealumination is very fast and 94 % of Al is removed. This period corresponds to the easy
elimination of the Al species. The second period (from 0.08 to 4 h) much slower corresponds to the
much more difficult elimination of the Al species. 2D 27Al 3Q MAS NMR allows to detect two kinds
of tetrahedral Al atoms which relative amounts depend on the Si/Al ratio and correspond to two
specific types T-sites.
P-2.2-19
Preparation of Highly Dispersed Pt on Beta by the Assistance of Cr
Yoshiyuki Izutsu1*, Yusuke Hidaka1, Yoshiki Nakajima1, Jun Fukuroi1, Kaname Yoshida2, Yukichi
Sasaki2, Masahiko Matsukata1
1Waseda University, Tokyo, Japan, 2Japan Fine Ceramics Center, Aichi, Japan,
yizutsu@aoni.waseda.jp
We investigated the effects of Cr addition on beta to increase Pt dispersion and the catalytic properties
of Pt, Cr-loaded beta for the skeletal isomerization of n-heptane. Chromium addition to Pt/beta
catalyst was effective to inhibit cracking. Based on the STEM/EDX, XRD, UV-Vis, XPS and
EXAFS/XANES results for the structure and valence states of Pt and Cr, we concluded that Pt
dispersion was much improved by the Cr addition, Pt was oxidized to give Pt-O bond, and Cr was
hexavalent. We propose two types of structures of PtCr/beta: (1) Pt formed a bond with oxygen that
would be in chromic acid stabilized in the micropores of zeolite beta, or (2) migration of Pt was
blocked by chromic acid located in the micropores.
P-2.2-20
Structure determination of a new interrupted zeolite PKU-14 by combining powder X-ray
diffraction, rotation electron diffraction, NMR and IR spectroscopy
Jie Su1, Jie Liang2, Yingxia Wang2*, A. Ken Inge1, Junliang Sun1,2, Xiaodong Zou1, Jianhua Lin2*
1Berzelii Centre EXSELENT on Porous Materials, and Department of Materials and Environmental
Chemistry, Stockholm University, Stockholm, Sweden
2College of Chemistry and Molecular Engineering, Peking University, Beijing, China
E-mail: jie.su@mmk.su.se, yxwang@pku.edu.cn, jhlin@pku.edu.cn
By combining powder X-ray diffraction, rotation electron diffraction, NMR and IR spectroscopy, a
new interrupted zeolite PKU-14 was solved. The structure is built by the [46612] cages connected with
D4R units, and all the hydroxyl groups point to the center of the [46612] cage. It can be considered as a
defective structure of ITQ-21 or ITQ-26. PKU-14 shows a three-dimensional 12MR channel system.
2.2. Advanced characterization techniques
232
P-2.2-21
Luminescence activity of irradiated SiO2-clathrate Melanophlogite
G. Buscarino1, L. Vaccaro1, M. Cannas1, F.M. Gelardi1 and R. Boscaino1
1 Dipartimento di Fisica dell’Università di Palermo, Via Archirafi 36, 90123, Palermo, Italy
gianpiero.buscarino@unipa.it
Here we report an experimental investigation on the optical properties of SiO2-clathrate Melanoflogite
subjected to β-ray irradiation. Our results indicate that irradiation generates a characteristic
photoluminescence (PL) activity. The emission profile, excited at 4.32 eV, is structured in a
succession of vibrational lines enveloped by a bell-shaped curve centered around 3.1 eV with
FWHM~0.4 eV. Also the excitation profile, monitored at 3.12 eV, consists of vibrational lines; their
envelope is centered around 4.2 eV with FWHM ~0.4 eV. Time resolved PL measurements indicate
that this PL band is characterized by a single exponential decay with a lifetime τ~40 ns. On the basis
of the analysis of the splitting between adjacent vibronic lines within the PL band, we suggest that the
center responsible for this optical activity should consist in a CH3• molecules trapped into the cages
of material. This conclusion is also supported by our preliminary EPR investigation.
P-2.2-22
Titanium Site Dispersion and Catalytic Epoxidation Activity Control in Mesoporous Silica
Capped using a Dipodal Organosiloxane
L. Fang1,2 B. Albela,1 B. Yang,2 Y. Zheng,1, 2 P. Wu,2 M.-Y. He2 and L. Bonneviot1
1 Laboratoire de Chimie, Ecole Normale Supérieure de Lyon, Institut de Chimie de Lyon, Université
de Lyon, Lyon, France, laurent.bonneviot@ens-lyon.fr
2 Shanghai Key Lab of Green Chemistry and Chemical Processes, Department of Chemistry, East
China Normal University, Shanghai,China
According to many reports on various Ti containing zeolites, it is considered that epoxidation of small
olefins is catalyzed by isolated Ti sites. Ti modified mesoporous silicas catalyse also epoxidation
alkenes that are too bulky for microporous zeolites. However, fixation of titanium by reacting Ti
alkoxides onto silanol groups yields mainly to titanium oxo clusters unless very low Ti loadings are
grafted. To overcome this drawback, the surface silanol of 2D hexagonal mesoporous silicas are here
partly capped before grafting titanium. Partial capping is obtained by partial surface masking using
adsorbed tetramethylammonium (TMA) cations regularly distributed by self-repulsion. Dipodal 1-2ethanebis(dimethylsilyl) moieties grafted on such a surface allow after removal of TMA to increase
drastically the fraction isolated Ti sites in comparison to unmodified surface. The covalently linked
organic layers acting as molecular stencil pattern is investigated using FT-IR, 29Si and 13C solid state
NMR while Ti isolation is evidenced by a drastic blue shift of the LMCT charge transfer band in
correlation with higher cyclohexene epoxidation activity.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.2-23
9,10-Anthraquinone Paramagnetic Complexes on Surfaces of Zeolites and Their Thermal
Transformations
A.V. Fionov1, I.Yu. Shchapin2,3, A.I. Nekhaev2, A.L. Maximov1,2, V.V. Lunin1
1Dep. of Chemistry, Moscow State University, Moscow, Russia, fionov@mail.ru
2A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia
3D.Mendeleyev University of Chemical Technology of Russia, Moscow, Russia
Paramagnetic complexes of 9,10-anthraquinone on zeolites surfaces have been studied by EPR
technique. One center anthrasemiquinone complexes (with one acid center) have been detected after
interaction of anthraquinone and D8-anthraquinone with zeolites at temperatures up to 423 K.
Thermal instability (at 473 K) of anthraquinone adsorbed on zeolites, as well as the coke-forming
ability of zeolites towards n-decane (at 443 K) changed in the row H-Y > H-Beta > H-ZSM-5 ~ HMordenite. The presence of air was found to be crucial for coking reactions under the interaction of ndecane with zeolites.
P-2.2-24
3D electron diffraction, a new solution for structural studies of micro-sized
porous crystalline solids
D.L. Zhang1, S.L. Qiu1
1 State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University,
Changchun 130012, China, zhangdaliang@jlu.edu.cn
Facing up to the challenge in structure solutions for micro-sized porous crystalline solid materials, a
new method using 3D electron diffraction (ED) obtained from transmission electron microscopes
(TEM) has been developed recently. The idea of the method is similar to the X-ray single crystal
diffraction. Based on the modification of TEM and programming, the whole procedure can be done in
a semi-automatic way. Using a special designed TEM, we have started to test and apply this new
method for solving structures of porous crystalline solids such as zeolite, MOFs and organic
framework materials. Although organic components are considered having extremely short living
time under electron beams, our studies show that it is possible to get valuable structure information
from 3D electron diffraction data.
P-2.2-25
The structure of two new disordered zeolites ITQ-38 and ITQ-39 solved
by electron crystallography
T. Willhammar1, J.L. Sun1, W. Wan1, P. Oleynikov1, D.L. Zhang1, X.D. Zou1, M. Moliner2, J.
Gonzalez2,3, C. Martínez2, F. Rey2, A. Corma2
1 Berzelii Centre EXSELENT on Porous Materials and Department of Materials and
Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden, 2Instituto de
Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia, E-46022 Valencia, Spain
3 Escuela de Ciencias Químicas, Universidad de Colima, Colima 28040, Mexico,
tom.willhammar@mmk.su.se
Structure elucidation is essential in order to understand and design the synthesis of zeolite materials
and identify their applications. Intergrowth and stacking disorders are often found in zeolites and
related materials. In this work we show how two complex intergrown zeolite structures, ITQ-39 and
ITQ-38, can be solved utilizing rotation electron diffraction and high resolution transmission electron
microscopy images.
2.2. Advanced characterization techniques
234
P-2.2-26
NMR and powder diffraction crystallography of a layered aluminophosphate : determination of
the average structure, description of non-periodic sub-networks and water cycle
B. Bouchevreau,1 C. Martineau,1 C. Mellot-Draznieks,2 A. Tuel,3 F. Taulelle1
1ILV/UVSQ, Versailles, France,
2LCPB, FRE 3488, Collège de France, Paris, France,
3IRCELYON, CNRS/UL1, Villeurbanne, France
Structure resolution of powders is still a huge difficulty for the discovery of new phases, in particular
for complex solids like zeolites, MOFs, metal-phosphates. We illustrate here, with the example of a
layered aluminophosphate, a method that combines synchrotron powder diffraction and solid-state
NMR data. This strategy provides an initial average model for AlPOs in a reduced amount of time
and with increased success rate. Further NMR experiments can be carried out, leading to a more
accurate description of the non-periodic sub-networks, and the localization of water molecules and
hydroxyl ions, species usually ignored because hardly detectable from diffraction data. Finally, the
dehydration-rehydration cycle was studied by powder X-ray diffraction and solid-state NMR.
P-2.2-27
Evaluation of texture of micro/mesoporous materials from standard nitrogen adsorption data.
A new practical approach.
Pavol Hudec
Department of Petroleum Technology and Petrochemistry, Institute of Organic Chemistry, Catalysis
and Petrochemistry, Faculty of Chemical and Food Technology, Slovak University of Technology,
Radlinského 9 812 37 Bratislava, Slovak Republic
pavol.hudec@stuba.sk
Parameter of BET-isotherm obtained by standard physical adsorption of nitrogen with apparatus
equipped with only standard pressure transducer using still the same relative pressure table and
linearized in the full standard BET-range (p/p0=0.05-0.30) – CBET constant - can give very important
and interesting data about micro-mesoporous character of measured solid. The dependence of CBET on
Vmicro is most sensitive mainly at the low micropore volumes up to 0.05 cm3/g. By such way it is
possible to recognize even the smallest volumes of micropores and to decide to use t-plot method for
their quantification.
P-2.2-28
Application of in situ and ex situ X-ray techniques for the study of metal ions substituted
microporous materials
G. Sankar, M. Martis, K. Simmance and A.J. Smith.
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK,
g.sankar@ucl.ac.uk
X-ray diffraction techniuqes are routinely used to determine the structure of microporous materials.
However, this method allows us to determine the over-all structure and seldom provide much needed
information on the short and medium range structures of these solids, in particular for heteroatom
substituted systems. X-ray absorption spectroscopy is used widely for this purpose, mainly for
transition metal ions substituted systems. While this technique is unique in providing local structure
of the metal ions, often provide an average information. With the availability of very high-energies at
the synchrotron sources, it is possible to obtain diffraction data over a wide q-range thereby the pairdistribution function can be obtained which can assist the determination of local and medium range
structures. Here we show how the combination of these methods provide detailed structural
information around hetero-atoms by taking examples of metal ions substituted aluminophosphate,
AlPO-18, heteroatoms substituted AlPO-5 and titanium substituted silicalite (TS-1).
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.2-29
Speciation of OH groups of steamed zeolites by H-D exchange and inversion of time resolved
FTIR spectra.
S. Sirotin1, A. Travert1, A. Vimont1, V. Valtchev1, J.-P. Gilson1, R. Bergstraesser2, S. Wellach2
1 Laboratoire Catalyse et Spectrochimie, Caen, France, sergey.sirotin@ensicaen.fr
2 Grace GmbH & Co. KG, Worms, Germany
While H/D exchange can be used to characterize steam deactivated zeolites, the assessment of
exchange rate of a particular OH is difficult. We developed a new methodology that inverts time
resolved IR spectra, leading a 2D map whose components are the OD bands separated along their
wavenumber () and exchange rate (k) dimensions. USY zeolites were analysed using this technique
and evaluated in n-heptane cracking. The 2D maps allow differentiating the OH groups by their H/D
exchange rates; moreover the amount of exchanged deuterium is proportional to the cracking activity,
showing the relevance of this new technique to the characterization of acidic zeolites.
P-2.2-30
Crystallographic Verification that Copper(II) Coordinates to Four of the Oxygen Atoms of
Zeolite 6-Rings in Two Single-crystal Structures of Fully Dehydrated, Largely Cu2+-exchanged
Zeolite Y (FAU, Si/Al = 1.56)
S. M. Seo1, W. T. Lim1,*, K. Seff2,*
1Department of Applied Chemistry, Andong National University, Andong 760-749, Korea,
wtlim@andong.ac.kr
2Departmet of Chemistry, University of Hawaii, Honolulu, Hawaii 96822-2275, USA
Two single crystals of mostly Cu2+-exchanged zeolite Y were prepared from an aqueous Cu(NO3)2,
followed by dehydration. Their crystal structures were determined by X-ray diffraction techniques
for |Cu32.6Na5.3H4.5|[Si117Al75O384]-FAU and |Cu33.0Na3.9H5.1|[Si117Al75O384]-FAU, respectively. Cu2+
ions occupy the 6-ring sites I’ and II, preferring I’; Na+ ions also occupy sites I’ and II; neither site is
filled. All Cu2+ ions in both structures coordinate not only to three trigonally arranged oxygen atoms
of their 6-rings, but also to a fourth oxygen atom of these 6-rings to achieve planar severely distortedsquare 4-coordination. With increasing Cu2+-exchange time, both the Cu2+ and H+ contents of the
zeolite increase.
P-2.2-31
How Acid Characteristics of Deactive Industrial Hollow TS-1 Zeolite Influences Its Catalytic
Oxidation Performance?
Changjiu Xia,Bin Zhu,Min Lin,Xingtian Shu
State Key Laboratory of Catalytic Materials and Reaction Engineering , Research Institute of
Petroleum Procesing, SINOPEC, Beijing, P. R. CHINA, minlin@tom.com
From XPS and TEM characterization results, it was inferred that these Ti aggregates in deactive
hollow TS-1 zeolite may be amorphous TiO2 or TiO2-SiO2 oxides, which are closely related to
catalytic deactivation of hollow TS-1 zeolite. According to structure-property relationships of
catalytic materials, the changes of distribution and chemical state of Ti atoms will lead to forming
new acid sites,The acid type and amount of deactive hollow TS-1 zeolite was investigated. NH3-TPD
result shows that weak and medium strong acid sites were produced. And the new Brönsted and
Lewis adsorption peaks in Py-IR spectrum could be assigned to the formed amorphous TiO2-SiO2
binary oxides, which is the active sites of inefficient decomposition of H2O2 in partial oxidation.
2.2. Advanced characterization techniques
236
P-2.2-32
Formation peculiarities of hollow copper particles supported on ZSM-5
S. A. Yashnik, V.I.Zaikovskii, Z.R. Ismagilov
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia, yashnik@catalysis.ru
Current communication is devoted to study of oxidation processes of copper nanoparticles supported
on ZSM-5 aiming to find correlation between structures of the copper-oxide particles such as
core/shell, hollow and bulk, and oxidation conditions. The TPR-H2, XRD, HRTEM, and the optical
spectra modeling were used to confirm the hypothesis about the structure and nature of copper
particles in Cu-ZSM-5.
The 2D and 3D copper-oxide nanoparticles are formed at oxidation of copper nanoparticles. And their
structures are found to significantly depend on oxidation temperature. At temperatures up to 100oC,
primarily a core(Cu0)/shell (Cu2O) nanoparticles are formed. Deep oxidation of core/shell
nanoparticles results in a formation of hollow Cu2O particles. At temperatures 500oC and higher, a
bulk CuO nanopacles are formed, but their optical properties are differ from coarsely dispersed CuO
phase.
P-2.2-33
MZ-35, a new layered pentasil borosilicate synthesized in the presence of large alkali cations
Rossella Arletti1, Enrico Mugnaioli2, Ute Kolb2, Francesco Di Renzo3
1Department of Earth Science, University of Torino, Torino, Italy, rossella.arletti@unito.it
2 Institute of Physical Chemistry, Johannes Gutenberg-University Mainz, Mainz, Germany,
3 Institut Charles Gerhardt de Montpellier, UMR 5253 Montpellier, France
Layered sodium silicates and crystalline silicic acids are a class of minerals which includes several
members whose structure has not been solved yet. The interest of these materials as precursors of
microporous materials has motivated the development of procedures for the synthesis of analogs of
natural-occurring ones or for the production of new synthetic phases. Several of these synthetic
phases require the presence of organics for their synthesis. The present paper reports the occurrence
of a new layered pentasil borosilicate synthesized in the presence of large alkali cations such as Cs.
The structure of this new phase consisting of an interrupted framework, was determined by coupling
Automated electron Diffraction Tomography (ADT) and X-Ray powder diffraction (XRPD).
P-2.2-34
The influence of bimodal porosity on ZSM-5 deactivation during methanol conversion studied
by operando AGIR spectroscopy
Louwanda Lakiss, Zhengxing Qin, Philippe Bazin, Karine Thomas, Valentin Valtchev and Christian
Fernandez
Laboratoire Catalyse et Spectrochimie, ENSICAEN/ Université de Caen/ CNRS, CAEN, France,
louwanda.lakiss@ensicaen.fr
The effect of bimodal porosity on the deactivation of ZSM-5 catalyst over MTH (Methanol To
Hydrocarbon) reaction was investigated for the first time using the AGIR technique. It consists in
hyphenating thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR)
in a single instrument. The catalysts used in this study, involved two types of bimodal porosity, either
the macro/micro or meso/micro porosity. The secondary porosity of zeolite catalysts was created by
basic (OH-) and acid treatment (F-). The prepared catalysts were fully characterized by
complementary conventional techniques prior to AGIR analysis and MTH catalytic tests. The alkaline
treated sample shows the highest longevity but the acidic properties of the catalyst and its selectivity
are altered. Interestingly, the fluoride treated sample shows extended lifetime while preserving the
acidic properties and the selectivity of the parent sample.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.2-35
3-D Location and Orientation of ZSM-5 Crystals within the Matrix of a Fluid Catalytic
Cracking Particle
C. Sprung, A. M. Beale, B. M. Weckhuysen
Inorganic Chemistry and Catalysis, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The
Netherlands, c.sprung@uu.nl
FCC catalyst particles consist of a complex mixture of various components. Locating these
components in a catalyst particle is challenging, especially performed noninvasive on intact particles.
We employ the well characterized large ZSM-5 crystals as a model system to prove the principle of
orientation/polarisation dependent interaction of light with such anisotropic crystals. This knowledge
was transferred to locate zeolite crystals within the matrix of an industrial FCC catalyst particle. By
rotating the particle under plane polarized excitation light, emitting fluorescence light would
disappear due to extinction at certain orientations. Thus, this confirms the presence of a crystalline
anisotropic material at this location.
P-2.2-36
Determination of the acidic properties of non-Brønsted acidic zeolites by using solvatochromic
probe molecule
M. Hureau1, A. Moissette1, K. Smirnov1, H. Jobic2
1 LASIR, Université Lille 1, 59655 Villeneuve d’Ascq, France, matthieu.hureau@univ-lille1.fr
2 IRCE Lyon UMR-CNRS 5256, 2 avenue Albert Einstein, 69626 Villeurbanne, France
Confinement and extraframework cation nature play an important role for the reactivity of zeolites.
To better understand the solvent behaviour of zeolites, we perform experiments with sorbed
salicylideneaniline molecule known for its solvatochromic properties.
The systems are characterized by the Raman scattering, infrared absorption, diffuse reflectance UVvisible absorption, fluorescence and Inelastic Neutron Scattering methods. The experimental results
are supported by the data of molecular modeling that reveal the influence of the nature of extraframework cations on the solvatochromic effect. The quantification of the different sorbed species by
using a solvatochromic equation allows the assessment of the acidic properties of non-Brønsted acidic
zeolites.
P-2.2-37
Solid-state NMR Characterization of Metal Center Environment in Metal-organic Frameworks
at Ultrahigh Magnetic Field
J. Xu1, P. He1, A. Sutrisno1, V. V. Terskikh2 and Y. Huang1.
1Department of Chemistry, The University of Western Ontario, London, Ontario, Canada,
yhuang@uwo.ca
2Measurement Science and Standards, National Research Council Canada, Ottawa, Ontario, Canada
Metal-organic frameworks are a class of new porous materials. Characterization is important because
understanding the relationship between the key properties and their unique structures is crucial to the
development of new applications and the performance improvement of their current uses. However,
many important MOFs contain metal ions whose NMR active isotopes are quadrupolar and
unreceptive. As a result, solid-state NMR (SSNMR) has rarely been used to directly characterize
these nuclei. In this presentation, we report our recent work on direct characterization of metal center
environment in several representative MOFs by Zn-67, Zr-91, Mg-25, In-115, Ba-137 SSNMR at
ultrahigh magnetic field of 21.1 T. The NMR results provide information complementary to X-ray
diffraction.
2.3. Mechanistic studies; impact of in-situ and operando techniques
238
P-2.3-01
Mobility of tert-Butyl Alcohol in MFI Framework Type Studied by Deuterium NMR
1Alena M. Nishchenko, 2Daniil I. Kolokolov, 2Anton A. Gabrienko,2 and Alexander G. Stepanov
International Tomography Center, Institutskaya 3a, 630090, Novosibirsk, Russia,
arlenushka@gmail.com
2Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt
Akademika Lavrentieva 5, Novosibirsk 630090, Russia
The molecular mobility of deuterated tert-butyl alcohol (TBA) adsorbed in MFI framework type
(silicalite-1 and ZSM-5 zeolite) has been studied by use of 2H NMR spectroscopy in the range of
106−453 K. In H-ZSM-5, the reorientation of the molecule as a whole is strongly restricted (τc≪ Q0−1
≈ 10−6 s) by hydrogen bonding to Brønsted acid sites (BAS). Being adsorbed to BAS, the motion of
TBA molecules is described by intramolecular rotations around two successive C3 and C3′ axes
(CD3−C and C−O bonds). In silicalite-1, the TBA molecule is additionally involved into
reorientational motions as a whole: one of the motions represents an exchange among orientations
provided by the directions of four framework channels driven by the translational jump diffusion. The
other motion represents a large-amplitude wobbling of the TBA molecule localized at a channel
intersection site cavity. This motion is described by a fast restricted wobbling of the molecular axis in
a sphere sector. The anisotropy of this motion persists even at 453 K, revealing the presence of a
strong intracavity barrier that blocks the TBA from free rotational diffusion inside the cavity.
P-2.3-02
Structure-directing effect of piperazine revealed by reverse temporal evolution processes
W.F. Yan1, X.Q. Tong1, J. Xu2, J.H. Yu1, F. Deng2, R.R. Xu1
1 State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun, China, yanw@jlu.edu.cn
2 State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute
of Physics and Mathematics, the Chinese Academy of Sciences, Wuhan, China
By solely changing the concentration of piperazine in the initial mixture containing boehmite,
phosphoric acid, piperazine and water, two layered aluminophosphates were obtained under
hydrothermal condition. The products of both compounds that were crystallized for different periods
of time were characterized using XRD and NMR techniques. To obtain the primary composite formed
in the very early stage of crystallization, a reverse temporal evolution process was applied to the
structure of both compounds. By comparing their primary composites, a new insight into the
structure-directing effect of piperazine in directing these two layered aluminophosphates was
obtained.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-2.3-03
In situ MAS NMR for Investigation of Acidity, Porosity and Reaction Mechanism of
Silicoaluminate and Silicoaluminophosphate Catalysts
S.T. Xu1, Y.X. Wei1, L.H. Chen2, P. Tian1, J.Z. Li1, J.R. Chen1, X. Su1, Q.Y. Wang1, Y. Zhou1, J.B.
Wang1, M.Z. Zhang1, B.L. Su2*, Z.M. Liu1*
1 National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean
Energy, Dalian Institute of Chemical Physics(DICP), Chinese Academy of Sciences, Dalian, P.R.
China, liuzm@dicp.ac.cn
2Laboratory of Inorganic Materials Chemistry (CMI), University of Namur (FUNDP), Namur,
Belgium
In situ MAS NMR spectroscopy has been proved to be powerful tool in the study of acidity, structure
and also the reaction mechanism of heterogeneous catalysis. The present study tried to elucidate the
heterogeneous catalysis of methanol conversion by employing well-established and powerful
technique of in situ solid state NMR spectroscopy. Confined organics in the cages of three catalysts
and their evolution were identified and correlated with the methanol conversion on the catalyst
surface. The use of hyperpolarized (HP) 129Xe NMR technique predominantly increase the detection
sensitivity and provide the informations of porosity of hierarchical porous Beta zeolite.
P-2.3-04
Deactivation of HTS catalyst for ammoximation of Acetone
Yi Wang, Shengjian Zhang, Yingxian Zhao
Ningbo Institute of Technology, Zhejiang University, Zhejiang, China, 21128179@zju.edu.cn
The deactivation of titanium silicalite with hollow structure (HTS) in the ammoximation reaction of
acetone with H2O2 to prepare acetoxime has been investigated. The fresh and spend catalyst samples
were characterized by elemental analysis, Fourier transform infrared spectroscopy (FTIR),
thermogravimetry/differential thermal analysis (TG/TDA) and gas adsorption. Two main reasons
causing HTS deactivation were suggested: (1) slow deactivation due to amine or ammoniums with
strong basicity absorbed on the active sites of catalyst surface, which can be regenerated with acid
solutions such as HNO3; (2) rapid deactivation due to by-products filling and blocking the pore of
catalyst. In this reaction system, 2,3-dimethyl-2,3-dinitrobutane (DMNB) formed by oxidative
coupling was determined to the main by-products, which can be removed from the deactivated
catalyst by washing with some organic solvents such as CH3Cl.
2.3. Mechanistic studies; impact of in-situ and operando techniques
240
P-2.3-05
Studies on the crystallization process of SAPO-35
P. Tian1, B. Li1,2, D. Wang1,2, L. Zhang1, S. Xu1, X. Su1,2, D. Fan1,2, Y. Qi1, Z. Liu1
1 National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean
Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R.
China.
2University of Chinese Academy of Sciences, Beijing, P. R. China
tianpeng@dicp.ac.cn
In the present work, we examine the crystallization process of SAPO-35 by using
hexamethyleneimine as a template. Attentions are also given to the Si incorporation and Si
distribution in the crystals. Many characterizations including XRD, SEM, XRF, XPS, EDS and
various solid-state NMR are applied to monitor the formation process of SAPO-35 and the
development of the local environments of Si, P and Al atoms as a function of crystallization time.
P-2.3-06
Differences in acid-base properties of Nb species located in the framework of zeolites and
mesoporous molecular sieves estimated by in-situ NO adsorption
I. Sobczak, A. Wojtaszek, M. Ziolek
Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland; sobiza@amu.edu.pl
Amorphous NbMCM-41 and crystalline NbY zeolite were characterized by in-situ adsorption of NO
(or O2 admission followed by NO adsorption) combined with FTIR measurements. XRD, XPS and
UV-vis results proved the lack of extra framework niobium species and the presence of Nb+5 cations
in a tetrahedral coordination involved in Nb-O-Si bonds in both types of materials. Despite these
common features, a substantial difference between the niobium species in these two types of materials
was indicated by NO adsorption and FTIR study. In NbMCM-41 unsaturated Nbδ+ (Lewis acid sites)
and NbOδ- species (basic centres) were identified. In NbY the niobium cations in the framework were
saturated. The basicity in NbY is not directly due to the Nb species (like NbOδ- in NbMCM-41), but it
results from an increase in the basicity of oxygen atoms in Si-O-Nb and Si-O-Al bridges caused by
Nb location in the framework.
17 IZC, 2013. POSTER COMMUNICATIONS
241
P-2.3-07
Direct identification of carbenium cations and their role during MTO conversion over SAPO
molecular sieves
J.Z. Li1, Y.X. Wei1, J.R. Chen1,2, S.T. Xu1, P. Tian1, B. Li1, Xiong Su1,2, Y. Zhou1,2, Q.Y. Wang1,2,
G.Y. Liu1,3, Z.M. Liu1, *
1National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean
Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China,
liuzm@dicp.ac.cn
2Graduate University of Chinese Academy of Sciences, Beijing 100049, China
3School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou
450001, Henan, China
Crucial carbenium ions, heptamethylbenzenium ion and pentamethylcyclopentenyl ion, have been
directly observed under the real methanol-to-olefins (MTO) reaction conditions over cage type SAPO
molecular sieves with 8-ring windows by in-situ NMR and ex-situ GC-MS. The confined species and
product distribution were well correlated with the cage structure. Combining the experimental
evidences with the theoretical calculations, the transition-state shape selectivity was believed to be
important for the product selectivity variation.
P-2.3-08
The investigation of interaction between modified ZSM-5 zeolites and dimethyl ether by means
of in situ high-temperature diffusive reflectance FTIR spectroscopy
A.S. Rodionov, G.N. Bondarenko, N.V. Kolesnichenko, G.N. Shirobokova, E.N. Khivrich
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, ASRodionov@ips.ac.ru
Active sites on the surface of zeolite based catalysts modified by different metals (Mg, Rh) and their
participation in DME conversion have been investigated by means of in situ high-temperature
diffusive reflectance FTIR spectroscopy. It was shown that mainly bronsted acid sites take part in the
formation of olefins and alkanes on zeolite catalysts, while effect of isolated hydroxyl groups is
directed toward the formation of methanol. Some kinetic features of the studied reactions have been
investigated. The resulting spectral data was confirmed by quantum-chemical modeling.
P-2.3-09
Elementary steps of light olefin cracking on MFI type zeolites
S. Schallmoser, A.C. van Veen, J.A. Lercher
TU München, Lichtenbergstr. 4, 85748 Garching b. München
Cracking of 1-pentene is studied as a model reaction with MFI type zeolites. Combining quantitative
assessment of the thermodynamics of adsorption with a detailed kinetic analysis, monomolecular and
dimerization cracking is quantitatively described on the level of elementary reactions. The van’t Hoff
plot of Kads determined in the Henry region of the isotherm as well as calorimetry result in a heat of
adsorption of 110 kJ/mol of 1-pentene, which is reversibly chemisorbed as alkoxide at the low
coverages,.
Between 430 and 570°C, one kinetic regime was observed for the dominating pathway to ethene and
propene with an intrinsic Ea of 192 kJ/mol, indicating that the cleavage of the C-C bond in a
carbenium ion, is nearly identical with the true Ea of protolytic cracking of pentane. Butenes are
formed via two pathways, clearly evidenced by two regimes of the formation rate. At high
temperatures (>500 °C), the monomolecular pathway dominates cleaving the terminal C-C bond and
yielding a methoxy group, which reacts subsequently with pentene to hexene. At temperatures below
470°C, butenes are formed via dimerization of pentene and subsequent cracking.
2.3. Mechanistic studies; impact of in-situ and operando techniques
242
P-2.3-10
Molecular and dissociative adsorption of H2O on Zn/ZSM-5 zeolite
A.N.Subbotin1, G.M.Zhidomirov1,2, I.R.Subbotina1, V.B.Kazansky1.
1 N.D. Zelinsky Institute of organic chemistry RAS,119991, Leninsky Prospect 47, Moscow, Russia,
alexniko.4242@yahoo.com
2 G.K.Boreskov Institute of Catalysis SB RAS, 630090, Pr.lavrentieva 5,Novosibirsk, Russia
Interest to H2O adsorption on cation-exchanged zeolites is associated with possibility of the reaction
Men+ (H2O) + [Si-O-Al]-1 ->MeOH(n-1)+ + Si-O(H)-Al, n=(1-3)
which creates Broensted acid activity of the cation-exchanged zeolites. The adsorption of water on
Zn/ZSM-5 at room temperature and subsequent heterolytic dissociative adsorption at moderate
temperatures have been studied by means of FT-IR spectroscopy. For theoretical modeling of the
process we considered 3 cluster models of the fragments of ZSM-5 zeolite lattice as a cation
positions: α-position and 5-membered ring on the wall of right channel of the zeolite and also the 10membered ring as a simple model of the right channel. DFT calculations of the molecular and
dissociative adsorption of H2O molecule on exchanged Zn2+ cations were carried out. Both
exothermal and endothermal dissociations of the adsorbed H2O molecules were found and it was
shown that spatial distance of the two lattice Al ions in the cation position of Zn2+ essentially favored
to dissociation of H2O molecules under their adsorption on the cation-exchanged zeolites.
P-2.3-11
Acidic properties of Ag- and Cu-exchanged Y zeolites prepared by solid state ion exchange
F. Benaliouche1, Y. Boucheffa1 and F. Thibault-Starzyk2
1Ecole Militaire Polytechnique (EMP), UER de Chimie Appliquée, BP 17 Bordj El-Bahri, 16111,
Algiers, Algeria, benaliouche.fouad@gmail.com
2Laboratoire Catalyse et Spectrochimie, CNRS-ENSICAEN-Université de Caen, 6 Boulevard
Marechal Juin, Caen Cedex 14050, France.
The Ag- and Cu-exchanged Y zeolites are prepared by the solid state ion exchange (SSIE) technique.
Compositional structural and textural investigations of all samples are performed by elemental
analysis, powder XRD, and nitrogen adsorption porosimetry. The acidity is investigated using FTIR
spectroscopy of pyridine adsorption. The progressive adsorption of pyridine doses on Ag- and Cuexchanged zeolites reveals that the acidity evolution is complex particularly at high exchange degrees
of copper. This is explained by the partial auto-reduction of Cu2+ and also by the pyridine-cation
interactions.
P-2.3-12
The study of the transformation of dimethyl ether in the presence of p-xylene on zeolite ZSM-5
catalysts by means of in situ high-temperature diffuse reflectance FTIR-spectroscopy
Y.V. Pavluk, G.N. Bondarenko, N.V. Kolesnichenko
1 A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, ypavluk@gmail.com
By means of in situ high-temperature FTIR diffuse reflectance spectroscopy the transformation of
DME in the presence of p-xylene on the surface of the zeolite catalyst ZSM-5 was studied. It was
shown that the conversion of DME mainly take place on the Bronsted acidic sites (BAS). A
comparison of the transformation products of DME in the presence of p-xylene in the unmodified and
modified by magnesium zeolite catalysts is presented. These results allow us to compare the spectral
characteristics of the surface of the zeolite in the presence and absence of aromatic compounds and to
draw conclusions about the role of the aromatic compounds present in the system on the catalytic
conversion of DME.
17 IZC, 2013. POSTER COMMUNICATIONS
243
P-2.3-13
NH3-SCR of NOx over Cu-zeolites for Diesel engine applications: reactivity and spectroscopy
study under real catalytic conditions
F. Giordanino1, S. Bordiga1, C. Lamberti1, F. Bonino1, P. Beato2
1 Dipartimento di Chimica - NIS Centre of Excellence, Università di Torino, Via P. Giuria 7, 10125
Turin, Italy filippo.giordanino@gmail.com
2 Haldor Topsøe, Nymøllevej 55, DK-2800 Kgs, Lyngby, Denmark
In the present work three different Cu2+-exchanged zeolites (ZSM-5, β, SSZ-13) devoted to NH3-SCR
of NOx were tested and characterized. In situ DRSUV-Vis-NIR and FTIR measurements were
performed in order to look at the oxidation and the aggregation state of Cu species and the
distribution of Brønsted acid sites in vacuo or in oxidative environment. In operando FTIR-MS
technique allowed us to identify the main adsorbed species on catalyst surface under typical SCR
conditions.
P-2.3-14
A study on Zn- and Ga- containing ZSM-5 catalysts for MTA reaction by in situ XAFS and
DFT calculation
Xianjun Niu1,2, Qing Miao1,2, Mei Dong1,*, Guofu Wang1, Weibin Fan1, Zhangfeng Qin1, Jianguo
Wang1,*
1 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, P.O. Box 165, Taiyuan 030001, China, mdong@sxicc.ac.cn; jgwang@sxicc.ac.cn
2 University of Chinese Academy of Sciences, Beijing 100049, China
Zn2+ and Ga3+ species were introduced to the framework, surface, and channel of ZSM-5 molecular
sieves with different crystal sizes to enhance the selectivity to aromatics in the products of methanolto-aromatics (MTA) reaction. Various techniques such as XRD, IR, XPS, NH3-TPD, and XAFS as
well as DFT calculation were used to characterize the structure, acidity, and local geometry of the
metal ions in the molecular sieves and to distinguish the active species; the roles of various Zn species
and Ga species played in the methanol aromatization were investigated. The results suggest that ZnOH species in Zn/ZSM-5 is responsible for the high selectivity of atomization reaction. For Ga/ZSM5, the framework Ga species offers the acidic sites, while the non-framework Ga species acts as the
active sites for methanol aromatization; proper amounts of non-framework gallium species matched
with certain acid sites can promote the formation of aromatics in MTA.
P-2.3-15
Photoinduced electron transfers in zeolites:
Impact of the aluminum content on the activation energies
M. Hureau1, A. Moissette1
1 LASIR, Université Lille 1, 59655 Villeneuve d’Ascq, France, matthieu.hureau@univ-lille1.fr
Zeolite are known to stabilize for long times charge separated states. Currently, all the energetic and
dynamic reasons involved in this stabilization process are not well understood and are still under
investigations. Among the energetic factors, the knowledge of the activation energy is of high
importance because it can help to show the correlation between the electron transfer rate and the free
energy by demonstrating a Marcus type dependance for such mechanisms.
Thus, in the present work, we report the experimental determination of the activation energy for a
radical cation-electron recombination after photoionization of 1,6-diphenyl-1,3,5-hexatriene
incorporated in the channels of sodium exchanged ZSM-5 zeolites.
We demonstrate experimentally that the stabilization of ejected electrons in zeolite does not depend
only on the electron acceptor properties of the zeolite but on the Al repartition.
2.3. Mechanistic studies; impact of in-situ and operando techniques
244
P-2.3-16
In situ spectral kinetic study of ethanol conversion over H-ZSM-5 zeolite catalyst
1V.F. Tretyakov, 1K.V. Tretyakov, 2O.N. Silchenkova , 2V.A. Matyshak
1A.V. Topchiev Institute of petrochemical synthesis of Russian Academy of Sciences
2N.N.Semenov Institute of Chemical Physics
tretjakov@ips.ac.ru
For the solution of a task on processing of renewable raw materials we developed process of catalytic
conversion of ethyl alcohol in hydrocarbons on zeolite catalysts. For the first time will reach a high
exit of hydrocarbons of a petrol row, olefins and aromatic hydrocarbons from ethanol that allow to
consider this process as alternative to existing technologies of saturation of the world market by
olefins and aromatic connections which can be used as high-octane components of motor fuels and
also as raw materials for petrochemical synthesis. As catalysts for ethanol transformation into
hydrocarbons zeolites were of the ZSM-5 type with various structuring additives chosen.
P-2.3-17
Role of radical “coke” in ethanol transformation into hydrocarbons over HZSM-5 zeolite
S. Hamieh1, L. Pinard1, K. Ben Tayeb2, H. Vezin2, C. Canaff1, S. Maury3, O. Delpoux3, Y.
Pouilloux1
1 IC2MP, UMR7285, Université de Poitiers, 4 rue Michel Brunet, 86022 Poitiers, France
2 LASIR, UMR8516, Université des Sciences et Technologies de Lille, 59655 Villeneuve d’Ascq,
France, karima.ben-tayeb-meziane@univ-lille1.fr
3 IFP Energies Nouvelles, Rond-point de l’échangeur de Solaize, BP3, 69390 Vernaison, France
During ethanol transformation into hydrocarbons at 350°C and 30 bar total pressure over a zeolite
HZSM-5(Si/Al = 40), the coke formation occurred inside the zeolite structure which generates radical
species. Coke is located within the zeolite micropores rather than at the surface of the catalyst and in
the mesopore. All aromatic compounds were sterically blocked in the zeolite pore. It was proved that
radical species intervene in the ETH transformation. A radical mechanism of carbon pool has been
elucidated.
P-2.3-18
Mechanism and kinetics of Metal-Organic Framework Crystallization investigated by TimeResolved X-ray Scattering
M.G. Goesten,1 J. Juan-Alcañiz, C. Gucuyener, E. Stavitski,2 A. Petukhov,3 E. Pidko,2 E.J.M.
Hensen, F. Kapteijn,1 J. Gascon,1
1 Catalysis Engineering group, Delft University of Technology, Netherlands
2 NSLS, Brookhaven National Laboratory, USA
3 Van ‘t Hoff Institute, Utrecht University of Technology, Netherlands
m.g.goesten@tudelft.nl
Small/Wide Angle X-Ray Scattering/Quick EXAFS (SAXS/WAXS/QEXAFS) was used in
combination with in-situ NMR and DFT to reveal the kinetics and growth mechanism of several of
the most popular MOF topologies; ZIF-7, NH2-MIL-53 and NH2-MIL-101. It was possible to study
the molecular and kinetic pathway at all relevant pathways, namely from atomic to full crystal scale.
Several important results were obtained: an DMF-promoted intermediate was found to be able to
improve the NH2-MIL-53 yield by a factor 3, and the study on the structure-directing chemistry of
diethyl amine and ZnCl2 in ZIF-7 synthesis paves the way to crystal engineering for this interesting
olefin/paraffin separating material.
17 IZC, 2013. POSTER COMMUNICATIONS
245
P-2.3-19
The high thermal stability of the zeolite K-L:
dehydration mechanism by in-situ SR-XRPD experiments
Lara Gigli1, Rossella Arletti2, Simona Quartieri3, Francesco Di Renzo4, Giovanna Vezzalini1
1Dip. di Scienze Chimiche e Geologiche, Univ. di Modena e Reggio Emilia, Modena, Italy,
lara.gigli@unimore.it.
2Dip. di Scienze della Terra, Univ. di Torino, Torino, Italy
3Dip. di Fisica e di Scienze della Terra, Univ. di Messina, Messina, Italy.
4Institut Charles Gerhardt de Montpellier, France.
The thermal induced structural modifications of the zeolite K-L have been studied by T-resolved
synchrotron XRPD between RT and 814° C. Neither structure breakdown or phase transitions occur
and a small cell volume increase of 0.6% is observed. This thermal expansion, very unusual for a
non-siliceous zeolite, is interpreted and compared with previous data reported in literature. The
release of the water molecules occurs between 80 and 240°C. During dehydration the framework
undergoes slight rearrangements, which allow an easier water release: the apertures of the main 12ring and of the 8-ring channels become more circular and the 6-membered rings become more
hexagonal.
P-2.3-20
Crystal Growth and Materials Discovery of Metal Organic Frameworks
Revealed by Atomic Force Microscopy
P. Cubillas, M. W. Anderson and M. P Attfield
Centre for Nanoporous Materials, School of Chemistry, The University of Manchester, Manchester,
UK, m.anderson@manchester.ac.uk
The crystal growth of the zeolitic imidazolate framework, ZIF-76, with the LTA framework topology
has been observed for the first time using in situ atomic force microscopy. The study reveals that
growth occurs through a process of nucleation and correlated spreading of meta-stable and stable sublayers and that growth of the framework is reliant on non-framework species to provide the necessary
stabilizing interactions to bridge the pores of the framework during growth. This indicates that the
low supersaturation surface crystal growth of a MOF consisting of more than one type of cage
structure occurs in the same manner as structurally simpler MOFs supporting the notion that this may
be a general mechanism of growth for MOFs and nanoporous materials. The work also demonstrates
the templating effect of the crystal surface of ZIF-76 to form a previously undiscovered ZIF with
LTA topology.
POSTER COMMUNICATIONS
SECTION 3:
“Industrial and emerging applications”
3.1. Oil refinery and petrochemistry
248
P-3.1-01
Preparation of Mesoporous Ce-Ni2P/SBA-15 Catalysts and Their Catalytic Performance for
Hydrodesulfurization of Dibenzothiophene
Qingyuan Li1, Pingyi Wu1, 2, Ling Lan 2, Shengfu Ji1,*, Hui Liu1
1State Key Laboratory o f Chemical Resource Engineering, Beijing University of Chemical
Technology, Beijing 100029, China, jisf@mail.buct.edu.cn
2Petrochemical Research Institute, PetroChina, Beijing 100195, China
A series of mesoporous Ce-Ni2P/SBA-15 catalysts with different Ce contents were prepared. The
catalytic activity for the hydrodesulfurization of dibenzothiophene was evaluated. The results showed
that only Ni2P phase was formed in Ce-Ni2P/SAB-15 catalysts with Ce loading of 0-5 wt%. Ni2P and
Ni12P5 phases existed in 7%Ce-Ni2P/SBA-15 catalyst. The addition of Ce to mesoporous Ni2P/SBA15 catalysts can improve the strength of the acid sites and total acid amount of Ce-Ni2P/SBA-15
catalysts, and decreased the Niδ+ relative concentration on the surface of the Ce-Ni2P/SBA-15
catalysts. In the hydrodesulfurization of dibenzothiophene reaction, Ce of the Ce-Ni2P/SBA-15
catalysts can increase the biphenyl selectivity at 360-380 oC comparison with the Ni2P/SBA-15
catalysts.
P-3.1-02
The influence of desilication and dealumination on the activity of mordenite catalysts in
alkylation of aromatics with 1-alkenes
M. Horňáček1, M. Horňáčková2, P. Lovás1, P. Veis2, P. Hudec1, A. Smiešková1, K. Velebná1
1Faculty of chemical and food technology, Slovak University of Technology, Bratislava, Slovakia,
michal.hornacek@stuba.sk
2Faculty of mathematics, physics and informatics, Comenius University, Bratislava, Slovakia
This paper deals with a comparison of dealuminated and desilicated mordenites, which were used in
the alkylation of benzene with 1-octene.
The surface properties were improved after dealumination and desilication. In both cases, secondary
mesoporous structure was created and thus improvement of transport phenomenon. Results showed
that the activity of treated mordenite was markedly higher in comparison to ammonium form of
mordenite. The difference between samples prepared by dealumination and desilication was in the
product composition. The decreasing of mordenite activity after dealumination happened because of
markedly decreasing of total acidity and B/L ratio however the mesoporous surface area is increased.
P-3.1-03
Reactivities of C6-8 hydrocarbons and effect of coexisting hydrocarbon for cracking on H-ZSM5 catalyst at high temperatures
Takashi Takahashi, Kohei Kubo, Hajime Iida, Seitaro Namba, and Akira Igarashi
Dept. of Applied Chemistry, Kogakuin University, Tokyo, Japan, namba@ntu.ac.jp
The cracking of C6-8 hydrocarbons on H-ZSM-5 (Si/Al=51) at high temperatures was carried out as a
model reaction of naphtha cracking to produce light olefin. The reactivity of n-paraffin increased with
an increase in its carbon number, but the selectivity to light olefin was almost constant. In the
cycloparaffin cracking, the selectivity to corresponding aromatics was very high, indicating the direct
dehydrogenation took place. Coexistent 1-hexene did not affect the reactivity of n-heptane, because of
the predominance of the monomolecular cracking, while coexistent cyclohexane and
methylcyclohexane affected it considerably, because of their slow diffusion rate in the pores of HZSM-5.
17 IZC, 2013. POSTER COMMUNICATIONS
249
P-3.1-04
The Research and Commercial Applications of the Catalysts for Ethylbenzene Production via
Benzene Ethylation in Gas Phase
Zhen-hao Shen, Hong-min Sun, Wei-min Yang
Shanghai Research Institute of Petrochemical Technology, No.1658, North Pudong Road, 201208,
Shanghai, P. R. China
zhshen1984@yahoo.com.cn
This paper provides an overview of catalysts which we developed for benzene ethylation in gas phase
to produce ethylbenzene (EB) in the past 20 years. Two series of catalysts for benzene ethylation in
gas phase were investigated and discussed, which are referred to different key preparation techniques.
In benzene ethylation with ethylene, a nano-particled ZSM-5 based catalyst modified by steaming and
pore expansion treatment was utilized, in order to increase selectivity and to reduce coking. In
benzene ethylation with ethanol, a di-functional catalyst was introduced, which has both dehydration
and alkylation activities. In order to acquire good hydro-thermal stability as well as high activity and
selectivity, a phosphorus modified binder-free ZSM-5 catalyst was innovatively used in this reaction.
The two kinds of catalysts were commercially applied on several industrial EB plants in Chinese
domestic areas and exhibited well performances.
P-3.1-05
Catalytic cracking of n-Hexane to Produce Propylene on Organic structure directing agent
(OSDA) Free Beta Catalysts
Yong Wang, Toshiyuki Yokoi, Seitaro Namba, Junko N. Kondo, Takashi Tatsumi
Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama, Japan,
wangyong347@126.com
Light alkenes, especially propylene, are acquiring more significance in chemical industry. Nowadays,
the catalytic cracking of naphtha to produce propylene has been drawing more attention. In this study,
the catalytic cracking of n-hexane to produce propylene on organic structure directing agent free Beta
(OFB) catalysts was carried out as a model reaction of naphtha cracking. The OFB catalysts
dealuminated by the ammonium hexaflurosilicate (AHFS) treatment followed by the acid leaching
showed the higher propylene selectivity and catalytic life in the catalytic cracking of n-hexane. This
could be attributed to the lower acid concentration and higher Brønsted/Lewis acid ratio.
P-3.1-06
Isomerization of n-Decane on Mesoporous Support Based Catalysts – Design of Experiments in
Combination with Kinetic Modeling
A. Rüfer, A. Werner, W. Reschetilowski
Institute of Industrial Chemistry, Dresden University of Technology, 01062 Dresden
Wladimir.Reschetilowski@chemie.tu-dresden.de
The current work deals with the investigation of the isomerization of n-decane on bifunctional
catalysts based on mesoporous silica supports, which are modified systematically in a Design of
Experiments (DoE): screened parameters include the calcination temperature, metal dispersion and
surface acidity.
In conclusion, the influence of calcination temperature was found to be negligible, as opposed to
metal dispersion and acidity. High dispersion increased the primary reaction rate to mono-branched
products and, at the same time, decreased cracking tendency. Low acidity decreased all rate constants,
but the cracking reaction was unexpectedly affected to a far greater extent.
3.1. Oil refinery and petrochemistry
250
P-3.1-07
Catalytic Dehydrogenation of Hydrocarbons over Iron-Silicate ZSM-5
Jang Ho Yun and Raul F. Lobo
Center for Catalytic Science and Technology, University of Delaware, Newark, DE 19716, USA,
jhyun@udel.edu
The acid sites in Al-containing zeolites are responsible for the monomolecular cracking and
dehydrogenation reaction of acid zeolites in hydrocarbon conversions. In contrast, different activity
and selectivity has been reported for the zeolites containing trivalent metal element (Fe3+, Ga3+, B3+)
other than Al3+. Here, we present an investigation of the chemistry at the acid sites in Fe-ZSM-5
zeolites using the monomolecular propane reaction. Very high dehydrogenation selectivity is
observed for the propane conversion over H-Fe-ZSM-5 while H-Al-ZSM-5 shows comparable
selectivity toward cracking and dehydrogenation. The results suggest that the reaction proceeds
through different mechanisms in H-Fe-ZSM-5 than in typical H-Al-ZSM-5.
P-3.1-08
Preparation of MCM-48 supported Mo catalyst via carbide and sulfided with elemental sulfur
for hydrodesulfurization
F. E. Imbert1, L. Contreras1, J. Brito2, P. Rodriguez1, M. Villarreal1
1Lab de Cinética y Catálisis, Dep de Química, Fac de Ciencias, Universidad de Los Andes, Mérida
5101, Venezuela, imbert@ula.ve
2Lab de Fisicoquímica de superficies, Centro de Química, Instituto Venezolano de Investigaciones
Científicas (IVIC), Caracas 1020-A, Venezuela
A series of Mo2S catalysts supported on MCM-48 was synthesized via carbide. The Mo was carbided
with a mixture CH4/H2 followed by sulfurization with S. The carbiding procedure formed Mo2C and
its sulfurization resulted in a mixture of Mo2C and MoS2. All the catalysts were active for direct
hydrodesulfuration of dibenzotiophene to biphenyl; and the activity increased with MoS2 proportion
present in the catalyst. The mix phases Mo2C and MoS2 offers catalytic stability and higher activity
per mass of MoS2.
P-3.1-09
The shape selective effect of BETA zeolite in FCC process
Beiyan Chen, Ying Ouyang,Yuxia Zhu,Yibin Luo
Research Institute of Petroleum Processing, SINOPEC, Beijing, China, chenby.ripp@sinopec.com
The shape selective effect of BETA zeolite in the complicated catalysis regime of FCC process is
studied. The special pore topology endows BETA with unique catalytic performance, especially C4
selectivity, which is acknowledged and can be ascribed to shape selective effect. Is it possible to
enhance isobutylene selectivity by incorporating BETA into FCC catalyst? To answer the question, a
modified BETA, HSB, has been prepared and shows good hydrothermal stability comparable to that
of USY. FCC naphtha, LCO and VGO were used as feeds respectively for testing different catalysts
containing HSB, USY and ZSM-5 zeolites respectively. In all cases, the catalyst containing HSB
always displays the highest concentrations for both butenes in LPG and isobutylene in total butenes.
The butene selectivity can be attributed to the characteristic pore topology of BETA. The isobutylene
selectivity originates from the pore structure as well as the optimized acid properties of specially
modified HSB.
17 IZC, 2013. POSTER COMMUNICATIONS
251
P-3.1-10
Obtaining synthetic oils on the basis esters of dicarboxylic acids
R.R. Shiriyazdanov 1,2), A.R. Davletshin 1,2), M.F. Kuzmenko 2), A.R. Karimova 1), U.I. Kazakbaev
1,2), E.G. Telyashev 1,2), M.N. Rakhimov 1)
1) Ufa State Petroleum Technical University, Ufa, Russia
2) GUP «Institute of Petroleum Refining and Petrochemistry of the Republic of Bashkortostan», Ufa,
Russia, davletshinar@list.ru
One of the most effective ways to improve the quality of motor oils is to use synthetic products as
components.
The authors have developed a technology for production of ester oils (esters of dicarboxylic acids) by
esterification of components of distillation residues of butyl alcohols rectification (KORBS),
containing up to 65% of the monatomic alcohols C8, in particular, up to 35% 2-ethylhexanol, with
terephthalic acid and its residue (SOC) at 120-150 ° C and 1.0-1.2 MPa on zeolite catalysts (structure
type FAU).
The obtained results show good potential for the application of EDA in production of motor oils, and
require further qualification engine tests in specialized centers.
P-3.1-11
Realumination of MCM-22 and its use in alkylation of benzene with LPG
Kefeng Liu1,2, Huijuan Wei1,2, Sujuan Xie1, Shenglin Liu1, Longya Xu1*.
1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, Dalian 116023, PR China, liukefeng07@dicp.ac.cn
2Graduate University of Chinese Academy of Science, Beijing 100049, PR China
MCM-22 zeolite is realuminated in Al(NO3)3 solution. Al atoms transfer from solution to zeolite by
two ways: depositing into zeolite with the amorphous form; inserting into the framework of MCM-22
zeolite by substituting Si atoms. Comparing with that in the parent zeolite, both Lewis and Bronsted
acid sites in the realuminated MCM-22 zeolites increase with increasing the concentration of
Al(NO3)3 solutions. Alkylation of benzene with analogy LPG is carried out over samples before and
after being realuminated. Over the realuminated samples, more olefins can be converted over the
surface, the diffusion of the produced large molecules into the supercage is impeded by the 10MR
opening, so the realuminated MCM-22 zeolites has higher catalytic activity and stability for olefins’
conversion.
P-3.1-12
Joint conversion of n-butane and methanol over modified hzsm-5 zeolites
D. B. Tagiyev, S. B. Agayeva, S. I. Abasov, R. V. Starikov, A. A. Imanova, N. S. Asadov, F.M.
Nasirova
Institute of Petrochemical Processes, Baku, Azerbaijan, dtagiyev@hotmail.com
Report describes a study of the effect of methanol (M) on the n-butane (B) conversion over Zn (Mg)
or/and Zr modified zeolite HZSM-5 (SiO2/Al2O3=64). Comparative studies of M, B and their
mixtures (M+B) conversions over synthesized catalysts showed that the named elements oxides
introduction into HZSM-5 facilitates rise of the B conversion from 38 to 60% at 673 K and change of
the conversion products distribution. Zn (Mg) is found to favor an increase of C1-C3 alkanes, benzene
and other aromatic hydrocarbons yield among (M + B) conversion products, while Zr containing
catalysts are characterized by excess formation of C2-C4 olefins and C5+ aliphatic hydrocarbons. The
distribution of products of the (M+ B) mixtures conversion over zirconium containing catalysts
depends on the reaction temperature. This dependence occurs as zirconium possesses the ability to
raise the hydroxyl groups concentration in the octahedral environment of Al, and therefore reduce the
aromatizing activity of HZSM-5.
3.1. Oil refinery and petrochemistry
252
P-3.1-13
Oxidative dehydrogenation of ethane over iron modified SBA-3
E. Janiszewska, J. Kowalska-Kus, K. Nowinska, S. Kowalak
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland,
eszym@amu.edu.pl
Oxidative dehydrogenation (ODH) of light paraffins is a promising alternative to conventional
methods of olefins production. The presented study was focused on catalytic activity of the Fe
modified silica and aluminosilicate SBA-3 materials for ODH of ethane with N2O as an oxidant. It
was shown that formation of iron species, active for ODH of light paraffins does not depend on the
presence of acidic centres on solid supports, while the selectivity towards ethene decreases with
increasing acidity of the samples. The UV-vis spectra show the presence of oligomeric Fe species
responsible for high activity for N2O decomposition towards oxygen species enable of transferring
paraffins into olefins.
P-3.1-14
Propene and Butenes from Selective Ethene Conversion Over Acidic 10-Membered Ring
Zeolites
S. Follmann, S. Ernst1
1Department of Chemistry, Chemical Technology, University of Kaiserslautern (TU), Kaiserslautern,
Germany, ernst@chemie.uni-kl.de
Ethene and propene are two major feedstocks in the petrochemical industry. Traditionally, they are
produced via the steam cracking process from e.g., naphtha. Since a couple of years, the demand for
propene is growing faster than that for ethene. Hence, alternative (so-called on-purpose) processes
have been developed for the production of propene independently of ethene. Among them are fluid
catalytic cracking (FCC), the metathesis of ethene with butenes, propane dehydrogenation and the
methanol-to-propylene (MTP) route. In the present contribution, the potential of acid catalyzed
conversion of ethene to mainly propene and butenes has been studied over 10-membered ring zeolites
with different pore architectures to explore the potential of direct propene synthesis from ethene.
P-3.1-15
Synthesis of zeolite-type sorbents for sorption of petroleum hydrocarbons
W. Franus1, M. Wdowin2, M. Franus1, L. Bandura1
1Department of Geotechnics, Civil Engineering and Architecture Faculty, Lublin University of
Technology, Nadbystrzycka 40, 20-618 Lublin, Poland
2Mineral and Energy Economy Research Institute of The Polish Academy of Sciences, Wybickiego 7,
31-261 Krakow, Poland, wdowin@meeri.pl
The paper presents the possibility of using synthetic zeolites (Na-P1, Na-X, Linde-A, sodalite and
mixture of Na-P1/Na-X/Linde-A - that properties was thermally modified) and natural zeolite
(clinoptilolite) as sorbents of petroleum hydrocarbons. The highest sorption for non-activated material
showed clinoptilolite (1.11-1.14 g/g of sorbent). For the synthetic zeolites, these values ranged from
0.63 for sodalite to 1.17 g/g of sorbent for zeolite Na-P1. With the increase in the activation
temperature up to 400°C sorption increased to 1.33-1.48 g/g sorbent.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.1-16
Synthesis of SAPO-41 using different templates and their catalytic performance in n-decane
hydroisomerization
Aijuan Zhao 1, Wei Wu1*, Rui Zhang1, Min Liu1, Huimin Wu1, Linfei Xiao1
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education ; School of
Chemistry and Material Sciences, Key Laboratory of Chemical Engineering Process&Technology
for High-efficiency Conversion, Heilongjiang University, Harbin 150080, China;
e-mail: wuwei@hlju.edu.cn
SAPO-41 molecular sieve was found suitable for obtaining high-yield isomers of long-chain nalkanes. In our work, SAPO-41 samples were synthesized using DBA and DPA as the templates,
respectively. The morphology of S41-P were octagonal prisms. Meanwhile, S41-B presented platelike crystals, which piled up the prisms. The catalytic activity of Pd/S41 samples dereased in the
following order: Pd/S41(0.6)-P > Pd/S41(0.6)-B > Pd/S41(0.2)-P > Pd/S41(0.2)-B, which is
consilient well with the mild strength acid site of the SAPO-41 samples. The 90.2% of n-decane
conversion and 89.4 % of selectivity for iso-decane was achieved at 350 oC over the Pd/S41(0.2)-P.
P-3.1-17
Effect of Impurities in Benzene on Benzene Ethylation over MCM-22
Shih-Yuan Chen1, Tsung-Han Lin1, Soofin Cheng,*1 Chyi-Woei Young 2
1Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
R96223149@ntu.edu.tw; *chem1031@ntu.edu.tw
2New Materials Research and Development Department(T64), China Steel Corporation, Kaohsiung,
812 ,Taiwan
Trace amounts of impurities (in ppm or ppb level) like thiophene, sulfur-containing and nitrogencontaining molecules were present in benzene produced from coal and tar. A fixed bed flow system
was used to investigate the effect of these impurities on benzene ethylation over MCM-22 catalyst.
MCM-22 synthesized by modifying the process disclosed by Corma's group was characterized by
XRD, N2 sorption, SEM and NH3-TPD. The catalytic activity decayed with time-on-steam when
thiophene content in benzene was higher than 0.16 ppm, while more drastic decay was seen with
nitrogen-content in ppb level.
P-3.1-18
Hydroisomerization of Long-Chain Paraffins
over Nano-Sized Zeolite Pt/H-Beta
K. Ficht1, F. Bauer1, T. Kuchling2, R. Gläser1
1Inst. of Chemical Technology, Universität Leipzig, Germany, frank.bauer@uni-leipzig.de
2Inst. of Energy Process Eng. and Chem. Eng., TU Bergakademie Freiberg, Freiberg, Germany
For boosting the octane number of gasoline, reducing the pour point of diesel, and improving the
viscosity properties of long-chain n-paraffins, hydroisomerization of n-alkane over nano-sized zeolite
Pt-Pd/H-Beta (with nSi/nAl ratios of 20-25) was studied. As a large-pore zeolite, nano-sized zeolite HBeta has shown its advantages especially in the isomerization of long-chain n-paraffins (C14-C22) due
to its distinct pore structure, reduced diffusion pathways, and “mild acidity”. Thus, in addition to
mono-branched isomers (25 wt.%) high contents of multi-branched isomers (45 wt.%) were obtained
at 80 % conversion (220 °C, 50 bar) without extensive cracking (10 wt.%). Pilot plant tests up to 30
days on-stream revealed the outstanding isomerization performance of zeolite Pt-Pd/H-Beta.
3.1. Oil refinery and petrochemistry
254
P-3.1-19
Catalytic properties of zeolite-containing cracking catalysts with controlled content of rare
earth elements
T.P. Sorokina1, V.P. Doronin1, P.V.Lipin1, O.V. Potapenko1, V.I.Gordenko2
1Institute of Hydrocarbons Processing of Siberian Branch Russian Academy of Sciences,
Omsk, Russia, sorokina@ihcp.ru
2Gazprom neft Omsk Refinery, Omsk, Russia, Gordenko.VI@omsk.gazprom-neft.ru
Rare earth elements (RE) as modifiers of the catalytic properties of catalytic cracking catalysts are
used from 60-s of the last century. Role of RE in the cracking catalyst consists of three main
functions:
- increase activity of cracking catalysts by generating Bronsted acid sites in the zeolite;
- increase the thermal stability of the zeolite component of catalytic cracking catalysts;
- enhance the contribution of hydrogen transfer reactions in the overall speed of the cracking
process.
The first two of these functions play a positive role to ensure high catalytic and thermal properties of
cracking catalysts. Along with this increase in the contribution of hydrogen transfer reactions in the
overall speed of the cracking process plays a negative role, because it leads to lower octane gasoline
characteristics due to saturation of the gasoline olefin series.
P-3.1-20
Hydrogenation of tetralin over Ir-TiO2/SBA-16
B. Ledesma, V. Valles, M. Martínez, O. Anunziata, A. Beltramone
Centro de Investigación en Nanociencia y Nanotecnología, Facultad Córdoba, Universidad
Tecnológica Nacional, Maestro López y Cruz Roja Argentina, 5016, Córdoba, Argentina.
e-mail: abeltramone@scdt.frc.utn.edu.ar
A titanium modified catalyst based on noble metal has been prepared with the main aim of obtaining
thiotolerant catalysts to be used in second stage processes of mild-hydrotreating. We study the
catalytic properties of 1 wt% Ir-containing mesoporous materials modified with TiO2 in the
hydrogenation of tetralin to decalin in the presence of 100 ppm of dibenzotiophene at 250°C and 15
atm of pressure of hydrogen, using a Parr reactor. Ir/mesoporos materials were prepared by wetness
impregnation using Iridium Acetylacetonate as source of Ir. Titanium oxide was added via post
synthesis with the purpose of improve iridium dispersion. The catalyst synthesized by us had good
activity measured in tetralin hydrogenation at mild conditions. The experimental data was
quantitatively represented by a modified Langmuir-Hinshelwood type rate equation. The preliminary
results show these materials as a promising catalyts for HDS/HDN reactions.
P-3.1-21
Mixed Naphtha-Methanol as Feedstock in the Catalytic Cracking Process
Y.Y Ji, M.S. Zhang, J.Z. Jiang
Beijing Research Institute of Chemical Industry, SINOPEC, Beijing, China, jiyy.bjhy@sinopec.com
With the development of coal chemical industry and C1 chemistry, methanol, as a potential substituted
petroleum feedstock, has been focused on. Here, Naphtha mixed with 7.0% (vol.) methanol was used
as feedstock in the catalytic cracking process over the ZSM-5 based catalysts in a fixed-bed reactor.
The reaction condition was: 550℃, WHSV=1h-1, mixed naphtha-methanol:water=1:1(weight). The
result showed that the addition of methanol in naphtha would lead to the decrease of C2= ~ C4= yields.
Meanwhile, propylene to ethylene ratios decreased. Oppositely, aromatics yield increased. The trial of
mixed naphtha-methanol as feedstock in the catalytic cracking process at 550℃ revealed that it was
not suitable for producing C2= ~ C4= at such condition due to more aromatics formed.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.1-22
Dehydrogenation of 4-vinylcyclohexene and ethyl benzene using carbon dioxide and molecular
oxygen on platinum-gallium pentasils modified with REE oxides
Alimardanov Kh.M., Jalilova A.A., Abasov S.I., Suleymanova E.T.
Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences, Baku,
AZ 1025 Fax number 99412 490 35 20 e-mail: arzu.jalilova@gmail.com
The present work is devoted to the study of the reaction of dehydrogenation of 4-vinylcyclohexene
(VCH) and ethylbenzene (EB) with molecular oxygen and/or carbon dioxide on the catalysts prepared
by modification of HNa-MFi zeolite by platinium, gallium and REE compounds. The activity and
selectivity of the catalytic system was established to be dependent on the nature of REE and oxidants.
The dehydrogenation of VCH to EB and ST as well as EB to ST using CO2, most effectively proceeds
on Pt-Ga/HNa-MFi, promoted by the mixture of oxides of gadolinium, neodymium and lanthanum.
Under the other similar conditions, the addition of a minor quantity of molecular oxygen has a
promoting effect on the process.
P-3.1-23
Synthesis of nanoscale sulfide catalysts based on tungsten and nickel for hydrodearomatization
processes
I.A. Sizova1, A.S. Vilesov1, D.V. Borisov1, S.I. Serdyukov1,2, A.L. Maximov1,2, E.A. Karahanov2
1A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, isizova@ips.ac.ru
2Dep. of Chemistry, Moscow State University, Moscow, Russia
In this research the method of preparing nanoscale Ni-W-S catalysts for the hydrogenation of
aromatic hydrocarbons has been proposed. This method consists of the mechanical and ultrasonic
dispersing of the active component in an environment containing surfactants. Nickel-tungsten
catalysts containing 2.2 wt.% Ni and 12 wt.% W, has been supported by the mesoporous
aluminosilicates Al-HMS (40), Al-HMS (100) and HMS. Mesoporous aluminosilicates catalysts
showed high activity and selectivity in the hydrogenation of naphthalene under a hydrogen pressure
of 50 atm at the temperature range 325-350oC.
P-3.1-24
Synthesis and investigation of catalytic properties of modified ZSM-5 type aluminosilicates
A.I. Terentyev1, A.V. Vosmerikov2, N.A. Yurkin1, Ya.E. Barbashin2, A.L. Khlytin1, E.G. Poduryan1
1JSC «Novosibirsk Chemical Concentrates Plant», Novosibirsk, Russia, terentjev@yandex.ru
2Institute of Petroleum Chemistry SB RAS, Tomsk, Russia
Metal-modified ZSM-5 structure aluminosilicates were synthesized and hydrocarbon conversion
catalysts were prepared on their basis. The catalytic properties were examined in the processes of
refining and hydro-refining of gasoline and diesel fractions of various sources. It was demonstrated
that the catalysts prepared from Zr-, Nb-Zr- and Co-Nb-modified aluminosilicates were effective for
producing of high-octane gasoline and low-freezing diesel fuel.
3.1. Oil refinery and petrochemistry
256
P-3.1-25
Effect of the channel system, aluminum content and acidity of H-zeolites in the activity and light
olefins yield during the cyclohexane cracking
Alexandre A. S. Gonçalves1, Ernesto A. Urquieta-Gonzalez1
1Laboratory of Catalysis, Department of Chemical Engineering, Federal University of Sao Carlos, C.
Postal 676, CEP 13565-905, São Carlos (SP), Brazil, urquieta@ufscar.br
Hydrocarbons can be activated on H-zeolites, where can occur cracking of heavy to light more
valuable molecules. Most of zeolites have been investigated for the cracking of linear paraffins.
Nevertheless, not suitable information is available to the naphthenes cracking. The objective of this
work was the application of commercial USY, ZSM-5, mordenite and ferrierite in the cyclohexane
cracking to better understand the effect of their textural and physico-chemical properties in the
activity and to the yield of light olefins. The zeolites were characterized by XRD, SEM, EDX and
NH3-TPD. Beside to have confirmed the kwon capacity of H-ZSM-5 zeolites to produce light olefins,
we also showed the potential of H-beta to be used in naphthenes cracking. The H-beta zeolite
(Si/Al=15) presented higher activity and yield to light olefin than a USY zeolite (Si/Al=3). That
performance was related to its higher external area, strong acidity and their 3D/12MR channel system.
P-3.1-26
Mesoporous Aluminosilicates-Supported Noble Metal Catalysts for Aromatic Hydrogenation
S.I. Shirokopoyas1, S.V. Lysenko1, S.V. Baranova1, A.L. Maximov1,2, S.V. Kardashev1,
A.B. Kulikov2, N.F. Kovaleva1, V.A. Ostroumova1, E.A. Karakhanov1.
1Dep. of Chemistry, Moscow State University, Moscow, Russia, shirokopoyas-s-i@yandex.ru
2A.V. Topchiev Institute of Petrochemical Synthesis of the Russian Academy of Sciences
Pt-Pd/Al-HMS and Pt-Pd/Al-SBA-15 catalysts based on mesoporous aluminosilicates were tested in
hydrogenation of tetralin, naphthalene and toluene mixture in n-heptane (feed a), and βmethylnaphthalene in n-heptane (feed b). The hydrogenation of toluene, naphthalene, and βmethylnaphthalene at 220-260oC and WHSV=1.7 h-1 occurs quantitatively on the both type of
catalysts, and no presence of the side reaction such as hydrogenolysis. The sulfur tolerance of
catalysts in the presence of dibenzothiophene (150-250 ppm S in feed) depends on acidity of
mesoporous aluminosilicate and it decreased when Si/Al increased.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.1-27
The effect of incorporation Zn species on the acidity and catalytic performance of the nanoZSM-5 zeolite in aromatization of 1-hexene
Gaoliang Wang, Wei Wu*, Wang Zan, Wenjing Wang, Xin Qi
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education;
Key Laboratory of Chemical Engineering Process&Technology for High-efficiency Conversion,
School of Chemistry and Material Sciences, Heilongjiang University, Harbin 150080, China;
e-mail:wuwei@hlju.edu.com
Outstanding aromatization performances have been observed over the ZSM-5 zeolite modified with
the incorporation of Zinc in terms of the selectivity and stability. The nano-ZSM-5 zeolite parent and
The nano-ZSM-5 zeolite of Al atom on framework partially isomorphously substituted by Zinc were
synthesized based on the use of preset crystal seeds solution free organic template, and the Zn/HNZ5
was obtained by impregnation methods. Compare with ZSM-5 zeolite,the samples were modified
with Zn species exhibited more Lewis acid, and a certain amount of middle strong acid sites were
formed owing to the Zn species combine with the Brønsted acid sites. The 1-hexene aromatization
stability and aromatics yield were significantly improved over the Zn-modified samples in order
Zn/Al-HNZ5>Zn/HNZ5>HNZ5.
P-3.1-28
Synthesis of aluminum modified 3D mesoporous TUD-1 materials and catalytic hydrotreating
of FCC diesel
Y. C. Deng1, A. J. Duan1, Z.G. Wang1, Z. Zhao1, J. Liu1, G. Y. Jiang1, Y. C. Wei1
1State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, P. R.
China;
* A. J. Duan:duanaijun@cup.edu.cn; * Z. Zhao: zhenzhao@cup.edu.cn
A novel aluminum modified 3D mesoporous TUD-1 material (AT) was synthesized using TEA and
TEAOH as co-template. The pore size from BJH model is 6.8nm. The sample shows a surface area of
701m2/g, and a total pore volume of 0.98cc/g. As the AT content in the supports was 30 m%,
NiMo/Al2O3-AT-30% catalyst exhibited the highest HDS activity of 97.5%, and the product with the
sulfur content of 31.7 mg⋅L-1 was achieved, satisfying the sulfur regulation of Euro IV specification
(<50 μg•g-1) of ultra clean diesel fuel.
3.1. Oil refinery and petrochemistry
258
P-3.1-29
Non-noble metal hydrcarbon hydroisomerization catalyt supported on SAPO-11 of small-size
and enhanced acidity
Lin Guo1,2, Yu Fan1,2, Gang Shi2, Xiaojun Bao1,2
1State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing102249,
China, baoxj@cup.edu.cn
2Key Laboratory of Catalysis, China National Petroleum Corporation, China University of
Petroleum, Beijing 102249, China
Pt/SAPO-11 catalysts are now considered as the best catalyst system for hydrocarbon
hydroisomerization and have been used for the catalytic dewaxing of lube oil basestocks. However,
conventional SAPO-11 can only produce mono-branched isomers but hardly allows the formation of
di-branched isomers because of its larger crystal size and limited acid sites. More seriously, the noble
metals Pd and/or Pt supported on SAPO-11 could be poisoned by sulfur-containing compounds. To
solve the above problems, herein we report a two-stage crystallization strategy to synthesize SAPO11 with small crystal size and enhanced acidity and a SAPO-11 supported NiMo catalyst. The results
obtained by using n-octane and a real sulfur-containing gasoline as feedstocks showed that the
NiMo/SAPO-11 catalyst had not only excellent di-branched isomerization abililty but also
outstanding tolerance to sulfur, which sheds a light for the industrial development of non-noble metal
based hydroisomerization catalysts.
P-3.1-30
Selective ring opening of tetralin on Pt/Beta catalysts
K.B. Chi1, Z.J. Tian2, L.J. Yan1, H.J. Ma2, T.F. Zhang1, S. Hu1, C. Luo1, R.S. Xu2
1Petrochemical Research Institute, PetroChina Company Limited, Beijing, China,
yanlj@petrochina.com.cn
2 Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
The removal of aromatics from diesel fuel with high aromatic content and low cetane number has
become a focus of intense research due to the stringent environmental legislations associate with
clean fuels. Selective ring opening (SRO), as a promising route to improve diesel fuel quality, can
give rise to a high cetane product without any loss of the reactant molecular weight. In this work, we
synthesized three types of Beta zeolites with different SiO2/Al2O3 mole ratios and loaded with Pt. We
investigated SRO of tetralin using Pt/beta catalysts in a 10ml fixed-bed reactor and studied the
influence of acidity of these three catalysts. The results showed that Pt/Beta catalyst with medium
Brönsted acidity exhibited highest SRO performance of tetralin and limited excessive cracking.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.1-31
Enhance catalytic properties of the MFI/MCM-41 composite materials
F. E. Imbert1, E. Sosa1, F. Aguirre1, L. Belandría1, P. Rodríguez1, A. Uzcátegui1, A. E. Mora2, G.
González3 and J. Fernandez2
1 Laboratorio de Cinética y Catálisis, Departamento de Química, Facultad de Ciencias, Universidad
de Los Andes, Mérida 5101. e-mail: imbert@ula.ve
2 LAQUEM Facultad de Ciencias, Universidad de Los Andes, Mérida 5101
3 Laboratorio de Materiales, Centro de Ingeniería III, Instituto Venezolano de Investigaciones
Científicas, Altos de Pipe, Carretera Panamericana Km 11, Los Teques
A MFI/MCM-41 composite material, a zeolite type MFI and Al-MCM-41 were synthesized from
kaolin, using TPA and CTAB as structure directing agents. The MFI/MCM-41 composite material
was synthesized in two steps. In the first, MFI was obtained and then treated with solutions of
different NaOH concentrations (1 – 4M), in the second step the reaction mixture was treated under
MCM-41 synthesis conditions. The materials were characterized by means of X-ray diffraction
(DRX), nitrogen adsorption/desorption isotherms, scanning electron microscopy (SEM), energy
dispersive X-ray (EDX), transmission electron microscopy (TEM) and ammonium thermodesorption
(TPD-NH3). The composite material type MFI/Al-MCM-41 with zeolite building units in the
mesoporous walls was synthesized with 2 - 3 M. This material showed a significantly higher density
of stronger acid site than MFI; consequently, higher catalytic activity and stability in the m-xylene
transformation reaction. The D/I ratio showed a maximum at 3 M, while the P/O ratio decreased as
alkaline concentration increased. The above results confirmed the unique characteristics of the
composite material MFI/Al-MCM-41 that comprise high activity (>MFI) and a selectivity similar to
that of MCM-41.
P-3.1-32
Oligomerization of dicyclopentadiene on some zeolites and mesoporous catalysts
Pugacheva A.A., Kulikov A.B., Maximov A.L.
A.V.Topchiev Institute of Petrochemical Synthesis, RAS, Moscow, Russia pugacheva.asja@mail.ru
High-energy fuels produced on basis of dicyclopentadiene oligomers (ODCPD) are notable for
excellent stability, high combustion heat and low temperature properties. The aim of this work was to
investigate activity of different heterogeneous catalysts for DCPD oligomerization to produce
components for high-energy fuels.
In this work we used several catalysts for DCPD oligomerization: β-zeolite in Н-form, sulfated
mesoporous aluminium oxide, Y-zeolite in Н-form and Al-MCF. For hydrogenation ODCPD we used
as a catalyst Pd/C. Oligomerization was conducted in batch reactor under 150°С in Ar under
atmosphere pressure 7-14 hours and hydrogenation was conducted in autoclave in H2 atmosphere,
under 50 atm, 7 hours, 135oC.
After 14 hours the highest oligomerization capacity had HY sample with total oligomer yield 35
mass.%, but the highest selectivity for tetramer CPD formation had β-zeolite, with total oligomer
yield 26 % mass. The yield of hydrogenated products was 95 - 98%.
3.2. Non-oil fossil feedstocks into end products
260
P-3.2-01
Fine tuning of MCM-22 acidity for improving its catalytic properties in MTO reaction
P.F. Wang1,2, L.Z. Huang1,2, M. Dong1, J.F. Li1, W.F. Fan1,*, J.G. Wang1,*
1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, Taiyuan, China, fanwb@sxicc.ac.cn, jgwang@sxixx.ac.cn
2University of Chinese Academy of Sciences, Beijing, China
The control of the produc distribution in MTO reaction remains a great challenge. The olefin
selectivity depends strongly on the zeolite topology, acidity and reaction parameters. MCM-22 zeolite
has a unique structure containing two non-intersecting pore systems of intralayer 10-MR sinusoidal
channel and interlayer 12-MR supercages, which makes it a potential catalyst in MTO reaction.
However, the high content of Al content in the framework has negative effect on the selectivity of
light olefins and the catalytic stability. In this context, the acidity of MCM-22 is finely adjusted
through the dealumination with various methods. A proper dealumination cannot only selectively
removes framework Al sites in MCM-22 but also decreases strong acid amount and adjusts the
Brönsted/Lewis acid ratio. As a result, the propene selectivity and the catalytic stability were
significantly improved.
P-3.2-02
Synthesis of size-controlled FeMFI zeolites and their catalytic activities
H. Kobayashi, M. Nakaya, K. Kanie, and A. Muramatsu
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, Japan,
wwbaba@mail.tagen.tohoku.ac.jp
We report the synthesis of size-controlled MFI-type Ferrisilicates (FeMFI) and their catalytic
properties on olefin synthesis. Change in HCl/Si molar ratio and preheating treatment was decisive
factor on the particle size of FeMFI. The catalyst lifetime of FeMFI became longer by decrease in the
size or increase in the acid site density. The introduction of Fe3+ in substitution for Al3+ enhanced the
light olefin selectivity.
P-3.2-03
Methane conversion into aromatics over Fe-Mo/ZSM-5 catalysts
L.L. Korobitsyna1, N.V. Arbuzova1, V.I. Zaikovskii2, V.V. Kozlov1, Vosmerikov A.V.1
1Institute of Petroleum Chemistry SB RAS, Tomsk, Russia, e-mail: kll@ipc.tsc.ru
2Boreskov Institute of Catalysis, SB RAS, Novosibirsk, Russia
Nonoxidative methane dehydroaromatization over ZSM-5-type zeolites modified by nanopowders of
molybdenum (4.0% wt) and iron (0.05-1% wt) was studied. It has been found out that the 4.0%
Mo/ZSM-5 catalysts modified with nanosized Fe powders ensures much higher methane conversion,
better selectivity of hydrocarbons and higher yields of benzene. The highest methane conversion was
achieved by adding 0.05% wt of Fe nanopowder.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.2-04
Deposition of ZSM-5 on structured supports using dip-coating for MTO
Jasper Lefeverea,b, Jasper Van Noyena, Steven Mullensa, Frans Snijkersa, Pegie Coolb, Vera Meynenb
a Flemish Institute for Technological Research (VITO NV), Belgium.
b University Antwerp, Laboratory of Adsorption and Catalysis, Belgium.
As zeolite catalysts in industrial processes such as MTO often suffer from high pressure drops and
heat and mass transfer limitations, coating of structured support materials can offer an alternative. The
macroporous architecture of these supports has a major impact on the mass and heat transfer
properties and pressure drop of the final catalyst. By using 3DFD technology the porous architecture
of the support can be precisely controlled and modeled. The goal in this work was to prepare a layer
of ZSM-5 zeolite on a structured stainless steel 3DFD support using dip-coating. The effect of
milling, addition of inorganic binder, pH and repeated dipping was investigated. The uniformity,
thickness and adhesion strength of the coating have been evaluated and optimized. Finally, a ready to
use coated structured catalyst for MTO reaction was obtained and catalytically evaluated.
P-3.2-05
Effect of Mo precursor on Methane dehydroaromatization over Mo-MFI with core-shell
structure
Z. Jin1,2, S. Liu1, L. Qin1, Z. Liu1, Y. Wang1, Z. Xie1,*, X. Wang2,*
1Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China.
Email: wangyd.sshy@sinopec.com
2Research Institute of Industrial Catalysis, ECUST, Shanghai 200237, China
Mo-MFI catalysts with core-shell structure were prepared by impregnation of HZSM-5-Silicalite-1
(HZ5@S1) with various Mo precursors. The effect of Mo precursor on the amount of active Mo
species associated with Brønsted acid sites inside the zeolite pores over Mo/HZ5@S1 was studied
with a combination of characterization techniques. Significantly higher concentration of active Mo
specie mainly retained in the deeper pore channel is found in the catalyst prepared from Mo(CO)6.
The catalytic performance shows that the methane conversion and the products distribution depend on
the synergy of the location and amount of active Mo species in bifunctional MDA catalyst.
Mo/HZ5@S1 from Mo(CO)6 results in higher shape selectivity to aromatics and catalyst stability in
MDA.
P-3.2-06
The influence of zeolite nature on the behavior of the composite catalyst
in Fischer-Tropsch synthesis
E.Yu. Khatkova1, L.V. Sineva1, V.Z. Mordkovich1,2
1 Technological Institute for Superhard and Novel Carbon Materials, Troitsk, Russia,
e.khatkova@tisnum.ru
2 INFRA Technology Ltd., Moscow, Russia
Heterogeneous catalysts of Fischer–Tropsch process contain an oxide component in addition to the
active metal. The oxide component may have its own impact on the catalytic properties, for example
enhance one of the catalyst’s functions such as isomerization and/or cracking ability.
The aim of this work was to study how the nature of zeolite affects the parameters of hydrocarbon
synthesis from CO and H2 if the zeolite is an oxide component of a composite cobalt catalyst. The
synthesis was performed in a flow fixed bed reactor.
All the studied samples were active in the synthesis of C5+ hydrocarbons from CO and H2. The
parameters of hydrocarbon synthesis, in particular the composition of produced hydrocarbons C5+
depend on the acidity and other properties of the zeolite, which was introduced into the catalyst.
3.2. Non-oil fossil feedstocks into end products
262
P-3.2-07
Effect of synthesis conditions of CON-type zeolite on MTO reaction activity
M. Yoshioka, T. Yokoi, T. Tatsumi
Chemical Resources Laboratory, Tokyo Institute of Technology, Japan, ttatsumi@cat.res.titech.ac.jp
[Al,B]-CIT-1 was successfully synthesized under tumbling conditions as well as static ones. SEM
measurements revealed that [Al,B]-CIT-1 synthesized under tumbling conditions has a smaller
particle size in comparison with static ones, whose crystal sizes are about 200-1000 nm. The 27AlMAS-NMR spectra of [Al,B]-CIT-1 synthesized under both static and tumbling conditions exhibited
one sharp peak at 55 ppm with shoulder peak at 51 ppm, which is assigned to tetrahedrallycoordinated Al species. There is no marked difference in the temperature of h-peak of NH3-TPD
profiles, suggesting that; the acid strength of both samples was similar. The catalyst prepared under
tumbling conditions showed a longer catalytic life time for the MTO reaction than that under static
ones, and main product was propene with selectivity of ca 57 % in both cases. CIT-1s are very
attractive catalysts for selective production of propene via methanol conversion.
P-3.2-08
Metal-containing zeolites: their preparation, investigation of physical and chemical properties
and activity in the ethane aromatization
L.N.Vosmerikova1, V.I.Zaikovskii2, A.V.Vosmerikov1
1Institute of Petroleum Chemistry, SB RAS, Tomsk, Russia, lkplu@ipc.tsc.ru
2Boreskov Institute of Catalysis, SB RAS, Novosibirsk, Russia
The gallo-and aluminosilicates of ZSM-5 structure type are synthesized. The catalysts containing
different amounts of Zn, Ga, Pt and Pd are prepared on their basis. The microstructure, composition,
acidity and catalytic activity of the resulting catalytic systems are investigated in the course of
conversion of ethane into aromatic hydrocarbons. An introduction of zinc alumosilicate and platinum
galloalumosilicate into the catalyst is shown to ensure the high activity and selectivity in the course of
ethane aromatization.
P-3.2-09
The influence of catalyst acid strength on reactions relevant to Methanol To Hydrocarbons
(MTH) catalysis
M. Westgård Erichsen, S. Svelle, U. Olsbye*
inGAP Centre of Research Based Innovation, Department of Chemistry, University of Oslo, N-0315
Oslo, Norway, m.w.erichsen@kjemi.uio.no
Acid catalysis is important in many chemical reactions, and elucidating how catalyst acid strength
affects key reactions is therefore a topic of major importance. Yet, few examples of such studies exist.
In this contribution, two isostructural catalysts with different acid strength, H-SSZ-24 and H-SAPO-5
(AFI), were compared as catalysts for the Methanol to Hydrocarbons (MTH) reaction as well as for
individual reactions steps that contribute to the overall MTH reaction mechanism. It was found that
the strongly acidic H-SSZ-24 catalyst produces more aromatics and light alkenes than the weaker acid
H-SAPO-5, and that the major reaction intermediates differ between the catalysts. Kinetic studies of
individual reactions are in progress and will be reported.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.2-10
Relationship between coking, intraparticle diffusion and product selectivity in DTO
Y.X. Li, J.H. Guo, M.Y. Zhang, D.Z. Wang, Y. Wang
Dep.of Chemical Engineering, Tsinghua University, Beijing, China, liyuxin10@mails.tsinghua.edu.cn
The methanol or dimethyl ether (DME) to olefins (MTO/DTO) process is an important non-petroleum
route to produce platform chemicals. Coking is inevitable in the MTO/DTO reactions and it has a
larger effect on the larger molecules such as propene and butene than on ethene, which leads to an
increase in the selectivity to ethene with deactivation. After DTO reaction for 100 min and 300 min at
623K, although 2-ring aromatics in the catalyst had increased from 6.1% to 10.6%, the C2=-C4=
selectivities remained almost unchanged. However, after reaction at 673 K when 3-ring aromatics
appeared, the selectivities showed significant changes although the coke amount in the catalyst was
similar to that at 623K. Thus 3-ring and larger aromatics affect the selectivity in the DTO reaction.
This was mainly due to how it led to different decreases in the diffusion rates of the olefins in the
coked catalysts.
P-3.2-11
The relationship between acid and catalytic properties of Сa,H-BEA zeolites in dehydration of
methanol to dimethyl ether
Yu.N. Kochkin, N.V. Vlasenko, A.V. Shvets, N.V. Kasyan
L.V.Pisarzhevskiy Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 pr.
Nauky, Kyiv 03028, Ukraine, natalkakasian@gmail.com
We have reported the investigation of acidity of Ca-modified BEA zeolites on their catalytic
performance in the reaction of methanol to dimethyl ether dehydration, associated with the optimal
concentration of weak acid centres. We found that increase of calcium content results in the
appropriate increase of total acid sites concentration and decrease of acid strength. Catalytic behavior
of Са,Н-ВЕА zeolites in DME formation is determined by the ratio of weak to strong acid sites
concentration. The highest DME productivity was observed for the samples with similar
concentration of weak and strong acid sites.
P-3.2-12
Effect of zeolite’s structure, acidity and crystal size on the methanol to dimethylether (DME)
reaction
S.S. Akarmazyan1, S.A. Karakoulia2, K.S. Triantafyllidis3,*, D.I. Kondarides1,*
1Dept. of Chemical Engineering, Univ. of Patras, akarmazyansiranush@chemeng.upatras.gr
2Chemical Process and Energy Resources Institute (CPERI/CERTH), Thessaloniki, Greece
3Department of Chemistry, Aristotle University of Thessaloniki, Greece
Dimethyl ether (DME) has received growing attention in recent years as a useful building block for
the synthesis of important chemicals, such as clean and environmentally benign fuels, and as a source
of hydrogen for fuel cell applications. In the present work, dehydration of methanol to DME has been
studied over a set of twenty zeolite catalysts with variable physicochemical characteristics. A
systematic investigation has been conducted to elucidate the effects of zeolite structure, and the
respective microporosity, acidity and crystal size (nano-sized zeolites) on catalytic activity, selectivity
and stability, both in the absence and in the presence of water vapor in the feed. The reaction
mechanism has been investigated with the use of in situ DRIFT spectroscopy. Results show that
catalytic performance depend strongly on the physicochemical properties of the catalysts (Si/Al ratio,
micro/mesoporosity, crystallinity) and mainly on the nature, population and strength of acid sites.
3.2. Non-oil fossil feedstocks into end products
264
P-3.2-13
Heterogeneous catalysis of methanol conversion over 8-ring SAPOs: aspect of coke formation
and deactivation
Y.X. Wei, C.Y. Yuan, J.Z. Li, S.T. Xu, J.R. Chen, Q.Y. Wang, Y. Zhou, Z.M. Liu*
National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean
Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R.
China, liuzm@dicp.ac.cn
In Methanol-to-Olefins process, maximizing the generation of target products, ethene and propene
and minimizing the production of by-products and coke is the first consideration of efficient
conversion. In the present work, employing the techniques of TEOM (tapered element oscillating
microbalance), GC-MS and solid state NMR, methanol conversion and coke formation were
investigated under different reaction conditions. Confined coke species and their variation with
reaction temperature corresponded to the performance evolution. The correlation between acid
concentration of SAPO molecular sieves and methanol conversion and coke generation was also
established.
P-3.2-14
Outstanding stability of SBA-15 for promoting the catalytic methane decomposition towards H2
production
David P. Serrano1,2, Juan A. Botas1, Patricia Pizarro1,2 and Gema Gómez1.
1Deparment of Chemical and Energy Technology, ESCET, Rey Juan Carlos University, c/ Tulipán
s/n, 28933, Móstoles, Madrid, Spain, david.serrano@urjc.es
2IMDEA Energy Institute, Avda. Ramón de la Sagra 3, 28935, Móstoles, Madrid, Spain.
Catalytic decomposition of methane (DeCH4) is considered a mid-term alternative for free-CO2
hydrogen production. However, this carbon is deposited onto the catalysts (usually metals or carbons)
surface causing their deactivation. One requisite to develop active catalysts with long-term stability is
providing them with accessible active sites and high surface areas, as it has been demonstrated using
ordered mesoporous carbons (CMK-type) in DeCH4. In this work, pure silica materials were
investigated including zeolites, amorphous silica and ordered mesoporous silicas. Among them, SBA15 showed the highest carbon deposition rate and stability. Nevertheless, there is a delay in starting
the CH4 decomposition suggesting that silica is a promoter of active centres instead of a real catalyst.
P-3.2-15
Propane-butane fraction aromatization on promoted zeolites
A.G. Dedov1, A.S. Loktev1, D. A. Levchenko1, S.D. Golikov1, I.K. Poliwina1, A.E. Gekhman1, I.I.
Moiseev1
1Gubkin Russian State Oil and Gas University, Moscow, Russia, genchem@gubkin.ru
2N. S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia
Zn and Cr promoted catalysts on the basis of industrial high-silica ZSM-5 structure zeolites were
synthesized and studied in propane-butane fraction aromatization. It was found that Zn and Cr copromoted zeolite without alumina binding demonstrate highest yield of aromatization products.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.2-16
Study of HZSM-5 and its modifications in the conversion of methanol to hydrocarbons
B.B.Guliyev, R.H. Ahmadova, F.A.Babayeva, H.J.Ibrahimov, M.I.Rustamov
Institute of Petrochemical Processes of ANAS, Baku, Azerbaijan, bquliyev@gmail.com
The conversion of methanol over HZSM-5 and its modifications such as CuO/HZSM-5,
La2O3/HZSM-5, ZrO2/HZSM-5 catalysts were studied in a small scale fixed bed reactor at 1
atmospheric pressure, various temperatures and space velocities. Loading of metal oxides on HZSM-5
zeolite catalyst significantly increased methanol conversion. The influences of metal oxides on the
catalytic properties of zeolite catalysts and product selectivity have been discussed.
P-3.2-17
The combined influence of Raney cobalt and zeolite on the composition of the products of
Fischer–Tropsch synthesis.
E.Yu. Khatkova1, L.V. Sineva1, V.Z. Mordkovich1,2
1 Technological Institute for Superhard and Novel Carbon Materials, Troitsk, Russia,
e.khatkova@tisnum.ru
2 INFRA Technology Ltd., Moscow, Russia
Fischer–Tropsch synthesis (FTS) is the main stage of the technology of synthetic oil and high-quality
fuel production from carbon containing feedstock. Cobalt catalysts are considered as the most
promising ones, however, "skeleton" cobalt (Raney cobalt) catalysts, which have not yet been
completely investigated, can be used in FTS as well.
The aim of this work was to study the effect of the ratio of Raney cobalt and zeolite in the granular
composite catalyst. Prepared catalysts were tested in laboratory fixed bed reactor.
All the studied samples were active in FTS. It has been shown that the introduction of the zeolite in
the composition of catalyst positively influences the conversion of CO and especially the productivity
of C5+ hydrocarbons. The composition of the produced hydrocarbons depends on the ratio of the
zeolite and Raney cobalt.
P-3.2-18
Effect of acid site distributions in the framework of Al-MWW on its catalytic properties in
methylation of ethene
L.Z. Huang1,2, P.F. Wang1,2, J.F. Li1, M. Dong1, J.G. Wang1, W.B. Fan1
1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, Taiyuan, China, fanwb@sxicc.ac.cn
2University of Chinese Academy of Sciences, Beijing, China
MWW-type zeolite possesses one sinusoidal 10-MR channels within layers and one 12-MR supercage
between layers. The selective modification of the acidity of specific sites in its framework would
make it show interesting catalytic properties. Thus, Al-MWW zeolite was silylated with differentsized silanes to selectively passivate acid sites in the framework and tune pore openings for the
purpose of clarifying the effect of the locations and amounts of acid sites on its catalytic properties in
methylation of ethene. It will be shown that that the acid sites on the external pockets have negative
effect on the catalytic stability and the propene selectivity. A further investigation through the
dealumination, the modification of the pore structure and the adjustment of Al locations in the
framework shows that Al distribution has a remarkable influence on the catalytic properties of AlMWW. By optimizing the amount and distribution of acid sites, the activity, propene selectivity and
catalytic stability of Al-MWW in methylation of ethene were significantly increased.
3.2. Non-oil fossil feedstocks into end products
266
P-3.2-19
Effect of platinum amount on the catalytic properties of beta nanozeolite for WGSR
M. C. Rangel1, L.H. Silva1, S.T.F. Grecco1, T.F. Silva2, J.M. Assaf2 and J.M. Grau3
1Grupo de Estudos em Cinética e Catálise, Instituto de Química, Universidade Federal da Bahia, 40
170-280, Salvador, Bahia, Brazil, mcarmov@ufba.br
2 Dep. de Engenharia Química, Universidade Federal de São Carlos, 13565-905, São Carlos, São
Paulo, Brazil
3 Instituto de Investigaciones en Catálisis y Petroquímica (INCAPE), (FIQ, UNL-CONICET),
Santiago del Estero 2654, S3000AOJ Santa Fe, Argentina
The effect of platinum amount (0.1, 0.5 and 1.0%) on the catalytic properties of beta nanozeolite
obtained by wet incipient impregnation was studied in this work. The addition of platinum does not
affect the structure of beta nanozeolite and neither their textural properties. All samples were active in
the water gas shift reaction (WGSR) and the activity increased with the amount of platinum and the
reaction temperature. The platinum-richest catalyst was the most active one while those containing
0.1 and 0.5% platinum led to close conversions.
P-3.2-20
Toward supported co-catalysts for the direct conversion of styrene to styrene carbonate in the
presence of O2 and CO2.
C. Rocha, M. Ramin, R. Sassine, T. Onfroy, F. Launay
Laboratoire de Réactivité de Surface, UPMC-CNRS, Site le Raphaël, 3, rue Galilée, 94200 Ivry-surSeine - France, catarina.carvalho_rocha@upmc.fr
One of the main applications of mesostructured materials deals with catalysis based on their
functionalization with organics or metal precursors often considered alone. However, it is important
to reduce the number of separation processes that are solvent-consuming steps. The aim of this study
was to develop a catalytic system allowing the conversion of olefins into carbonates. The idea was to
make catalytic functions co-exist on SBA-15: Mn(Salen) for the epoxidation of styrene in the
presence of dioxygen and quaternary ammonium salts for the reaction of styrene oxide with CO2.
Mn(Salen) coordinated to dihydroimidazole groups and quaternary ammonium salts directly anchored
on silica SBA-15 exhibited similar activities to their analogs in benzonitrile. In this work, the effort
has focused on improving the heterogeneous quaternization process. First tests of styrene conversion
to styrene carbonate were carried out with a mixture of both heterogeneous catalysts used first with
O2 and CO2 without any separation step. The next issue of this work is the functionalization of SBA15 by both active phases and the study of their reaction in O2 and CO2 simultaneously.
P-3.2-21
New catalytic systems for synthesis of gasoline hydrocarbon components from dimethyl ether
on zeolite ZSM-5.
E.E. Kolesnikova, E.N. Khivrich, L.E. Kitaev, Z.M. Bukina, N.V. Kolesnichenko.
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia,
kolesnikova@ips.ac.ru
New samples of zeolite catalysts modified with Zr, Ti, S, Zn and Pd were synthesized. It was shown
by the complex of physical and chemical methods that modifiers (zirconium and titanium) are
chemically bound to the zeolite without changing the structure of the molecular sieve, and the
subsequent sulfation results in forming of superacid centers. The catalytic properties of the samples in
the conversion of DME to hydrocarbon components of gasoline were studied. The influence of the
operating parameters in the process of conversion of DME to synthetic hydrocarbons and changes in
activity and selectivity to the desired product in the oxidative regeneration were investigated.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.2-22
Study on DME conversion over modified zeolite catalysts using high-temperature diffusive
reflectance FTIR spectroscopy in situ
G.N. Shirobokova, E.N. Khivrich, T.I. Batova, A.S. Rodionov, N.V. Kolesnichenko, G.N.
Bondarenko, A.E. Kuzmin.
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, shirobokova-gn@ips.ac.ru
Some features of DME conversion over zeolite catalysts have been studied using high temperature
diffusive reflectance FTIR spectroscopy in situ. It is revealed that intermediate structure mostly
depends on the modifying component’s nature and it is different on the Mg-HZSM-5/Al2O3 and RhHZSM-5/Al2O3 catalysts. At low temperature (170oC) ketene is appeared to be form over Mg-HZSM5/Al2O3 whereas Rh-HZSM-5/Al2O3 produces ethanol as major intermediate. At higher temperature
(320oC) these intermediates convert to the main products of synthesis. Difference in the surface
compounds structure influences the product composition: ethylene is mainly formed over Rh-HZSM5/Al2O3 catalyst; Mg-HZSM-5/Al2O3 leads to propylene formation. The model of Luis and Bronsted
active sites on the modified zeolite catalysts was proposed.
P-3.2-23
Methanol conversion into light olefins over silicoaluminaphosphates coated with silica
S.V. Konnov1, I.L. Aranovich2, E.E. Knyazeva,1,2 I.I. Ivanova1,2
1A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, konnov_sv@ips.ac.ru
2Dep. of Chemistry, Moscow State University, Moscow, Russia
Silicoaluminophosphates with intergrown CHA/AEI phases were synthesized and coated with
tetraethoxysilane or polymethylsiloxane by chemical vapour deposition and incipient wetness
impregnation techniques, respectively, were investigated in conversion of methanol to light olefins.
The amount of silica was varied from 0.6 to 1.9 wt. %. The catalysts were characterized by XRD,
SEM, nitrogen adsorption, TG-DTA, IPS-MS, TPD of ammonia and tested in MTO process at 400
oC. The best effect in terms of stability of catalytic activity was observed over CHA/AEI materials
modified by 0.6-0.7 wt. % of silica: the lifetime over these catalysts was increased by 1.5 times. The
effect is due to poisoning of the acid sites on the external surface, which prevents the formation of
coke and blockage of the pore entrances. Further increase of the amount of the silica on the surface
results in narrowing of the entrances of the pores and leads to faster deactivation due to the pore
blockage.
P-3.2-24
The decomposition of nitrous oxide and partial oxidation of methane over ZSM5 catalysts; the
effect of cobalt or iron loading
N. A. Khan, M. Scollay, A. Crowfoot, E. Kennedy, B.Z. Dlugogorski, M. Stockenhuber
Priority Research Centre for Energy (PRCfE), University of Newcastle, Callaghan NSW 2308,
Australia, Michael.stockenhuber@newcastle.edu.au
The large stability of the methane molecule is the main barrier for its conversion to valuable products
at relatively lower temperatures and is reliant on the reactivity of oxygen and catalytic selectivity. We
studied the dissociation of nitrous oxide and partial oxidation of methane over cobalt and iron
catalysts, loaded on a zeolite and alumina support. The temperature, pressure, oxidant, molar ratio
(CH4:N2O), and metal loading affects the conversions of methane and nitrous oxide. The temperature
for dissociation of pure nitrous oxide over Co-ZSM5 was lower as compared to Fe-ZSM5. Selective
oxidation of methane was found to compete with nitrous oxide decomposition.
3.2. Non-oil fossil feedstocks into end products
268
P-3.2-25
Nanosized ZSM-5 Synthesized with Different Templates for MTP reaction
Lanlan Zhang, Yanjun Gong*, Qing Zhang, Wenlong Li, Shaolong Zhang, Feiying Yang, Wugang
Wang, Tao Dou
The key laboratory of Catalysis of CNPC, China University of Petroleum, Beijing 102249, China,
gongyj@cup.edu.cn
Nanosized ZSM-5 zeolites were successfully synthesized with high crystallinity by various templates
(TPAOH, TPABr, BTA). SEM revealed that ZSM-5 synthesized with different templates showed
different morpholpgy and particle size. The average crystal size was increased in the following order:
HZA (prepared by TPAOH) < HZB (prepared by TPABr) < HZC (prepared by BTA). And HZB
aggregate the particles of approximately 200 nm, which was formed by some 30-50 nm nanoparticles,
thus giving the biggest BET surface area of 405.6 m2 g-1. Compared with HZA and HZC, HZB has
good performance and higher catalyst lifetime in methanol conversion due to a suitable acid sites and
less diffusion limit from nanosized ZSM-5 crystal aggregation. After the 180 h of reaction, the HZB
catalyst exhibits a higher propylene selectivity (45.80%) and P/E ratio (7.7).
P-3.2-26
Mesoporous Zeolite SBA-15 and MCM-41 as Supports of Ni Catalysts for Carbon Dioxide
Reforming of Methane
Huimin Liu, Dehua He
Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education,
Department of Chemistry, Tsinghua University, Beijing 100084, China, hedeh@mail.tsinghua.edu.cn
Mesoporous zeolite SBA-15 and MCM-41 were used as the supports, and β-cyclodextrin (CD)
modified impregnation method was employed for preparing Ni catalysts (Ni/SBA-15-CD and
Ni/MCM-41-CD). The physicochemical properties of the catalysts were characterized by BET, XRD,
TPR, TPO and TEM. The catalytic performance of these catalysts in carbon dioxide reforming of
methane (CRM) were evaluted in a fixed bed reactor under the conditions of atmospheric pressure,
700 oC and GHSV of 1.2×104 mLg-1 h-1. For comparison, amorphous SiO2 was also used as support
and the prepared Ni/SiO2-CD was also evaluted. The results showed that the ordered mesoporous and
larger specific surface areas of SBA-15 (or MCM-41) lead to the stronger interactions between Ni and
SBA-15 (or MCM-41) and better dispersion of Ni on Ni/SBA-15-CD and Ni/MCM-41-CD.
Compared with Ni/SiO2-CD, SBA-15 and MCM-41 supported Ni/SBA-15-CD and Ni/MCM-41-CD
catalysts exhibited not only higher catalytic activities but also better stability in CRM.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.3-01
Kinetics of N2O decomposition over combined micro-mesoporous zeolites
M.Rutkowska1, L. Chmielarz1, B. Gil1, L. Obalová2
1Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland, rutkowsm@chemia.uj.edu.pl
2Technical University of Ostrawa, 17. listopadu 15, 708 33 Ostrava, Czech Republic
Due to increasing number of reports proving the successful synthesis of mesoporous zeolites there is a
need to examine the kinetics of the catalytic processes over this new group of hierarchical materials.
The undertaken studies were focused on the evaluation of the kinetic data of N2O decomposition over
mesoporous Beta and ZSM-5 zeolites using the linear regression method. The studies were performed
in inert conditions and in the presence of oxygen.
P-3.3-02
Epoxidation of Biodiesel with H2O2 over Hierarchically Structured TS-1 Catalysts Prepared by
Desilication and Transformation
N. Wilde, S. Gebhardt, W. Suprun, R. Gläser
Institute of Chemical Technology, Universität Leipzig, 04103 Leipzig, Germany, nicole.wilde@unileipzig.de
Epoxidized fatty acid esters and their derivatives are attractive as renewable feedstocks for a broad
range of large-scale industrial syntheses of chemicals and intermediates. TS-1, have been widely
studied for the selective epoxidation of a variety of organic substrates using aqueous H2O2 as the sole
oxidant. However, the utilization of TS-1 for the conversion of fatty acid esters is limited due to the
size of its micropores. Therefore, zeolites with hierarchical porosity are attractive alternatives. The
present work was, thus, devoted to synthesize TS-1 with a hierarchically structured pore system and
to investigate its potential for the heterogeneously catalyzed liquid-phase epoxidation of biodiesel
with H2O2.
P-3.3-03
Development of Lanthanide-incorporated Fe-based Zeolite Catalysts for Selective Catalytic
Reduction of NO
Sayeda Halima Begum1,3, Xiaoxiang Han2, Chin-Te Hung1, Shing-Jong Huang3, Shang-Bin Liu1,4*
1Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan,
sayedacu@gmail.com
2College of Food Science and Biotechnology, Zhejiang Gongshang University,Hangzhou 310035,
China
3Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
4Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan
Fe-based zeolites are promising catalysts for SCR of NO by NH3, which is limited by the activity at <
300 0C. A series Fe-based ZSM-5 catalysts were prepared by incorporating Ce, Pr, Nd, Sm via reflux.
The catalysts were categorized by EA, XRD, BET, TEM, XPS, NH3-TPD, and NMR. FeCeZSM-5
showed the best NO conversion > 90%. NH3-SCR are allied with the Brønsted acidity, as referred by
results obtained from both NH3-TPD and 31P NMR of adsorbed TMPO.
3.3. Environmental catalysis and conversion of biomass
270
P-3.3-04
Effect of preparation procedure on the structural and catalytic properties of Fe-ZSM-5 as NH3SCR catalyst
Alexander Shishkin, Per-Anders Carlsson, Hanna Härelind, Magnus Skoglundh
Competence Centre for Catalysis, Chalmers University of Technology, SE-41296, Göteborg, Sweden,
shishkin@chalmers.se
Fe-ZSM-5 catalysts have been prepared by different methods: incipient wetness impregnation using
Fe(NO3)3∙9H2O as iron precursor and either methanol or 50-% methanol in water as solvent and
conventional aqueous ion exchange using FeCl2 as iron precursor.
All the catalysts have been characterized by BET, ICP-AES, XRD, XPS, NH3-TPD and NO-TPD and
evaluated for NH3-SCR, NH3- and NO oxidation.
It was found that the catalyst preparation route of Fe-ZSM-5 is of significant importance for the
activity and selectivity to N2 for NH3-SCR. In addition, experiments in the absence of water have
been performed and the presence of water was found to have strongly influence on the catalytic
performance.
P-3.3-05
N2O decomposition over Cu-exchanged nanosheet ZSM-5
Wei Zou1,2, Pengfei Xie1, Yinghong Yue1*, Weiming Hua1, Dejin Kong2, Weimin Yang 2, Zi Gao1
1Department of Chemistry, Fudan University, Shanghai 200433, China, *yhyue@fudan.edu.cn
2Shanghai Research Institute of Petrochemical Technology SINOPEC, Shanghai 201208, China
Nitrogen oxides remain a major source of air pollution. The direct catalytic N2O decomposition
represents the simplest and most attractive solution for N2O abatement. Here, a comparative study of
nanosheet and conventional copper-exchanged ZSM-5 type zeolite catalysts in direct N2O
decomposition is presented.
The nanosheet type ZSM-5 was synthesized using C22-6-6Br2 as template. The Si/Al molar ratios of
both zeolites are 34 and 35 respectively.
The activity data are expressed as turnover frequencies (TOF) measured at different temperatures. It
is clear that the nanosheet catalyst is more active than the conventional one. The ultrathin thickness
along b-axis reduces the diffusion path length of reactant molecules in micropores.
P-3.3-06
Design of Ru loaded Zeolite Catalysts for Hydrogen-free Production of Conjugated Linoleic
Acids and Conjugated Oils
A. Philippaerts, J. Van Aelst, P. Jacobs, B. Sels
Centre of Surface Chemistry and Catalysis, KU Leuven, Heverlee, Belgium,
an.philippaerts@biw.kuleuven.be
Conjugated linoleic acids (CLAs) and conjugated vegetable oils are interesting compounds in the
coatings, paints and polymer industries as well as in the food industry.
This contribution presents the direct production of CLAs over Ru supported on zeolites. Ru/Cs-USY
was identified as the most active and selective catalyst for isomerisation of methyl linoleate to CLA at
165 °C. Interestingly, no hydrogen pre-treatment of the catalyst or addition of H-donors is required to
achieve industrially relevant isomerisation productivities.
The Ru/USY catalysts were also successfully evaluated in the isomerization of vegetable oils.
Because of the particular synthesis procedure, extra mesopores are created in the USY support
facilitating transport of the bulky triglyceride molecules to the active centers of the catalyst.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.3-07
A zeolite catalyst for transesterification of vegetable oils by ethanol
L.K. Patrylak1, K.I.Patrylak1, M.V. Okhrimenko1, V.V. Ivanenko1, A.M. Levterov2,
V.P. Marakhovskyi2, D.V. Savytskyi2, S.V. Konovalov1, Yu.G. Voloshyna1
1Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of Ukraine,
Kyiv, Ukraine, lkp@ukrpost.net
2A.M. Podgorny Institute for Mechanical Engineering Problems of National Academy of Sciences of
Ukraine, Kharkiv, Ukraine
Non-traditional catalyst for biodisel production on the base of ethanol and plant oils has been used.
Aklali zeolite A demonstrates high activity in ethanolysis. Biodiesel synthesized in comparison with
mineral diesel demonstrates some decrease of power indices, which are inessential for stable engine
work. Its ecological characteristics are far better: lesser emission of CO2, CO, CH and dust particles.
In contrast to methyl esters of fatty acids, ethyl esters show clearly the decrease of NOx content in
exhaust gases.
P-3.3-08
Trimetallic (Cu-Ag-Zn)/Mordenite system obtained via microwave radiation: characterization
and catalytic activity in NO reduction
I. Rodríguez Iznaga1, F. F. Castillón Barraza2, A. Simakov2, V. Petranovski2.
1Instituto de Ciencia y Tecnología de Materiales (IMRE) - Universidad de La Habana. Cuba.
inocente@imre.oc.uh.cu
2Centro de Nanociencias y Nanotecnología – Universidad Nacional Autónoma de México. Ensenada,
B.C. México. vitalii@cnyn.unam.mx
(Cu2+-Ag+-Zn2+)/Mordenite system was prepared via microwave-radiation assisted ion-exchange. The
exchange via microwave radiation doesn't affect the mordenite crystalline structure. Zn2+ and Cu2+
exchange is more favored by this method referring to the traditional exchange. Surface area and
micropore volume of monometallic Cu2+ and Zn2+ exchanged samples increased, while for Ag+
exchanged sample decreased. Evaluation of the catalytic activity of such mono- and tri-metallic
system to NO reduction with CO/C3H6 was done. All trimetallic samples have higher catalytic
activity than monometallic. The activity increase when Cu content is raised, and when Cu species are
stabilized in trimetallic samples.
P-3.3-09
Preparation of TiO2/Cr-Beta Zeolite as Photocatalyst
Shu-Hua Chien*, Bai-Lin Chen, Wen-Kai Tu
Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwan, chiensh@gate.sinica.edu.tw
In this study, a highly active photocatalyst, chromium-containing beta zeolite supported TiO2
(TiO2/Cr-Beta), was successfully prepared. Anatase TiO2 layer was grafted on the surface without
blocking the microporous channels or significantly affecting the structure of beta zeolite. The
photodegradation of methylene blue over TiO2/Cr-Beta and TiO2/H-Beta catalyst follows the firstorder kinetics. The incorporation of chromium can enhance the sensitization of TiO2 in both the UV
and visible-light regions. As a result, the photocatalytic activity of TiO2/Cr-Beta catalyst, under either
UV or visible-light, is remarkably improved as compared to that of TiO2/H-Beta catalyst.
3.3. Environmental catalysis and conversion of biomass
272
P-3.3-10
Co-conversion of vegetable oils and vacuum gas oil under catalytic cracking
P.V. Lipin, O.V. Potapenko, T.P. Sorokina, V.P. Doronin
Institute of Hydrocarbons Processing of Siberian Branch Russian Academy of Sciences, Omsk,
Russia, lipin@ihcp.ru
The present work was aimed at studying the transformation of a blend feed consisting of hydrotreated
vacuum gas oil and various vegetable oils under catalytic cracking.
Co-conversion of vacuum gas oil and vegetable oils under catalytic cracking conditions allow
increasing the total conversion of the blend feed and the yields of gasoline fraction and light olefins.
Maximum promoting effect is provided by the addition of 5-10 wt.% vegetable oil. The introduction
of 5 wt.% sunflower oil to vacuum gas oil upon cracking increases the yield of gasoline by 10 wt.%
as compared to the value calculated from the additivity. Upon cracking of the blend feed containing
oils with high content of unsaturated acids, the maximum effect is observed at lower oil contents. The
conversion grows mainly due to increasing yield of the gasoline fraction.
P-3.3-11
Selective conversion of lignin to chemicals via catalytic fast pyrolysis over zeolites
Zhiqiang Ma1, Ekaterina Troussard1,2, Jeroen A. van Bokhoven1,2
1 D-CHAB, ETH Zurich, Zurich, Switzerland zhiqiang.ma@chem.ethz.ch
2 Laboratory for Catalysis and Sustainable Chemistry, PSI, Villigen, Switzerland
High yields of liquid and selectivity to aromatic hydrocarbons can be obtained by catalytic fast
pyrolysis of lignin using zeolites. Tuning the selectivity of the liquid fraction is possible and high C/O
ratios can be obtained. Application of zeolites significantly improves the quality of liquid. The
catalysts play dual roles in this process. They transform the depolymerized intermediates into
desirable products, and they also stabilize the depolymerized intermediates and prevent the
repolymerization and thus coke formation. These processes depend on the amount of catalyst, their
Si/Al ratio and the pore size. H-USY showed the best results among all the catalysts tested.
P-3.3-12
A comparative study relating to active sites and mechanisms in the selective catalytic reduction
of NOx over Fe zeolites
I. Ellmers1, R. Velez2, A. Brückner2, U. Bentrup2, H. Huang3, V. Schünemann3, W. Grünert1
1Laboratory of Industrial Chemistry, Ruhr-University Bochum, Germany w.gruenert@techem.rub.de
2Leibniz-Institute for Catalysis e.V., Rostock, Germany,
3FB Physics, Technical University Kaiserslautern, Germany
Fe-ZSM-5 catalysts for the selective catalytic reduction by ammonia (NH3-SCR) were investigated
combining catalytic measurements of relevant reactions (NO oxidation, standard and fast SCR) with
comprehensive characterisation work to acquire new insights into the nature of active sites and
reaction steps.
Fe-ZSM-5 catalysts with varying distributions of Fe sites exhibit different catalytic properties with
respect to the test reactions; of special interest was a series made by SSIE into partially pre-exchanged
Ca/Na-ZSM-5 with nearly the same Fe content. This suggests that these reactions all proceed on
different active sites. Further, in case of NO oxidation an activation effect apparently caused by a
redox step was observed.
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P-3.3-13
Ethanol conversion to alkanes and aromatics over pilot Pd-Zn/Al2O3/MFI catalyst
A. V. Chistyakov, M.A. Gubanov, M.V. Chudakova, V. Yu Murzin, M.V. Tsodikov
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, chistyakov@ips.ac.ru
Here we present the study relates to peculiarities of ethanol conversion towards alkane-aromatics
fraction over pilot Pd-Zn/Al2O3/MFI catalyst. Aim fraction yield of hydrocarbons C3-C12 achieved 95
wt.%. Shown that ethanol converts towards alkanes and aromatics via two independent pathways.
Ethylene and diethyl ether were found to be the most probable reaction intermediates. Studied catalyst
was found to be stable during more than 48 hours on-stream. High activity and stability of considered
catalyst was found to be provided with [Pd0.5Zn0.5] clusters formation on the support surface with
average size 2-7 nm. Using a number of X-ray methods catalysts genesis was investigated.
P-3.3-14
Hydrogen-rich syngas production from catalytic steam pyrolysis-gasification of biomass on
Ni/MCM-41
Z. Wang1, C. Wu2, L. Wang1, P. T. Williams2,*, J. Shi1, J. Huang1,*
1 Laboratory for Catalysis Engineering, School of Chemical and Biomolecular Engineering, The
University of Sydney, NSW 2006, Australia, Tel: #61 9351 7483; Email: jun.huang@sydney.edu.au
2 Energy & Resources Research Institute, The University of Leeds, Leeds, LS2 9JT, UK, Tel: #44
1133432504; Email: p.t.williams@leeds.ac.uk
Ni/MCM-41 catalysts were applied for hydrogen production from steam pyrolysis-gasification of
biomass, wood sawdust in a two-stage fixed bed reaction system. The synthesised MCM-41
mesoporous catalyst supports were impregnated with different Ni loadings (5, 10, 20 and 40 wt.%),
which were characterized with XRD, SEM, TPR, TEM and TPO. NiO particles were homogeneously
dispersed inside the pores Ni/MCM-41 catalysts, except more bulk NiO particles (up to 200 nm
particle size) were detected outside the pores with Ni loading up to 40 wt.%. Gas production was
increased from 40.7 to 62.8 wt.%, hydrogen production was increased from 30.1 to 50.6 vol.% of
total gas composition with Ni loading increased from 5 to 40 wt.%. The low coke deposition (from
0.5 to 4.0 wt.%) with valuable bio-oil by-products were obtained using the Ni/MCM-41 catalyst. This
indicates that highly efficient biomass gasification to hydrogen and bio-oil on Ni/MCM-41 catalysts
via two-stage reaction is a promising method for the development of the biorefinery concept.
P-3.3-15
Dehydration of Renewable Feedstocks Using Single Site Heterogeneous Catalysts
Danni Sun1, Matthew. E. Potter1, Martha I.C. Angel2, Robert Raja1
1School of Chemistry, University of Southampton, Southampton, UK, ds7e10@soton.ac.uk
2Facultad de Ingeniería, Universidad de La Sabana, Campus Universitario Puente del Común,
Cundinamarca, Colombia
A series of isomorphously substituted aluminophosphate and silico-aluminophosphate molecular
sieves with AFI and CHA type framework were synthesized and studied as possible catalysts for
ethanol dehydration. CHA-type catalysts showed higher ethylene selectivity than their corresponding
AFI-type solid-acid catalysts, suggesting the CHA framework architecture is very effective for the
selective formation of ethylene. In particular, the bimetallic CHA-analogues, containing Co(II) and
Si(IV) as solid-acid centers (e.g. CoSAPO-34), displayed high ethylene conversions (98 %) with
ethylene selectivities approaching 93 %, under mild reaction conditions, facilitating considerable
energy savings for its commercial implementation.
3.3. Environmental catalysis and conversion of biomass
274
P-3.3-16
Valorization of crude glycerol into fuel additives over molecular sieves
J. Kowalska-Kuś, A. Held, A. Kuźnicka, K. Nowińska, S. Kowalak
Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland, jolakow@amu.edu.pl
Condensation of glycerol with acetone to produce solketal has been performed under mild reaction
conditions over SBA-3 and SBA-15 materials modified with Al, Zr, Nb by introduction into structure
or by impregnation. These materials were applied for the first time as catalysts for the studied
reaction. The conversion of glycerol over metal modified mesoporous catalysts differs significantly
regarding the way of metal introduction. The samples with metal cations introduced upon synthesis
are significantly more active than those prepared by impregnation. The acid sites generated in metal
cations modified materials are efficient in glycerol acetalization reaction. The tested catalysts do not
suffer from leaching and are promising catalysts for this reaction.
P-3.3-17
Lewis-Acid Catalyzed Conversion of Biomass-Derived Dimethylfuran to p-Xylene
E.M. Mahmoud, P. Do, R.F. Lobo
Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716
(USA), lobo@udel.edu
A renewable route to p-Xylene from biomass-derived dimethylfuran and ethylene is investigated with
zeolite catalysts. The capability of extra-framework cations in the zeolite framework– such as Na, Li,
K, Ag, and Cu – in faujasites Y (Si/Al=40), Y (Si/Al=2.55) and X (Si/Al=1.25) to catalyze this
reaction was investigated.
P-3.3-18
Preparation of Nano Metal Oxides through One-pot Synthesis Associated with Mesoporous
Silica and their Catalytic Applications
M.J. Suh1, S.K. Ihm1
1Dep. of Chemical & Biomolecular Engineering, KAIST, Daejeon, Republic of Korea,
skihm@kaist.ac.kr
One-pot synthesis method associated with mesoporous silica(SBA route) was applied for the
preparation of various metal oxide catalysts. Lanthanum cobaltites(LCO) and hybrid catalyst(Cu-AlSBA-15) with high surface area were successfully prepared via simultaneous formation of the
mesoporous structure(SBA-15) and the metal oxides. The crystallite size of LCO was controlled by
varying the pore size of SBA-15. The catalytic activity of LCO for toluene oxidation was in good
correlation with their surface area. The hybrid catalyst(Cu-Al-SBA-15) showed better performance in
the steam reforming of DME for H2 production than the physically mixed catalyst(Cu/Al-SBA-15).
The nano metal oxides prepared through one-pot synthesis method must be good candidates for
environmental catalysts.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.3-19
Effect of CO2 on deNOx activity of Cu/zeolite catalysts for NH3/SCR
Y.J. Kim1, I. Heo1,a, S. Sung1,b, K.M. Min1, J.K. Lee1, S.B. Hong1, I.-S. Nam1,*, B.K. Cho1
1Department of Chemical Engineering/School of Environmental Science and Engineering, Pohang
University of Science and Technology (POSTECH), Pohang, Korea;
(*)Corresponding author, E-mail: isnam@postech.ac.kr
The low-temperature deNOx activity of Cu/zeolite catalysts was significantly inhibited by the
presence of CO2 in the NH3/SCR feed stream. The inhibition effect of CO2 was much stronger over
CuSSZ13 than over CuZSM5, suggesting that the pore size of zeolites may play an important role in
the low-temperature deNOx activity of Cu/zeolite catalysts.
Present address: a Department of Chemical Engineering, University of Michigan, Ann Arbor, MI b
Environment Research Department, Advanced Technology Institute, Hyundai Heavy Industries CO.,
LTD.,, Ulsan, Korea
P-3.3-20
The role and peculiar properties of α-sites in N2O decomposition over FeMFI
L.Pirutko, V.Chernyavsky, E.Starokon, A.Kharitonov
Boreskov Institute of Catalysis S B R A S , Novosibirsk, Russia, pirutko@catalysis.ru
Search for ways to reduce nitrogen oxides in industrial emissions gives pulse to the study the Fecontaining zeolites (MFI, FER or BEA), which are highly active in N2O decomposition. When Fe is
introduced at the stage of hydrothermal synthesis the title reaction has been found to proceed on a
particular form of Fe2+, so called α-sites. But the postsynthesis introduction of Fe open more
opportunities for effective catalysts . The role of α-sites in activity of such systems is still debated.
The data to be presented confirm that catalytic properties are really determined by α-sites, whose
activity does not depend on the Fe content. At the same time the activity of α-sites are very strongly
influenced by the activation procedure. The samples calcined at 900 ° C show values of kα (the rate
constant for unit active site) to 2 orders of magnitude larger than steamed at 700°C samples
demonstrate. The report analyzes the causes first found heterogeneity of α-sites.
P-3.3-21
Cooperative effect of Lewis and Brønsted acid sites on Beta zeolites in dehydration of sugars
R. Otomo1, T. Yokoi1, J. N. Kondo1, T. Tatsumi1
Chemical Resources Laboratory, Tokyo Institute of Technology, ttatsumi@cat.res.titech.ac.jp
Herein, we report the modification of acid properties of Beta zeolites by post-synthetic methods to
improve a catalytic performance in dehydration of sugars such as glucose. Through detailed
investigation of the acid properties, we have successfully found that a cooperative effect of Lewis and
Brønsted acid sites on Beta zeolite is essential for the dehydration of glucose to HMF; Lewis acid
sites on the zeolites catalyze isomerization of glucose to fructose and Brønsted acid sites catalyze
dehydration of fructose to HMF.
3.3. Environmental catalysis and conversion of biomass
276
P-3.3-22
Gas phase glycerol dehydration to acrolein over catalysts derived from MWW layered
precursor: effect of molar ratio SiO2/Al2O3
A. J. S. Mascarenhas1,2, C. S. Carriço1, M. B. Santos1, D. S. Oliveira1, F. T. Cruz1, H. M. C.
Andrade1,2, H. O. Pastore3
1 Instituto de Química, Universidade Federal da Bahia, Brazil, artur@ufba.br
2 Instituto Nacional de Ciência e Tecnologia em Energia e Ambiente, Brazil
3 Instituto de Química, Universidade Estadual de Campinas, Brazil
MCM-22, MCM-36 and ITQ-2 were synthesized with molar ratio SiO2/Al2O3 = 30, 50 and 80,
characterized by DRX, FTIR, TG, SEM, textural analyses, EDX and NH3-TPD and catalytically
evaluated in gas phase glycerol dehydration to acrolein. The glycerol conversion was high for all
materials, but delaminated ITQ-2 (SiO2/Al2O3 = 30) has shown the highest acrolein selectivity, due to
its improved acidity and textural properties. The increase of SiO2/Al2O3 molar ratio causes a decrease
of both glycerol conversion and acrolein selectivity. The materials deactivate by coke formation,
which can be removed by oxidative treatment. ITQ-2 showed a good conversion and selectivity
recovery after 3 cycles of 10 h.
P-3.3-23
Suppression of the formation of N2O in selective reduction of NO with NH3 over Fe-zeolitepromoted commercial V2O5-WO3/TiO2 catalysts
M.H. Kim1, S.W. Ham2, C.H. Shin3
1Dep. of Environmental Engineering, Daegu University, Gyeongsan, Korea, moonkim@daegu.ac.kr
2 Dep. of Chemical Engineering, Kyungil University, Gyeongsan, Korea
3 Dep. of Chemical Engineering, Chungbuk National University, Cheongju, Korea
This study is to inquire a possibility to suppress the extent of N2O formation in the selective reduction
(SCR) of NOx by NH3 using Fe-ZSM-5-promoted commercial V2O5-WO3/TiO2 catalysts that have
been prepared using a commercial 1.68% V2O5-7.6% WO3/TiO2 catalyst and a Fe-ZSM-5 with a 96% exchange level via a solid state ion-exchange. The commercial SCR catalyst yielded the N2O
formation of 3-50 ppm at 400-480oC. When a small amount (8%) of the Fe-ZSM-5 was added into the
commercial catalyst, the extent of N2O formed was less than 2 ppm even at 480oC, and conversion
values for NOx were comparable in both cases. Larger quantities of the Fe zeolite led to significant
decrease in deNOx efficiency, although they all could also give very low N2O production levels.
P-3.3-24
Hydrotreatment of Vegetable Oil over Pt/Zeolite for Producing High Quality Diesel-Range
Fuels
Congxin Wang1,2, Qianhe Liu1,2, Lijun Yan3, Chen Luo3, Zhijian Tian1*
1 Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian, China, tianz@dicp.ac.cn
2 University of Chinese Academy of Sciences, Beijing, China
3 Petrochemical Research Institute, PetroChina, Beijing, China
Effective conversion of lipids to fuels attracted growing interest. In the last decade, many supported
metal catalysts were found to be active in converting vegetable oil to n-alkanes. In this work, the
Pt/SAPO-11 and Pt/ZSM-22 were prepared and used as catalyst on which the soybean oil was
converted to iso-alkanes in a single-step hydrotreatment process. Over the catalyst with less strong
lewis acidity, 100% conversion of soybean oil, 80% liquid yield, 100% alkanes selectivity and 63%
isomerization selectivity were achieved.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.3-25
Activity and stability Cu-SAPO-34 as NH3-SCR catalyst: parameters governed for the
reactivity
Radka Nedyalkova1, Foad Faghihinia1, Mariana Trifonova2
1 Chalmers University of Technology, Competence Center for Catalysis, Gothenburg, Sweden
radka@chalmers.se ; Alternative e-mail: rnedialkova76@yahoo.com
2Service for Scientific and Technical Resources, Rovira i Virgili University, Tarragona, Spain
Here, we show how the nature and the amount of copper precursor affect the NOx activity in NH3SCR. These parameters are important especially for the small pore zeolite as a consequence of the
small pore opening which limits the exchange level. In addition, it was shown that zirconia
prominently enhances the hydrothermal stability of the aged catalysts.
P-3.3-26
AgAlBEA and AgSiBEA zeolites as promising catalysts for selective reduction of NO with
ethanol and butanol
N. Popovych1, P. Kyriienko1, S. Soloviev1, S. Orlyk1, S. Dzwigaj2
1L.V.Pisarzhevsky Institute of Physical Chemistry of the NASU, Kyiv, Ukraine,
nataliepopovich@mail.ru
2Laboratoire de Réactivité de Surface, UMR 7197 CNRS, UPMC, Paris, France
The crystallinity of BEA zeolite is preserved after dealumination and incorporation of silver ions in
zeolite framework. Dealuminated SiBEA and AgSiBEA zeolites do not show extra-framework
crystalline phase or long-range amorphization, as evidenced by XRD. It is the first time that
incorporation of silver in the framework of BEA zeolite is evidenced by DR UV-vis and FTIR. This
isolated framework Ag+ species are less active in SCR of NO by ethanol and butanol than Agnδ+
clusters formed in AgAlBEA in extra-framework position. The activity of AgAlBEA increases after
its treatment with H2 which involve the reduction of silver species and the formation more amount of
extra framework Agnδ+ clusters.
P-3.3-27
Di-n-butyl ether synthesis using continuous flow reactor
V.O. Samoylov, A.I. Nekhaev, D.N. Ramazanov, A.L. Maximov
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia, max@ips.ac.ru
Di-n-butyl ether (DBE) is one of numerous butanol-1 derivatives which can be synthesized via its
dehydration. DBE has some noticeable properties as possible diesel and biodiesel fuel additive. It
melts at -95°С, improves lubricity when added to diesel, has cetane number about 100.
Acid-catalyzed butanol-1 conversion is one of test reactions used for characterization of catalysts. We
have attempted to move reaction selectivity towards DBE formation and at the same time to test
various heterogeneous catalysts using flow reactor – a laboratory plant.
Catalytic behaviour of zeolites BEA, zeolite Y, zeolite-containing catalyst Zeocar Z-600 is described
and compared with data for γ-Al2O3 and Amberlyst-70. Kinetic curves are built; conversion and
selectivity dependence from temperature, pressure, space velocity and water content is defined.
Chemical composition of reaction products is evaluated by GC/MS. Optimal conditions for obtaining
DBE or mixture of C4-oligomers are found.
3.3. Environmental catalysis and conversion of biomass
278
P-3.3-28
Delaminated zeolites as effective supports for the preparation of bioethanol steam reforming
catalysts with high activity, selectivity and stability
J.F. Da Costa-Serra, S. Sayas, A. Chica*
Instituto de Tecnología Química de Valencia, UPV-CSIC, Avda. de los Naranjos S/N, 46022
Valencia, Spain
* Corresponding author: achica@itq.upv.es
Support plays an important role in the steam reforming of bioethanol (SRB) since it helps in the
dispersion of metal catalyst and enhances its activity via metal-support interactions. The singular
structure of delaminated zeolites, and particularly the very high and well-defined external surface
area, makes these materials attractive to be used as supports for dispersing active metal phases. Here
is presented the catalytic activity of two delaminated zeolites (ITQ-2 and ITQ-18) promoted with Co
in the SRB. The characterization of these materials by DRX, BET area, TPR, SEM and TEM, has
allowed to establish interesting relationship between their catalytic and physico-chemical properties.
The high activity, selectivity, and stability of these materials have been attributed to the absence of
acid sites, high external surface (>600 m2/g), which provide a large surface for coke deposition and
help to slow down the deactivation effects, and to their particular structure formed by array of “cups”,
which would provide an excellent position for the stabilization of the Co metal particles improving
their dispersion and preventing their agglomeration.
P-3.3-29
Enhancement of low temperature NH3-DeNOx performance of Fe-Beta by modification with
manganese
D.S. Krivoruchenko, N.S. Telegina, I.S. Mashkovsky, A.Yu. Stakheev.
N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia, lasso2007@yandex.ru
In this study we made an attempt to increase the catalytic activity of the Fe-Beta catalyst at low
temperatures by promoting with Mn species (0.3 – 16 wt. %). It was found that the catalytic activity
of the Mn-Fe-Beta strongly depends on the concentration of manganese. When the content of
manganese is less than 2 wt. %, Mn cations occupy cation positions of zeolite and partially displace
Fe3+ cations, which lead to a decrease in the activity of the catalyst. The increase in manganese above
2 wt. % improves the catalyst activity. It was revealed that the formation of manganese oxide particles
enhances No to NO2 oxidation and favors fast-SCR pathway over Fe3+ cations. This effect
significantly enhances activity of Mn-Fe-Beta at 150-250 oC.
P-3.3-30
Oil refinery wastewater treatment by catalytic ozonation with mesoporous zeolites (FAU) and
Al-MCM-41
Jullian Vittenet1, 2, Jeremy Rodriguez1, Julie Mendret2, Stephan Brosillon2, Anne Galarneau1
1 Institut Charles Gerhardt Montpellier, Montpellier, France.
2 Institut Europeen des Membranes, Montpellier. France. jullian.vittenet@iemm.univ-montp2.fr
The evolution of environmental regulations for industrial wastewater treatment requires the
development of new technologies for the removal of priority hazardous substances as phenols and
Polycyclic Aromatic Hydrocarbons. In the present study, we show that mesoporous faujasite,
prepared by pseudomorphic transformation of FAU crystals, and Al-MCM-41 are highly suitable
ozonation catalysts to eliminate rapidly pollutants from petrochemical wastewater. Mesoporous
faujasite enhances remarkably the ozonation process by eliminating pollutants under the required
limits within 20 min and most of all enhances by a factor 2 the removal of all organics present in the
solution in comparison to single ozonation.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.3-31
Efficient Sugar to Lactate conversion with Bifunctional Carbon Silica Hybrid Catalysts
M. Dusselier1, F. de Clippel1, L. Giebeler2, P.A. Jacobs1, B.F. Sels1
1Center for Surface Chemistry and Catalysis, KU Leuven, Belgium,
michiel.dusselier@biw.kuleuven.be
2Institute for Complex Materials, Leibniz-Institute for Solid State and Materials Research, Dresden,
Germany
The synthesis of alkyl lactates or lactic acid from sugars is an important biomass route towards
valuable industrial products. Alkyl lactates are e.g. considered green solvents. Lactic acid itself is a
building block for polymers and considered an important platform molecule. The current synthesis of
lactic acid via fermentation has a lot of disadvantages. We here report a green chemocatalytic route
for the synthesis of lactic acid and its esters from common sugars based on a new class of carbonsilica composite catalysts with tunable bimodal porosity. This value-added biomass conversion
requires multiple catalytic functions and ideally demonstrates the versatility and tunability of this new
class of composite materials. Both composing parts bear a different catalytic functionality.
P-3.3-32
Influence of channel topology and zeolite defects on the catalytic etherification of HMF to
biofuel additives
Paola Lanzafame1, Daniel Montalto1, Siglinda Perathoner1, Gabriele Centi1, Anastasia Macario2,
Alfredo Aloise2 and Girolamo Giordano2
1 Dep. of Electronic Engineering, Industrial Chemistry and Engineering, University of Messina and
CASPE-INSTM, Messina, Italy, perathon@unime.it
2 Dep. of Chemical Engineering and Materials, University of Calabria, Cosenza, Rende, Cosenza,
Italy
HMF, obtained in the acid-catalyzed conversion of lignocellulosic biomass, is considered the most
interesting platform molecule to obtain monomers for polymers, valuable intermediates for fine
chemicals and above all biodiesel components [1,2].
In this work the role of structural properties of different zeolite materials (MFI, MOR and BEA) in
the etherification of HMF by ethanol to obtain biofuels and other valuable chemicals such as 5(ethoxymethyl)furan-2-carbaldehyde (EMF), 1,1-dietoxy ethane (DE) and ethyl 4-oxopentanoate
(EOP) was explored. Moreover the influence of zeolitic defective sites on the catalytic behavior of
Silicalite-1 and Boron-Silicalite-1 in the above cited reaction was studied.
The results evidence that the different channel topology of the zolites strongly affects the distribution
of the products and that an interesting biodiesel additive, like EMF, can be obtained selectively using
zeolites with a multidimensional channel system like BEA and MFI. With reference to the role played
by zeolitic defective sites of Silicalite-1 and Boron-Silicalite-1 catalysts the results evidenced that the
presence of defective sites plays an important role on the selectivity to the products.
References
[1] P. Lanzafame, D.M. Temi, S. Perathoner, G. Centi, A. Macario, A. Aloise, G. Giordano, Catalysis
Today, 2011, 175, 435– 441
[2] P. Lanzafame, D.M. Temi, S. Perathoner, A.N. Spadaro, G. Centi, Catalysis Today, 2012, 179
178– 184
3.3. Environmental catalysis and conversion of biomass
280
P-3.3-33
Use of zeolite ZSM5 and hydrotalcite based mixed oxides in the dehydration of glycerol
Sz. Mészáros1, J. Halász1, I. Pálinkó2, Z. Kónya1
1Dep. of Applied and Environmental Chemistry, Univ. of Szeged, Hungary
szilvi.meszaros@gmail.com
2Dep. of Organic Chemistry, Univ. of Szeged, Hungary
Via glycerol dehydration carried out by reactive distillation valuable acetol and acrolein can be
produced. The catalysts were zeolites ZSM5 and mixed oxides (MO) obtained by calcination of
hydrotalcites.
During the reaction the lamellar structure of Mg-Al and Ni-Mg-Al MOs was restored and they were
used in a further reaction having activity and selectivity similar to that over the freshly prepared
sample. Even if the conversion is moderate in the presence of latter catalysts, their ability for
restoration during the reaction and their high acetol selectivity (> 80 %) make them promising. Since
the MOs are environmentally benign and relatively cheap, the CuCr-Mg-Al MO having the highest
activity and acetol selectivity is worth mentioning, even if there are problems with its regeneration.
The zeolite ZSM5 didn’t show considerable activity and selectivity comparing with MOs.
P-3.3-34
Conversion of Methyl Mercaptan and Methanol to Hydrocarbons over Zeolites: a Comparative
Study
V. Hulea1, C. Cammarano1, A. Lacarriere1, B. Coq1, R. Durand1, E. Huguet2, R. Cadours2, C. Leroi3
1Institut Charles Gerhardt Montpellier, UMR 5253 CNRS/ENSCM/UM2/UM1, 8, rue de l'Ecole
Normale, 34296 Montpellier Cedex 5 (France) ; vasile.hulea@enscm.fr
2TOTAL SA, Exploration & Production, 2 Place Jean Miller – La Défense 6, 92078 Paris, La Défense
Cedex (France)
3TOTAL SA, Exploration & Production, 126, Avenue Larribau, 64018 Pau Cedex (France
Methyl mercaptan (MM) is a harmful impurity in natural gas. The commercial desulfurization
processes need additional reactants and some of them produce dialkylsulfides or disulfides. Here we
studied the catalytic conversion of MM into hydrocarbons and H2S, which can be further efficiently
captured by absorption. As a general comment, this process could have some similarities with the
very well known process methanol to hydrocarbons. Consequently, MM and methanol conversion
into hydrocarbons has been carried out under similar conditions on zeolites with MFI, FAU and FER
topology. The similarities and the differences between two processes are analyzed taking into account
the mechanism/reaction pathway involved in each process.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.3-35
Role of isolated mononuclear iron in decomposition of N2O and SCR
of NO with ammonia on FeAlSiBEA and FeSiBEA zeolite catalysts
P. Boroń1, L. Chmielarz1, J. Gurgul2, K. Łątka3, T. Shishido4, S. Dzwigaj5
1Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków, Poland
2Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
Niezapominajek 8, 30-239 Kraków, Poland
3Marian Smoluchowski, Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków,
Poland
4Department of Molecular Engineering, Kyoto University, Kyoto, 615-8510, Japan
5Laboratoire de Reactivite de Surface, UMR 7197, CNRS, UPMC, 3 rue Galilee, 94-200 Ivry-surSeine, France, stanislaw.dzwigaj@upmc.fr
A two-steps postsynthesis method allows incorporating of iron atoms into framework of BEA zeolite
and obtaining FexAlSiBEA and FexSiBEA with mononuclear iron species as evidenced by DR UVVis, XAS, XPS and Mössbauer. These zeolites materials are active catalysts of N2O decomposition
and SCR of NO. They catalytic activity strongly depends on the speciation and amount of iron
introduced into zeolite structure as well as their acidity.
P-3.3-36
Bio-fuels production from biomass: improving ZSM-5 resistance to phenolic compounds
I. Graça, A.M. Carmo, C. Sá Couto, J.M. Lopes, M.F. Ribeiro
IBB, Institute for Biotechnology and Bioengineering, Centre for Biological and Chemical
Engineering, Instituto Superior Técnico, UTL, Av. Rovisco Pais, 1049-001 Lisboa, Portugal,
filipa.ribeiro@ist.utl.pt
To evaluate the possibility of using desilicated ZSM-5 additives to reduce phenolic compounds
additional deactivation, when co-processing phenolic-rich bio-oils with traditional Fluid Catalytic
Cracking (FCC) feedstocks, the transformation of n-heptane was performed in presence of phenol
over desilicated HZSM-5 samples, at 450 ºC. The results obtained were compared with those
previously found for the parent zeolite. Desilicated zeolites, presenting some generated mesoporosity,
show a quite improved resistance to phenol, due to the enhancement of molecules diffusion inside the
ZSM-5 pore network, thus decreasing the phenol pore blocking effect.
3.3. Environmental catalysis and conversion of biomass
282
P-3.3-37
Synthesis, Characterization and Catalytic Activity of Molecular Sieves
Containig Bismuth (SABiOs)
A. J. S. Mascarenhas1,2, F. T. Cruz1, H. M. C. Andrade1,2.
1 Laboratório de Catálise e Materiais, Instituto de Química, Universidade Federal da Bahia (UFBA),
Salvador-BA, Brazil, artur@ufba.br.
2 Instituto Nacional de Ciência e Tecnologia em Energia e Ambiente (INCT-E&A), Brazil.
Molecular sieves containing bismuth (SABiOs) of MFI topology were prepared with different molar
ratios Bi/Al, using Bi(NO3)3.5H2O as precursor. The samples were characterized by XRD, FTIR,
TGA/DTG, EDX, textural analyses, SEM, DRS (UV-Vis), XPS, TPR and TPD-NH3. The presence of
Bi2O3 nanoclusters entrapped in the channels of the structure was confirmed by TPR, DRS (UV-Vis)
and XPS. The materials were catalytically evaluated in the dehydration of glycerol to acrolein in gas
phase. The catalysts were very active in the conversion of glycerol (χ > 60%), but less selective to the
desired product, which is acrolein (S ≈ 30%), than ZSM-5 catalyst. In all cases, a fast deactivation by
coke formation was observed. The maximum selectivity was observed for the sample with ratio Bi/Al
= 0.50.
P-3.3-38
Niobium-containing mesoporous molecular sieves as catalysts for catalytic oxidations
A. Feliczak-Guzik, A. Wawrzynczak, J. Goscianska, I. Nowak
Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614 Poznań, Poland,
asiagosc@amu.edu.pl
Using of environmentally friendly oxidants, namely aqueous hydrogen peroxide, in the presence of
heterogeneous catalysts, that may be easily recyclable, is a challenging purpose for the fine chemistry.
During our studies 2D/3D mesoporous materials were synthesized under various conditions, applying
different niobium sources, synthesis temperatures and amounts of surfactants. The influence of
parameters like: cavitation, pore size, pore blockage and acidity on the catalytic activity in the
oxidation of cyclohexene, methylphenyl sulfide and limonene/geraniol with H2O2 was checked.
P-3.3-39
Direct conversion of fatty acid triglycerides on zeolite catalysts
A.G. Dedov1, A.S. Loktev1, E. A. Isaeva1, S.D. Golikov1, E.V. Rogaleva1, A.E. Gekhman2, I.I.
Moiseev1
1Gubkin Russian State Oil and Gas University, Moscow, Russia, genchem@gubkin.ru
2N. S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia
Promotion of the high - silica zeolite with zinc and chromium ions affords efficient catalysts for the
synthesis of aromatic hydrocarbons and light olefins from fatty acid triglycerides of vegetal origin.
Aromatic hydrocarbons are valuable petrochemical products and are usable as an octane booster
additive for motor fuels. Light olefins are a valuable petrochemical semiproduct as well.
17 IZC, 2013. POSTER COMMUNICATIONS
283
P-3.3-40
TCE oxidation over metal exchanged zeolite BETA
N.Blanch-Raga1, A.E. Palomares1, J. Martínez-Triguero1, G. Fetter2, P. Bosch3.
1 Instituto de Tecnología Química, UPV-CSIC, Valencia, 46022, Spain, jomarti@itq.upv.es
2 Facultad de Ciencias Químicas, UAP, Puebla, PUE, 72570, México.
3 Instituto de Investigaciones en Materiales, UNAM, México D.F., 04510, México.
Zeolite Beta and hydrotalcites containing Cu or Co were tested in the oxidation of trichloroethylene
(TCE). Zeolite Beta was metal exchanged and hydrotalcites were prepared by the conventional
method of co-precipitation at constant pH. XRD of zeolites showed peaks associated to Cu or Co
oxides dispersed on the catalyst surface. No changes were observed after reaction. XRD of calcined
HT-CuAl presented signals associated to CuO species while HT-CoAl presented signals associated to
spinels Co3O4 and CoAl2O4, which have been described as active species. Cu and Co-zeolite showed
more activity in the oxidation of trichloroethylene than hydrotalcites, due to a better dispersion of
metals on the zeolite surface.
P-3.3-41
Discrimination of Fast SCR and Standard SCR pathways in NH3-DeNOx over Fe Beta zeolites
A.I. Mytareva, G.N. Baeva, G.O. Bragina, D.A. Bokarev, A.Yu. Stakheev
N.D. Zelinsky Institute of Organic Chemistry, Moscow, Russia, AIMytareva@gmail.com
In this study we attempted to differentiate Fast SCR and Standard SCR pathways using different
techniques and to compare efficiency of Fe Beta catalysts with different Fe content in Fast SCR
reaction. The use of non-stoichiometric NO2/NO (1:3) mixture and “NO2 slip” measurements allowed
us to discriminate activities Fe Beta zeolites with low iron loading in Fast SCR. It was found, that
0.02 % Fe/Beta is significantly more active than 0.002 % Fe/Beta, which indicates positive role of
Fe3+ species in Fast-SCR.
P-3.3-42
Influence of iron content on the activity of Fe/SBA-15 catalysts for methylene blue removal
from aqueous effluent
M. C. Rangel1,2, O. B. da Silva1,2, S. T. F. Grecco2, H.C. F.Santos2, S. Borges2 and S.G. Marchetti3
1Grupo de Estudos em Cinética e Catálise, Instituto de Química, Universidade Federal da Bahia, 40
170-280, Salvador, Bahia, Brazil, mcarmov@ufba.br
2Mestrado em Engenharia Química, Universidade Federal da Bahia, 40 210-630 , Salvador, Bahia,
Brazil
3CINDECA, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 1900, 47 y 115, La
Plata, Argentina
The influence of iron amount (10, 20 and 30%) on the catalytic properties of Fe/SBA-15 catalysts for
methylene blue removal from aqueous effluent was studied in this work. Iron causes a decrease of
specific surface area and pore volume of SBA-15 related to a disordering and/or to a partial blockage
of pores by iron oxide particles. The poorest-iron sample was the most active catalyst, a fact that was
related to the smallest particles size, able to perform the redox cycle during reaction.
3.3. Environmental catalysis and conversion of biomass
284
P-3.3-43
FTIR Spectroscopic Study of NO + O2 Coadsorption on H-SSZ-13:
Formation and Stability of NO+
J.A. Loiland, R.F. Lobo
Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716
(USA), jloiland@udel.edu
Coadsorption of NO and O2 flowing gases on H-SSZ-13 (Si/Al = 12) has been investigated using
DRIFT spectroscopy to observe the formation of nitrosonium cations (NO+) by the heterolytic
dissociation of N2O4 (N2O4 → NO+ + NO3-). We confirmed NO+ formation at Brønsted acid sites
within the zeolite micropores by the observance of a peak at 2170 cm-1 in the IR spectra (NO+) and
concomitant ‘negative’ bands at 3660 and 3610 cm-1 (acid sites). Control studies using siliceous SSZ13 (no acid sites) and Na-SSZ-13 showed no formation of NO+, indicating further support that the
Brønsted sites are necessary for the N2O4 disproportionation reaction. NO+ was found to be thermally
stable on H-SSZ-13 from 25⁰C to 300⁰C in the presence of NO. Flowing He caused the IR band at
2170 cm-1 to broaden and decrease significantly in intensity.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.4-01
Oxidation of Phenol to Dihydroxybenzenes by N2O over MFI zeolites
L.V. Pirutko, D.P. Ivanov and G.I. Panov
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia, pirutko@catalysis.ru
Gas phase oxidation of phenol by N2O for preparation of dihydroxybenzenes (DHBs), i.e.
hydroquinone (HQ), resorcinol (RS), and catechol (CH) is of significant interest. Present-day
processes of their production are imperfect and environmentally unfriendly. MFI zeolites were shown
to be efficient catalysts for the title reaction, which supplied productivity on DHBs on the level of 23 mmol/g⋅h in studied conditions. An unusual isomeric distribution of DHB depending on reaction
conditions, catalysts acidity and coke loading was found. The ratio of HQ/CH depends on the BAS
(Bronsted acid sites) concentration and may be regulated by known methods of changes in catalyst
acidity. Formation of RS is a feature of the reaction, although the fraction of RS is not high. A
comparison with the current liquid-phase processes of phenol oxidation by H2O2 shows that the
oxidation by N2O may open a new promising way for alternative production of DHBs in the gas
phase.
P-3.4-02
Disproportionation of Trimethylbenzene over Modified Beta Zeolite
Y.W. Chen, S.J. Zhu
Dep. of Chem. Eng., National Central University, Jhongli, Taiwan, ywchen@ncu.edu.tw
A series of beta zeolites with various Si/Al ratios and modified with Zr(OC4H9)4 or Si(OC2H5)4 has
been synthesized. The conversion of 1,3,5- and 1,2,4-trimethylbenzene (TrMB) was conducted in a
fixed bed reactor. The conversion of TrMB decreased with increasing Si/Al ratio of the zeolites. The
zeolites with low Si/Al ratio favored the disproportionation, those with high Si/Al ratios favored the
isomerization. In the disproportionation, the selectivity of tetra-methylbenzene (TeMB) decreased in
the order of 1,2,3,5- > 1,2,4,5- > 1,2,3,4-TeMB. The zeolites modified with Si(OC2H5)4 by CVD
method blocked all the acid sites on the external surface and shrink the pore mouth, resulting in better
shape selectivity. The disproportionation activity of 1,2,4-TrMB on modified zeolite beta was much
greater than that of 1,3,5-TrMB.
P-3.4-03
A comparative study of glycerol dehydration catalyzed by desilicated
micro/mesoporous MFI zeolites
L. G. Possato1, R. N. Diniz1, T. Garetto2, S. H. Pulcinelli1, C. V. Santilli1, L. Martins1
1. Instituto de Química, UNESP - Prof. Francisco Degni 55, 14800-900 Araraquara-SP, Brazil
2. INCAPE - Santiago del Estero 2654, Santa Fe, Argentina
Various catalysts have been studied in the heterogeneous catalysis for dehydration of glycerol
including zeolites. The main similarities between the catalysts are the presence of acid sites
responsible for the dehydration of glycerol. The application of zeolites as highly active, selective and
stable catalysts in large-scale technologies is widespread. However, the catalytic conversion of
glycerol is hindered in microporous systems restricted by the transport of molecules in the channels of
the zeolitic structure and also obstruction of the pores by the deposition of coke during the reaction.
The methodology for minimizing diffusion limitations and increasing efficiency involves the
production of hierarchically structured zeolites, characterized by the formation of secondary pores in
the mesopore region in the zeolite crystals. In this study we compare and discuss the catalytic
dehydration of glycerol to acrolein using microporous MFI zeolites and desilicated ones. The effect of
desilication in the conversion of glycerol, the distribution of the products and also the control of
diffusion constraints and deactivation by different location of coke formation in the pores is shown.
3.4. Chemicals and fine chemicals
286
P-3.4-04
Titanium containing Solid core Mesoporous silica shell : A novel efficient catalyst for
ammoxidation reactions
N. Venkatathri*, M. Nookaraju, A. Rajini and I.A.K. Reddy
Department of Chemistry, National Institute of Technology Warangal,
Warangal-506004, Andhra Pradesh, India, venkatathrin@yahoo.com
A novel titanium containing solid core mesoporous silica shell has been synthesized from
octadecyltrichloro silane and triethylamine for the first time. Small angle powder X-ray diffraction
analysis shows the synthesiszed material is probably mesoporous. Energy dispersive X-ray analysis
shows that the sample contains Octadecyltrichloro silane and Triethylamine on surface. It is having
spherical morphology with 300 nm particle size and 50 nm shell size. TG/DTA analysis shows that
the sample lost almost half of its weight on calcinations. Nitrogen adsorption analysis shows it is
having BET surface area of 550 m2/g. The 960 cm-1 peak at Fourier transform Infrared spectrum
shows that titanium is incorporated inside the tetrahedral silica framework. UV-Visible spectrum
shows a peak at 300 nm for titanium in tetrahedral co-ordination. X-ray photoelectron spectrum
shows a peak for titanium in tetrahedral co-ordination. 29Si MASNMR spectrrum for as-synthesized
sample shows the presence of Si: Ti: 3Si, Si: 2Ti: Si and Si: 3Cl: C species. It is found to be an
effecient catalyst for synthesis of caprolactam from cyclic ketones via ammoxidation reactions.
P-3.4-05
Engineering Single-Site Lewis Base Catalysis in Mesoporous Silica for Desirable Industrial
Transformations
S. H. Newland1, D. J. Xuereb1, R. Rios Torres1, R. Raja1
1School of Chemistry, University of Southampton, Southampton, UK, shn1g08@soton.ac.uk
Enantioselective formation of C-C bonds is vital in the synthesis of fine chemicals for the
pharmaceutical industries. Typically these reactions are effected via the use of basic homogeneous
organocatalysts. In such systems, the homogeneous nature of the catalyst encourages aggregation of
active centers, which impedes recyclability preventing industrial implementation of the catalysts. The
immobilization of organocatalysts onto porous supports is a promising, yet unexploited, resource that
can afford superior enantioselective catalysts.
We have created an array of Lewis base functionalized mesoporous nanostructures and have
highlighted their catalytic potential to effect industrially significant asymmetric C-C bond formations.
P-3.4-06
Efficient one-pot synthesis of 2, 5-disubstituted 1,3,4-oxadiazoles catalyzed by nano-ZSM-5
catalyst
Abbas Teimouri1,* , Alireza Najafi Chermahini2
1 Chemistry Department, Payame Noor University, 19395-4697, Tehran, I. R. of Iran,
a_teimouri@pnu.ac.ir
2 Department of Chemistry, Isfahan University of Technology, Isfahan, 841543111, Iran
1,3,4-Oxadiazoles are a class of heterocycles, which have attracted significant interest in medicinal
chemistry, pesticide chemistry and material science. Among the 1,3,4-oxadiazoles, 2,5-unsymmetrical
disubstituted derivatives have attracted considerable attention because of their pharmaceutical and
biological activity.
In the recent years, the use of nano-ZSM-5 zeolite, catalysts has received considerable interest in
organic synthesis.
Here in we report an efficient process for synthesis of 2,5-disubstituted 1,3,4-oxadiazoles, in the
reaction of different aromatic aldehyde with acyl hydrazide using nano-ZSM-5 zeolites, as the
catalyst.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.4-07
Shape-Selective Catalysis Determined by the Volume of a Zeolite Cavity: Selective production
of Propylene
Toshihide Baba, Yasuyoshi Iwase, Akimitsu Miyaji, Ken Motokura and To-ru Koyama
Tokyo Institute of Technology, Department of Environmental Chemistry and Engineering, 4259
Nagatsuta, Midori-ku, Yokohama, Japan. tbaba@chemenv.titech.ac.jp
The catalytic performance of various zeolites is examined to investigate the role of pore volume in the
selective conversion of olefins (C2H4, C4H8, C5H10) into C3H6, using zeolites with 8-, 10-, and 12MRs with various cavity volumes. Highly selective production of C3H6 from olefins can be
accomplished by employing a new concept: adjusting the pore volume of a zeolite to accommodate
the volume of the specific carbenium cations, as opposed to a conventional molecular sieve approach.
P-3.4-08
Metallocene immobilized on zeolite support as catalysts for olefin polymerization
I.N. Meshkova1, V.G.Grinev1, S.A.Skornikova2, N.Yu. Kovaleva1, O.I. Kudinova1,
L.A. Novokshonova1
1 Semenov Institute of Chemical Physics RAS, Moscow, Russia, meshko va.in@yandex.ru
2 Irkutsk State Technical University, Irkutsk , Russia
The synthetic zeolites are interesting as supports for heterogenization of the olefin polymerization
catalysts. The metalcomplex catalysts of olefin (ethylene and propylene) polymerization immobilized
on zeolite have been developed. For preparing of these catalysts anchored aluminoxanes have been
synthesized by the reaction of aluminium alkyls (AlMe3, AlEt3 and AliBu3) with water contained on
surface and in intracrystalline cavities and pores of zeolites (NaY, NaZSM-5, HZSM-5, NH4ZSM-5,
ZSM-12, Beta, mordenite). These aluminoxanes with zirconocenes, vanadium chlorides form the
heterogenized metalorganic complexes which are active in the polymerization of ethylene and
propylene. The nature of zeolites (the content and mobility of zeolite water) affects the formation
process of anchored aluminoxanes and activity of immobilized catalysts. Polyolefin obtained in the
presence of the immobilized on zeolites zirconocene catalysts demonstrate higher molecular mass and
a wider molecular-mass distribution than those received with the analogous homogeneous catalysts.
The stereoselectivity of supported catalysts depends on the composition, structure of metallocene and
zeolite nature.
P-3.4-09
Selectivity comparison of 2,6-dimethylnaphthalene by methylation of naphthalene with
methanol on different zeolites
Ye Zhang, Mingxian Du, Zhanjun Lv, Xuekuan Li
Institute of Chemistry, Chinese academy of Sciences, Taiyuan, P.R.China, 030001
yzhang@sxicc.ac.cn
2,6-Dimethylnaphthalene (2,6-DMN) is an important precursor of 2,6-naphthalene dicarboxylic acid,
which is used as a monomer of polyethylene naphthalates (PEN). While, the cost of 2,6-DMN and its
limited availability on the market restrict the wider use of PEN. The B.P-Amoco process has the
disadvantages of being environmentally unfriendly, a difficult process to execute and expensive. A
desirable pathway to prepare 2,6-DMN is the methylation of naphthalene with methanol. In the
present work, selective synthesis of 2,6-DMN from naphthalene and methanol was carried out over
different zeolites under atmospheric pressure. Better selectivity to 2,6-DMN, higher 2,6-DMN/2,7DMN ratio and longer catalyst life were obtained over SAPO-11 compared with HZSM-5,Hβ and
HUSY. SAPO-11 was proved to have the more suitable pore structure and acidity for naphthalene
methylation to 2,6-DMN. The high selectivity and stability of SAPO-11 made it a promissing and
attractive catalyst for 2,6-DMN production by methylation of naphthalene with methanol.
3.4. Chemicals and fine chemicals
288
P-3.4-10
Microwave-assisted Sonogashira Cross-Coupling Reaction Catalyzed by Pd-MCM-41 under
Solvent-free Conditions
W. Chang1, *, J. Shin1, G.H.Chae2, S. R. Jang2, B. J. Ahn2,*
1 Department of Advanced Materials & Nano Science and EM R&D Center, Jeonju University,
Jeonju 560-759, Korea
2 Department of Chemistry Education, Institute of Fusion Science, Chonbuk National University,
Jeonju 561-756, Korea, ahnbj@jbnu.ac.kr
In this paper microwave-assisted Sonogashira reactions of phenyl acetylene with aryl iodide using
palladium modified Pd-MCM-41, Pd-Y, Pd-VSB-5 and Pd-SBA-15 under solvent-free or aqueous
conditions were described. The reaction's optimal duration (40 min) was found by measuring the
progression of yield at 120 ℃ with 300 W microwave power. The microwave-assisted reaction of
phenyl acetylene with phenyl iodide using Pd-Y or Pd-MCM-41 as catalysts and DBU as a base under
solvent-free conditions gives 85 % with Pd-Y and 93% with Pd-MCM- 41. DBU was shown to be a
suitable base for microwave-assisted reaction of phenyl acetylene with phenyl iodide using Pd-Y or
Pd-MCM-41.
P-3.4-11
Vanadium modified mesoporous and amorphous solid matrices applied for propene epoxidation
A. Held, J. Kowalska-Kuś, K. Nowińska, S. Kowalak
Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland, awaclaw@amu.edu.pl
Vanadium oxide systems supported on silica and alumina-silica mesoporous materials as well as
amorphous Al2O3, MgO and TiO2 were used for propylene epoxidation reaction with nitrous oxide as
an oxidant. Catalytic activity of vanadium bearing samples was strongly affected by the nature of the
used matrices. The best catalytic results were observed over vanadium species supported on
mesoporous silica carrier. Titania and alumina supported vanadium species showed relatively high
propene conversion, however, they mainly catalyzed the total oxidation reaction. Spectroscopic study
indicate the role of N2O adsorption in propene epoxidation. FTIR spectra confirmed that N2O adsorption
on V/SBA-3 occurs through nitrogen atom with the formation of weakly electrophilic oxygen.
P-3.4-12
Skillful design of new direct oxidation catalyst: Dual functional titanosilicate
Chunfeng Shi, Jun Long, Min Lin, and Bin Zhu
Research Institute of Petroleum Processing, Beijing, P. R. China, chfshi@yahoo.com.cn
Direct oxidation technology, involving in situ H2O2 production with simultaneous conversion to
organic oxides in the same reactor without refining, are being regarded as more promising technology
to the production of organic oxides, for its good potentials for ulterior savings in capital and
production costs. The catalysts used are dual functional and mostly consist of noble-metal and
titanosilicate. One of our aims is to design and preparation of this dual functional catalyst with intraparticle voids. In this presentation, firstly, our own work on dual functional catalysts especially for
their skillful design and characterization will be summarized. Furthermore, our recent advance in
developing titanosilicate with intra-particle voids will be also introduced concisely.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.4-13
Mesoporous hollow silica supported Pt based bimetal catalysts: effect of promoter and thermal
treatment
Xu Yang, Shijun Liao
Key Laboratory for Fuel Cell Technology of Guangdong Province, School of Chemistry and
Chemical Engineering, South China University of Technology, Guangzhou, China,
chsjliao@scut.edu.cn
Catalytic hydrogenation of phenol is of commercial significance because cyclohexanone is an
important intermediate. Therefore, developing high performance catalysts for this process has been an
attracted topic. In this work, we prepared a series of Pt based catalysts with mesoporous hollow
sphere silica (MHSS) as support, and with Pd, Au, Ru and Ir as promoters. It is found that all these
MHSS supported Pt-M catalyst showed superior activity over the commercial supported Pd catalyst.
The addition of promoter can influence the catalysis behavior of Pt based catalysts toward
hydrogenation of phenol, the addition of Pd could slight decrease the activity of the catalyst.
However, the addition of any one of other three metal, Au, Ru and Ir, could enhance the activity
significantly, with sequence of Au P-3.4-14
EISA prepared mesostructured titanium-silicate as highly efficient catalyst for selective
oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone
M. S. Mel’gunov, I. D. Ivanchikova, M. K. Kovalev, O. A. Kholdeeva
Boreskov Institute of Catalysis, Novosibirsk, e-mail: max@catalysis.ru
The development of a simple, user-friendly procedure for the synthesis of mesoporous titaniumsilicate catalyst that would combine high selectivity with stable recycling behavior in organic
substrates oxidation with aqueous H2O2 still remains an open task. The possible way to achieve this
goal is to apply special synthetic conditions that would allow combination of intimately mixing of
catalyst compounds and relaxation of Si-O-Si and Si-O-Ti bonds. One of the procedures that allow
fulfillment of such conditions is evaporation-induced self-assembly (EISA). The contribution shows
that Ti-silicates obtained by EISA procedure are highly efficient in partial oxidation with environment
friendly 30% aqueous H2O2, true heterogeneous and recyclable catalysts for the synthesis of
quinones.
3.4. Chemicals and fine chemicals
290
P-3.4-15
Isomerization of α-pinene oxide to campholenic aldehyde over Fe-modified micro- and
mesoporous materials
M. Stekrova1,2,3, N. Kumar1, P. Mäki-Arvela1, D. Yu. Murzin1
1Laboratory of Industrial Chemistry and Reaction Engineering, Åbo Akademi University, FI-20500
Turku, Finland, dmurzin@abo.fi
2Institute of Chemical Technology Prague, Department of Organic Technology, Prague 6, Czech
Republic
3VÚAnCH Litvínov, a. s., Ústí nad Labem, Czech Republic
Alpha-pinene oxide is a very reactive substrate which isomerizes rapidly in the presence of acid,
forming thereby many products. The industrially most desired compound is campholenic aldehyde
because it is an useful intermediate in the manufacture of sandalwood-like fragrance chemicals.
Wide range of zeolites with varying structures such as Mordenite, Ferrierite, Y, ZSM-5, ZSM-12,
Beta-75 and Beta-300 were modified by iron, characterized and tested for campholenic aldehyde
preparation. As a comparison Fe-H-MCM-41 was synthesized and tested for isomerization of αpinene oxide. Two methods of catalyst synthesis were used in this research, namely conventional
liquid phase ion-exchange method and solid state ion exchange method.
Formation of campholenic aldehyde was observed to be influenced by the structure, the amount and
strength of Brønsted and Lewis acid sites of supports andcatalyst preparation method. Minor
encountered products are fencholenic aldehyde, trans- and cis-carveol, p-cymene, transpinocamphone and pinocarveol.
The highest selectivity to campholenic aldehyde was achieved using Fe-Y-12 SSIE, Fe-Beta-75 IE
and Fe-H-MCM-41 SSIE. The total conversion of α-pinene oxide was achieved within 15 minutes
using these catalysts at 70 ˚C. The highest selectivity to the desired product was obtained over large
pore zeolite, Fe-Y-12 SSIE, exhibiting the highest Brønsted acidity and the moderate Lewis acidity.
Activity and selectivity of the prepared catalysts were correlated with their physico-chemical
properties.
P-3.4-16
Novel Aibassov-Yuriev reaction of furan in its analogs - phosphorane, arsanol, stibinol, and
vismutol
Aibassov Erkin Zhakenovich, Baiguzhin Adil Alibekovich, Umirkulova Zhanar Sempekovna,
Serikbaeva Gulbarshyn Kuanyshkanovna
LTD "Chemical Solution", Almaty, Kazakhstan, Zhamakaeva Str., 126, Tel. (7272)718044,
e-mail: erkin53@mail.ru
We first discovered a new reaction conversion of five-membered (furan) and six-membered (pyran)
heterocycles in its analogs - pentamerous (phosphorane, arsanol, stibinol and vismutol) or sixmembered (pyran, pyridine, etc.) heterocycles, where X = AsH, SbH, BiH, PH, NH, S, Se in the
interaction of phosphine, arsine, and stibine bismuthine with five- and six-membered heterocycles of
alumina containing acid sites, at 400-450 ° C.
Thus, we first observed that the AsH3, SbH3, BiH3 by passing the mixture through a modified furan
halides zeolite - clinoptilolite - gives arsol, stibol and vismutol.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.4-17
Alkylation of naphthalene with methanol in synthesis of 2,6-dimethylnaphthalene on CoAPO-11
molecular sieve
Min Liu1 , Wei Wu1*, Linfei Xiao1,Aijuan Zhao1,and Xiaoran Liu1
1Key Laboratory of Environmentally-friendly Chemical Technology, College of Heilongjiang
Province; Sino-Russian Joint Laboratory of Catalysis, School of Chemistry and Material Sciences,
Heilongjiang University, Harbin 150080, Heilongjiang, China, wuwei@hlju.edu.cn;
In our work, CoAPO-11 molecular sieves CoA11-N and CoA11-A were synthesized using Co(NO3)2
or CoAc as cobalt sources, respectively. UV-Vis results confirmed the incorporation of Co(Ⅱ) into the
CoAPO framework. SEM image exhibited that the size of CoA11-A in diameter seemed smaller.
CoAPO-11 molecular sieves synthesized using different cobalt sources exhibited high activity in
shape-selective alkylation of naphthalene with methanol and selectivity to 2,6-Dimethylnaphthalene
(2,6-DMN). Obviously, higher naphthalene conversion of 58.8% and slightly lower selectivity to 2,6DMN were achieved over CoA11-N which may be due to more acidic sites and the higher ratio of
B/L.
P-3.4-18
The synthesis of esters on micro- and micro-mesoporous metallsilicates
N.G. Grigorieva, A.M. Suleimanova, S.V. Bubennov, V.A. Veklov, B.I. Kutepov
Institute of Petrochemistry and Catalysis of RAS, Ufa, Russiaб, ink@anrb.ru, ngg-ink@mail.ru
It was investigated the activity and selectivity of zeolites HY, NMOR, HBeta, HZSM-12 and
mesoporous aluminum silicate (MAS) and the aluminumzirconium silicate (MAZS) in esterification
reactions of mono-(C2-C10) and dicarboxylic (C2-C10) acids with alcohols and unsaturated
compounds.
It was shown that the most active catalyst of the reaction of carboxylic acids with alcohols is zeolite
HBeta. The selectivity the formation of esters depends on the reaction conditions. Monocarboxylic
acids esterification by vinylarenes and norbornene proceeds with whole conversion of unsaturated
compounds in the presence of zeolite HBeta and mesoporous catalysts. Esters of vinylarenes are most
selectively formed products over MAS catalyst and norbornene esters – over MAZS catalyst.
P-3.4-19
The liquid phase oxidation of styrene with silver supported mesoporous carbons as a catalysts
Joanna Goscianska, Robert Pietrzak, Izabela Nowak
Faculty of Chemistry, Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614 Poznań,
Poland, asiagosc@amu.edu.pl
Mesoporous carbons are important in many areas of modern science and technology, including water
purification and catalysis. Because of well-developed surface area, ordered structure and specific
chemical properties, these materials offer almost unlimited possibilities of surface modifications. The
subject of the research work reported was to synthesize the series of mesoporous carbons (from
various silica templates, e.g. SBA-15, KIT-6) as supports for silver nanoparticles and to establish their
catalytic activity in oxidation of styrene under microwave irradiation. Our results have shown that
modification of mesoporous carbons with silver causes decrease of their surface area and pore
volume. Moreover, Ag loaded samples indicate domination of redox character thanks to that they
appeared to be attractive for the oxidation of styrene. In general, the activity of the samples increased
as expected with an increase in the Ag loading, at the expense of the selectivity to styrene oxide with
increasing selectivities to other products (mainly acetophenone) observed at higher Ag loadings.
3.4. Chemicals and fine chemicals
292
P-3.4-20
Benzylation of benzene with benzyl chloride on iron-containing mesoporous mordenite
Y. Sun*, K. Leng
School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin, China,
yysun@hit.edu.cn
Iron-containing mesoporous mordenite (Fe-M-Mor) was prepared by ion-exchanged method. The
obtained material showed excellent catalytic performance in the benzylation of benzene with benzyl
chloride. The apparent reaction rate constant for Fe-M-Mor is about ten times as that for ironcontaining microporous mordenite (Fe-Mor). Such big difference in catalytic activity should be
mainly attributed to the existence of mesopores and more active iron sites in Fe-M-Mor. The study
on heterogeneous nature demonstrated that Fe-M-Mor is a heterogeneous catalyst and could be
reused. Additionally, the catalyst has found potential application in other Friedel-Crafts alkylations,
especially towards large molecular reactions.
P-3.4-21
Acid modification of natural mesoporous aluminosilicate catalyst
A.Yu. Sidorenko, G.M. Sen’kov, V.E. Agabekov
Institute of chemistry of new material, camphene@gmail.com
Clays (natural mesoporous aluminosilicates) are perspective hydrocarbon transformation catalysts.
The aim of this work is to establish the effect of conditions of natural aluminosilicate modifying on its
catalytic and physicochemical properties. Clay was treated by 10% (25-250 ml/g) and 1-20% (50
ml/g) HCl for 3 h at 50 0С, washed, dried (105 0С) and calcined (125 0С). α-Pinene isomerization was
carried out at 130 0С and catalyst concentration is 0,5 wt.%. The catalyst consisted of clay minerals
(illite, kaolinite) and admixtures (feldspar, quartz, calcite and dolomite). Clay modification by 25-100
ml/g 10% HCl leads to the exchange of part of replacing cation to H+, catalyst acidity increases as a
result and the transfer of part of cations, excluding aluminum to the solution occurs. Also the
admixtures – calcite and dolomite are eliminated from Al-Si RB’s composition. Catalysts treatment
by 175 and 250 ml/g of modifier besides cation exchange causes partial removal of aluminum iron
and magnesium ions what leads to the decrease of acidity and specific surface of the catalyst.
α-Pinene conversion over initial clay for 6 h of reaction was 2,7 %, and after modified of its by 50
and 250 ml/g of 10% HCl increased to 89,4 and 62,3 % respectively (Fig. 1). After the treatment of
aluminosilicate by 50 ml/g of 10% HCl the selectivity to camphene increased from 55 to 60% and to
dipentene decreased from 29 to 24%. Conversion of α-pinene at modifier concentration of 1,0 and
20,0% is 18,0 and 26,5 % respectively. It is shown, that catalyst, modified by 50 ml/g of 10% HCl
possesses greatest catalytic activity and selectivity to camphene.
P-3.4-22
The basicity of Y zeolite containing alkylammonium cations
K.A. Almeida, D. Cardoso
Catalysis Laboratory, Chemical Engineering Department, Federal University of São Carlos, 13565905-São Carlos, Brazil www.labcat.org, dilson@ufscar.br
This paper compares the catalytic activity per site of Y zeolite contain carbocations branched and
linear with even number of carbons in the Knoevenagel condensation. For steric reasons, cation
exchange was restricted to the faujasite supercavity and the degree of ion exchange decreased with
the radius of the organic cation. The basicity of the catalysts was analyzed using X-ray photoelectron
spectroscopy (XPS) and the Knoevenagel condensation reaction, with good correlation obtained
between the results of the two methods. The best catalytic activity was observed for the Y zeolite
exchanged using the buthylammonium cation. The better performance of this catalyst was attributed
to increased accessibility of the reactants to the catalytic sites.
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P-3.4-23
Structure and selective reduction of benzonitrile to benzylamine with zeolite catalysts
Ateeq Rahman*, and Anitha S. Deshpande and Faris Al Naomy
Ibra College of technology, Ministry of Manpower Ibra, Sultanate of Oman
Email Id: ateeqr786@yahoo.com
The abstract deals with brief account on recent developments structure and applications of Nanoporous zeolites. And nano-porous materials are characterized by their relatively high surface areas
and pore volumes within a small amount of material. These properties, together with the fact that they
have (uniform) channels and voids in the nanometer range, make them ideal candidates for
implementation in several applications [1-5]. Reduction of benzonitrile to benzylamine is one the
important transforamtions in organic synthesis and have industrial significance. Since there is quite
often formation of secondary amine, tertiary amine with LiAlH4, DIBAL, Pd to name few catalysts
[1,6,7]. Inorder to synthesize selectively benzyl amine from benzonitrile we have developed PdMCM-41 catalsyts. The Pd MCM-41 catalysts is prepared by sol-gel method by adding surfactant and
then adding TEOS in propanol and water and used for reduction of benzonitrile to benzyl amine.
Various ratios of Pd, Rh, Ru catalysts have been used for nitrile reduction the most suitable evolved
was palladium 0.25mmole which resulted in maximum conversion >100% selectivity. The products
were characterized by by H & 13C NMR and compared with standard compounds. Various ratios of
Pd were studied and Rh-MCM-41 catalysts gave interesting results. But Pd-MCM-41 catalysts have
evolved to be the best comparing with Rh-MCM-41 catalysts. The catalysts is recycled for 6 times,
reusability is retained. When 0.50 mmole, 1mmole the conversion of benzonitrile to benzylamine
resulted in less conversion 80% and 75% compared to 0.25 which gave 90% conversion this is
attributed to the uneven distirbution of palladium in MCM-41 matrix. Hence we conclude that 0.25
mmole of Pd his highly suitable for selective reduction of benzonitrile to benzylamine. Similar results
were obtained with Rh MCM-41. The products were characterized by H & 13C NMR and compared
with standard compounds.
1. C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359_1992.710.
2. .L. Kantam, T. Bandyopadhyay, A. Rahman, N.M. Reddy, B.M. Choudary, J. Mol. Catal. A
133 (1998) 293.
3. A. Rahman, S.B. Jonnalagadda, Catal. Lett. 123 (2008) 264.
4. Ateeq Rahman, et. al; Cat. Commun (2008) 9, 2417-2421.
5. Ateeq Rahman and S B Jonnalagadda J Mol. Cat A: (2009) 299, 98-101.
6. Periasamy, M.; Thirumalaikumar, M. J. Organometallic Chem. 2000, 609, 137.
7. Khurana, J. M.; Kukreja, G. Synth. Commun. 2002, 32, 1265.
P-3.4-24
HZSM-5 zeolite in partial oxidation of aromatic compounds by nitrous oxide
in supercritical conditions
A.L. Kustov1, A.E. Koklin1, V.I. Bogdan1,2, L.M. Kustov1,2
1 N.D. Zelinsky Institute of Organic Chemistry RAS, kyst@list.ru
2 Chemistry Department of M.V. Lomonosov Moscow State University
For the first time the reaction of catalytic partial oxidation of aromatic compounds was studied under
supercritical conditions on a catalyst based on HZSM-5 zeolite. Oxidation of benzene, toluene and
some other benzene derivatives was performed. Both the organic substrate and the oxidant (N2O)
were in the supercritical state. The reactions were studied in a wide range of temperatures and
pressures. Under supercritical conditions, the catalysts preserve their activity compared with the gas
phase process. In reactions with substituted aromatic compounds, it was shown that the presence of
substituents in contrast to benzene leads to undesirable disproportionation reaction.
3.4. Chemicals and fine chemicals
294
P-3.4-25
Effect of the Support on the Hydrogenation of 3-Hexyne to Cis-3-Hexene Over
Palladium Catalysts
G. Alvez-Manolia, T.J. Pinnavaiab, Z. Zhangb, D.K. Leeb, K. Marín-Astorgac, P. Rodriguezc, F.
Imbertc, P. Reyesd, N. Marín-Astorgaa
a Center for Applied Catalysis, Seton Hall University, South Orange, NJ 07079, USA
b Department of Chemistry, Michigan State University, East Lansing, MI 48824-1322, USA
c Departamento de Química, Universidad de Los Andes, Mérida, Estado Mérida, Venezuela.
karinamarinastorga@hotmail.com
d Departamento de Fisicoquímica, Universidad de Concepción, Concepción, Chile
This paper studies the effect of mesostructured materials in the stereo-selective hydrogenation of 3hexyne at 298K and 40 psig of pressure over Pd-supported catalysts at different substrate:palladium
(S:Pd) molar ratios. The catalysts were prepared by impregnation to obtain a metal content close to
1% wt. over SBA-15, MCM-48 and MSU-ɤ alumina . All the supports were characterized by nitrogen
adsorption–desorption isotherms at 77 K, TEM, XRD and H2 chemisorption and TEM measurements.
The reactions were found to be zero order with respect to 3-hexyne concentration. The starting 3hexyne produces primarily cis-3-hexene, which subsequently is either hydrogenated to hexane or
isomerized to trans-3-hexene and 2-hexenes that are found in very small amounts depending on the
nature of the support used. Palladium catalysts supported on SBA-15 was the most active and
selective catalyst.
P-3.4-26
Catalytic synthesis of alkoxy norbornanes
G.Z. Raskildina1, A.M. Suleimanova2, K.K. Gorshunova2, B.I. Kutepov2, S.S. Zlotsky1
1 Dep. of Chemistry, Ufa State Petroleum Technological University, Ufa, Russia,
graskildina444@mail.ru
2 Institute of Petrochemistry and Catalysis of RAS, Ufa, Russia
Interaction of a norbornene with different kinds of alcohols (aliphatic, allylic, benzyl, cyclic acetal
and ethylene glycol) in the presence of the zeolite catalyst H-Beta was investigated. It was established
that this reaction occurs with aliphatic C1-C10, allylic, benzyl, cyclic acetal alcohols and ethylene
glycol with complete conversion of the norbornene and selectivity of the formation of alkoxy
products 80-98% practically.
The products of the interaction of norbornene with cyclohexyl alcohol are dimers of a cyclohexen and
of the norbornene. The highest selectivity of the formation alkoxynorbornans is reached at 50-60°C
and a mol ratio the norbornene : alcohol = 1:3.
P-3.4-27
Synthesis of pyridine and picolines over H-beta zeolite catalyst
N.A. Filippova1, N.G. Grigor’eva2, I.S. Faizrakhmanov1, B.I. Kutepov2
1Dep. Of Chemistry, Bashkir State University, Ufa, Russia, nadezhda.filippova@mail.ru
2Institute of Petrochemistry and Catalysis Russian Academy of Sciences Ufa, Russia.
The reaction of ethanol, formaldehyde and ammonia over H-beta zeolite catalyst was studied. It was
found that in this reaction the main products of the reaction are pyridine, methyl pyridine and
dimethylpyridine. The effect of temperature and WHSV on the conversion of ethanol and selectivity
N-containing compounds was investigated. With the increase of temperature to 400 oC and decreased
of WHSV to 0.5 h-1 conversions increased. The pyridine selectivity over H-beta zeolite was achieved
58 -60 %.
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P-3.4-28
Facile and Fast Laboratory Upscaling Synthesis of ZIF-8 Nanocatalyst and Application in
Monoglyceride Synthesis Process
L.H. Wee1, T. Lescouet2, J. Ethiraj3, F. Bonino3, R. Vidruk4, E. Garrier5, D. Packet5, S. Bordiga3, D.
Farrusseng2, M. Herskowitz4, J.A. Martens1
1Centre for Surface Science and Catalysis, KU Leuven, Kasteelpark Arenberg 23, Heverlee, B3001,
Belgium, likhong.wee@biw.kuleuven.be
2Institut de Recherche sur la Catalyse et l’Environnement de, Lyon (IRCELYON), University Lyon 1,
CNRSC, Villeurbanne, France
3Centre of Excellence and INSTM Centro di Riferimento, Dipartimento di Chimica IFM, Università di
Torino, Torino, Italy
4Blechner Center for Industrial Catalysis and Process Development, Ben-Gurion University of the
Negev, Beer-Sheva, Isreal
5Novance, Compiegne, France
Under the EU FP7, the NanoMOF project, we would like to report on facile laboratory upscaling
synthesis of ZIF-8 nanomaterials with unprecedented microporosity and pore volume. ZIF-8
nanocatalyst was demonstrated for a very first time as active heterogeneous catalyst for catalyzing the
demanding esterification reaction of oleic acid with glycerol under mild reaction conditions.
P-3.4-29
A novel zeotype palladium dodecylamino phosphate : Efficient catalyst for the Suzuki coupling
reactions
A. Rajini, M. Nookaraju, A. Ajay kumar, N. Venkatathri and I.A.K. Reddy
Department of Chemistry, National Institute of Technology Warangal,
Warangal - 506 004, Andhra Pradesh, India.
e-mail: venkatathrin@yahoo.com (+91- 9491319976)
A novel zeotype palladium dodecylamino phosphate was synthesized for the first time at room
temperature and characterized by various physicochemical techniques such as PXRD, SEM, FT-IR,
UV-Vis DRS, 31P and 13CMASNMR. The structural phase of the material has been revealed from
PXRD. Fibrous nature has been confirmed from SEM. The presence of PdO and PdN framework
vibrations and bands related to PdO in the material has been confirmed from FT-IR and UV-Vis DRS
spectroscopy. 31PMASNMR spectrum reveals that all the P atoms are equivalent. The 13C chemical
shifts correspond to the presence of methylene and methyl groups of dodecylamine. The aim of the
study was to develop a novel efficient procedure for Suzuki coupling reactions catalyzed by
palladium dodecylamino phosphate without any ligand to synthesize biaryls. Influence of various
reaction parameters such as effect of bases and solvents on the reaction has been investigated.
Interestingly, the coupling of arylhalides with phenylboronic acid using DMSO and methanol at 70
OC in the presence of potassium carbonate (base), gave high yields of coupled products. Low loading
of catalyst was sufficient for the reaction. In conclusion, palladium dodecylamino phosphate is
simple, inexpensive, stable, recyclable, easily separated and can be reused for three times without a
significant loss in its catalytic activity.
3.5 Adsorption and separation
296
P-3.5-01
Eradication of TCA from aqueous solutions using zeolites as adsorbents
L. Ferreira1, M.F. Ribeiro1, A. Fernandes1, C. Henriques1.
1IBB - Instituto de Biotecnologia e Bioengenharia, CEBQ, Instituto Superior Técnico, 1049-001
Lisboa, Portugal, filipa.ribeiro@ist.utl.pt
2,4,6-trichloroanisole (TCA), a chlorinated anisole derivative, is responsible for cork taint in wine.
Beverage industry (winery) and in a larger extent, food industry, need to meet an efficient way to
limit such molecules to contaminate products during their preparation. Zeolites are aluminosilicates
with a microporosity of about 2 nm that allows these materials to be used in adsorption/separation
industrial processes. Zeolites have already been used as adsorbents for off-flavor compounds removal
in food packaging and beverage industries. Here a comparative study concerning TCA removal
evaluation from aqueous solutions using FAU zeolites with different physicochemical properties is
presented. It showed that framework Si/Al ratio was the main parameter that controls the TCA
removal capacity of the different samples as the ones with Si/Al > 10 were considered to be efficient.
However, other parameters (crystals size, compensating cation, etc.) have to be also studied to better
understand the exact mechanism of TCA removal from zeolites.
P-3.5-02
Selective adsorption of tobacco specific nitrosamines (TSNA) in smoke
Y. Zhou, W.G. Lin, M.M. Wan, J. Yang, Y. Wang, J.H. Zhu
College of Chemistry and Chemical Engineering, Nanjing University, 22 Hankou road, Nanjing
210093, China wangy@netra.nju.edu.cn, jhzhu@netra.nju.edu.cn
Selective adsorption in environment protection is faced a challenge arisen from tobacco smoke where
the TSNA are adhered on the particles in gas stream. Common zeolite and mesoporous material
cannot trap the TSNA because the sizes of particles exceed their pore diameters, while some materials
with 3D-net or fiber-like morphology suffer from the unnecessary trap of the particles. New
adsorbents are synthesized in acidic system with mild shearing force, and they own the same textural
properties as mesoporous silica but different morphology. The mode of “polishing apple” is suggested
to selectively adsorb the TSNA in smoke. New adsorbents are put into the filter of cigarettes to
eliminate TSNA in mainstream smoke, and many zeolites and mesoporous silicas are utilized for
comparison. New additives can selectively trap 30% of TSNA but 3.3% of particles in tobacco smoke
for the first time.
P-3.5-03
Properties of a novel binderless Y-type zeolite for thermal adsorption storage applications
J. Jänchen1, T. Herzog1, K. Schumann2, A. Brandt2, B. Unger2
1 Technical University of Applied Sciences Wildau, 15745 Wildau, Germany, jochen.jaenchen@thwildau.de
2 Chemiewerk Bad Köstritz GmbH, 07568 Bad Köstritz, Germany
Novel binderless zeolite beads of the type Y (KÖSTROLITH®, NaYBF) have been synthesized
following a new approach of manufacturing. This new product have been characterized by scanning
electron microscopy, mercury intrusion, nitrogen adsorption, thermogravimetry, water adsorption
isotherm measurements, cyclic hydrothermal treatments, and thermal adsorption storage tests. The
NaYBF shows an improved adsorption capacity because of the missing binder, excellent
hydrothermal stability, and enhanced specific energies as found previously for binderless A- and Xtype zeolites. A comparably high adsorption lift keeping a certain discharging temperature lift for
lower charging temperatures makes NaYBF more suitable for low temperature applications such as
solar energy than A- or X-type zeolites.
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P-3.5-04
Сhoice of preactivation conditions of zeolites Х by design of experiments
Ivanova E.N., Alekhina M.B, Aknazarova S.L., Konkova T.V.
D.I. Mendeleyev University of Chemical Technology of Russia
Miusskaya sq. 9, Moscow, Russia, 125047, katjuchka1@mail.ru
Adsorption properties of zeolites for air macro components strongly depend on conditions of their
preliminary activation. Search of optimal activation conditions was carried out by use of design of
experiments. The results, received according to the plan were used for researching of parametrical
sensitivity of the chosen technological indicators (factor of nitrogen-oxygen mixture separation and
others) for changing of four factors (temperature, composition of blowing-off gas, speed and duration
of heating). The activation conditions, allowing receiving the greatest factor of nitrogen-oxygen
mixture separation were picked up. It was shown, that availability of carbon dioxide in blowing-off
gas positively influences the factor of separation, increasing adsorption capacity of zeolite for
nitrogen.
P-3.5-05
Performance of Mesoporous Materials in Adsorptive Desulfurization
Y.C. Qin1,2, X.C. Shao2, X.T. Zhang2, Y. Wang2, Y.J. Ruan2, L.H. Duan2, L. Song1,2,*
1 College of Chemistry and Chemical Engineering, China University of Petroleum (East China),
Qingdao, Shandong 257061, China
2 Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning, Liaoning ShiHua
University, Fushun 113001, China
The aim of this paper is to provide the correlations between the adsorptive desulfurization
performance and surface acidities of the adsorbents, and to explore the interactive style between the
host-guest species. A series of MCM-41 samples containing molybdenum oxide as active species in
the mesoporous channels loaded by a solid-state grinding method have been prepared. It is found that
MoO3 can be highly dispersed up to 16.67% (wt.) in the MCM-41 channels. Also copper oxide active
species were incorporated into SBA-15 mesoporous materials by similar routes with as-prepared
SBA-15. It is learned that CuO up to about 20% (wt.) loading can be highly dispersed on the support
by use of as-prepared SBA-15 mesoporous molecular sieves. The desulfurization performance is
closely related with the amounts of Lewis acid of the samples. The solid-state grinding strategy is an
efficient way to fabricate mesoporous materials with high quantum confinement properties.
P-3.5-06
Synthesis and characterization of LTA/carbon hierarchical structured composite for cobalt (II)
uptake
David A. De Haro-Del Rio1, S. Holmes1
1School of Chemical Engineering and Analytical Sciences, The University of Manchester, Sackville
St. Manchester, M13 9PL, UK, david.deharodelrio@postgrad.manchester.ac.uk
A hierarchical zeolite LTA/Carbon composite has been synthesized to improve the accessibility to the
adsorption and ion exchange sites for dissolved metals. Carbon was conditioned reusing one of the
main Mexican agro-industrial residues,corn husk. Following a thermal route to create large pores.
Zeolitic material was grown on the carbon using colloidal precursors in order to reduce crystal size
and consequently improve the coverage over the surface. XRD, SEM and TGA were used to
characterise the material. Kinetic experiments show that, once equilibrium is reached, zeolite
contained in the composite has an improved cobalt uptake (285mg/g) compared to pure zeolite LTA
(90 mg/g).
3.5 Adsorption and separation
298
P-3.5-07
Dual temperature ion-exchange separation on zeolites
V. A. Ivanov1, R. Kh. Khamizov2, O. T. Gavlina1, A. A. Madani3
1Dep. of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119899, Russia
E-mail: ivanov@physch.chem.msu.su
2Vernadsky Institute of Geochemistry and Analytical Chemistry of RAS, Moscow, Russia
3King Abdul Aziz University, Thermal Engineering and Desalination Technology Department, Jeddah
21413, Saudi Arabia
The application of zeolites as ion exchangers for concentration and purification of substances is
hampered due to the difficulties with finding efficient and inexpensive chemical agents for their
regeneration in operation cycles. To avoid this problem, the idea of reagent-less thermally-driven
separation on zeolites was successfully used for some tasks. The first promising way of applications
of temperature-swing technique on zeolites are the ion-exchange processes for alkali metal salts highgrade purifications from other alkali metals admixtures. The other, most promising application is the
extraction of potassium from seawater using natural zeolites like clinoptilolite. Such separations are
based on strong influence of temperature on the ion-exchange selectivity: zeolites sorb the target
components from an initial solution at the temperature providing high selectivity; thereafter, these
components are eluted by the same solution at the other temperature ensuring the diminished
selectivity.
P-3.5-08
The First Tethered Organo-AlPO as a Versatile Precursor for Tackling Environmental Issues
D.J. Xuereb1, M.E. Potter1, W. Mothersole1, C. Hinde1, S. Newland1, R. Raja1
1Dep. of Chemistry, University of Southampton, Southampton, UK, djx1e08@soton.ac.uk
The development of novel zeotype materials is paramount in tackling environmental issues such as
sustainable energy production and carbon capture. Herein we discuss the design and characterisation
of the first tethered organo-AlPO species, which displays promising potential in gas adsorption,
organocatalysis and demanding selective aerobic oxidations. Pendant thiol groups permit a range of
functional groups to be encapsulated for gas adsorption whilst simultaneously acting as hosts for gold
nanoparticles. Further, novel hierarchical systems facilitate the immobilisation of a range of
organocatalytic species. Optimisation of design strategy paves the way for adroit modifications,
expanding the scope to specific target catalytic applications.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.5-09
Removal studies of UO22+ and Cu2+ ions onto synthetic NaA zeolite
D. Nibou1, S. Amokrane1, A. Krobba1, H. Mekatel1 and M. Barkat2
1Mater. Tech. Laboratory, Sciences and TechnologyUniversity Houari Boumediene, Algeria,
dnibou@Yahoo.fr
2Nnuclear Research Center, Draria,Algeria
The removal of UO22+ and Cu2+ ions from aqueous solutions on zeolite NaA was studied. The effect
of solution pH, initial concentration C, solid/liquid ratio R and temperature T has been considered.
NaA was synthesized according to a hydrothermal crystallization. Dubinin-Radshkevich, Freundlich
and Langmuir models were applied and the adsorption equilibrium has been found to follow the
Langmuir adsorption isotherm. Kinetic studies showed that the pseudo second-order sorption model
was the most predominant for the adsorption of Cu2+ and the pseudo first-order sorption model was
the most prevalent for the adsorption of UO22+. The rate mechanism of the exchanged cations appears
to be controlled by chemical sorption process. Rate limiting investigations show that the diffusion
was the determining step. The thermodynamic parameters were also determined and the negative
values of adsorption entropies indicated that no significant change occurred in the framework of the
NaA zeolite during the sorption of UO22+ and Cu2+. The obtained optimal parameters were applied to
real effluents containing UO22+ and Cu2+ ions.
P-3.5-10
Phytase Immobilized on Hierarchical Heteroatomic Fe-ZSM-5 Zeolite as Composite Feed
Additive for Enhanced Phytate-Phosphorus Bioavailability
Wenzhong Zhang1, Fang Xu1, Deju Wang2
1School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai,
China, xufangzh@sjtu.edu.cn
2Shanghai Research Institute of Petrochemical Technology, Sinopec, Shanghai, China
After phytase was selectively immobilized on hierarchical heteroatomic Fe-ZSM-5 zeolite, the
acquired composites were studied as novel feed additive with enhanced phytate hydrolysis activity for
phosphorus bioavailability. The nano-environment of the Fe-ZSM-5 zeolite and its interaction with
phytase were characterized using scanning electron microscope (SEM) and atomic force microscope
(AFM) respectively. The adsorptive immobilization process was completed within 100 min and the
monolayer maximum adsorption capacity was calculated to be 2.04 mg mg-1. Effect of solution pH
and ionic strength on immobilization was tested. Compared to free phytase, the improved enzymatic
stability and stabilization of the composites had been systematically investigated.
P-3.5-11
Adsorption of 2,3-DCDD on FAU and EMT-type zeolites: influence of the nature and the
content of charge compensating cations
M. Mercury1,2, N. Zouaoui2, A. Simon-Masseron2, Y. Zerega1, C. Reynard-Carette1, R. Denoyel1, M.
Carette1, A. Janulyte1, J. Patarin2
1 Univ de Haute Alsace (UHA), CNRS, Equipe Matériaux à Porosité Contrôlée (MPC), Institut de
Science des Matériaux de Mulhouse (IS2M) LRC 7228, ENSCMu, 3bis rue Alfred Werner, 68093
Mulhouse Cedex, France, Angelique.Simon-Masseron@uha.fr
2 Aix-Marseille Université, LISA EA 4672, 13397, Marseille cedex 20, France
FAU and EMT- type zeolites have been selected to trap selectively 2, 3-dichlorodibenzo-p-dioxin.
This study shows that the nature and the level of exchangeable cations (Na+, Ca2+, Li+, Mg2+, Ag+,
K+) have an influence on the adsorption of dioxin. A higher dioxin adsorption rate was observed for
the sodium forms. For a similar Si/Al molar ratio, the adsorption of dioxin is greater for EMT-type
zeolite.
3.5 Adsorption and separation
300
P-3.5-12
Mordenites, ZSM-5 and Beta Zeolites Modified with Cations as Adsorbents for Control of
Hydrocarbon Cold-Start Emissions
V.Golubeva1*, A.Korableva1, L.Kustov2, G.Kapustin2, U.S.Rohatgi3, M.V.Viola4
1RFNC-VNIIEF, 2ZIOC RAS, 3US NNSA DOE, 4GM R&D, USA
Hydrocarbons emissions released during the first 5-10 min of the engine cold-start make about 80%
of the total hydrocarbon emissions. Efficient adsorbents capable of holding hydrocarbons up to
temperatures of 250-350ОС would be the solution to the problem of hydrocarbon cold-start emissions.
In this work we have studied the modification of mordenite, ZSM-5, and Beta zeolites with diverse
cations to meet the requirements for cold-start emission adsorbents. The adsorbents have been studied
by the method of temperature-programmed desorption (TPD) of toluene.
Introducing Li, Na, K, Zn, Co cations in ZSM-5 and some other zeolites results in the appearance of temperature peaks (200-350oC) on the toluene TPD curve. Quite a number of zeolites high modified
with diverse cations showed very promising results as potential adsorbents to control the cold-start
engine hydrocarbon emissions.
P-3.5-13
Interaction between the framework of silicalite-1 and OH group
in sorbate molecules
N. Kamiya1, T. Oshiro1, S. Tan1, T. Koike1, K. Nishi1, Y. Yokomori1
1Dep. of Applied Chemistry, National Defense Academy, Yokosuka, Japan, natsumi@nda.ac.jp
The adsorption process of sorbate molecules with the hydroxyl group on silicalite-1 zeolite was
studied by a single-crystal X-ray diffraction method. Based on the results of the structure analysis of
phenol-silicalite-1, it is clear that hydrogen bonds were present in the framework. Double oxygen 10membered rings of the straight channel and the sinusoidal channel were distorted and the framework
structure was stressed by the adsorption of phenol molecules. In the case of ethanol-silicalite-1, there
is no distortion of double oxygen 10-membered rings. The degree of the framework stress of
phenol8.0-silicalite-1 was higher than that of hydrocarbon compounds adsorbed crystals because of
the hydrogen bonds.
P-3.5-14
Features of flavonoids sorption on MCM-41 and composite materials based on MCM-41
S.I.Karpov1, F. Roessner2, N.A. Belanova1, V.F. Selemenev1, E.O. Korabelnikova1, O.O.
Krizhanovskaya1, I.V. Nedosekina
1Dep. of Chemistry, Voronezh State University, Voronezh, Russia, karsiv@pochta.ru
2Industrial Chemistry 2, Carl von Ossietzky University, D-26111, Oldenburg, Germany
One of the most perspective areas of analytical chemistry is sorption isolation of flavonoids by solidphase extraction and liquid chromatography. Normal and modified silica gels, activated carbon,
polymeric resins are increasingly used for these purposes. There are recent works that are used for
this aim highly ordered materials such as MCM-41. To manage the process of separation of
flavonoids were studied sorption equilibrium parameters of quercetin on the original MCM-41, the
silylated sample and at the material synthesized in the presence of quercetin. Sorption isotherms of
quercetin on mesoporous materials indicate the possibility of multilayer adsorption of substance. The
distribution coefficients for quercetin by the sorption on mesoporous adsorbents more than 100. This
fact indicates a high degree of affinity of sorbent to a substance.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.5-15
Equilibrium of adsorption of α-tocopherol and β-sitosterol onto mesoporous composites
O.O. Krizhanovskaya1, E.V. Borodina1, S.I. Karpov1, F. Roessner2, V.F. Selemenev1
1Chemical Department, Voronezh State University, Voronezh, Russia, o.krizhanovskaya@gmail.com
2Faculty of Mathematics and Natural Sciences, Carl von Ossietzky University, Oldenburg, Germany
The equilibrium of α -tocopherol and β-sitosterol adsorption from hexane solution onto parent MCM41 and aminosilane and chlorotrimethylsilane composites has been studied. The distribution
coefficients of these biological active substances between solution and an adsorbent have been
calculated. Langmuir and BET models have been applied for description of equilibrium isotherms and
calculation thermodynamic parameters of sorption. A significant influence of the sorbate-sorbate,
sorbate-sorbent, sorbate-solvent interactions has been established.
P-3.5-16
Adsorption isotherm of pure gases at high pressures on Na-LTA zeolites of different crystal
sizes
R. E. Bazan1, C. G. Maciel1, D. C. Melo2, D. Cardoso1
1Department of Chemical Engineering, Catalysis Laboratory, Federal University of São Carlos,
Brazil, www.labcat.org
2Cenpes – Petrobras, Rio de Janeiro, Brazil
bazan@ufscar.br, dilson@ufscar.br
Zeolites are excellent adsorbers of most small molecules, including H2O, NH3, H2S, NO2, SO2, and
CO2, as well as linear and branched hydrocarbons, aromatic hydrocarbons, alcohols, and ketones, in
both liquid and gaseous phases. The most important application of zeolite A is in the drying of gases.
The adsorbents were prepared conventionally according to the Verified Synthesis of Zeolitic
Materials procedure. The Z4-04 zeolite was used to measure adsorption of CO2, CH4, and N2, and the
data obtained for CH4 were used as a reference for comparison with adsorption by the zeolites
synthesized in the laboratory.
P-3.5-17
Non-monotonic chain length dependent adsorption and diffusion of 1-alcohols in SAPO-34
J. Cousin Saint Remi, G. Baron and J. Denayer.
Dep. of Chemical Engineering, Vrije Universiteit, Brussels, Belgium, jcousins@vub.ac.be
SAPO-34, a member of the silico aluminophosphates minerals, exhibits the same framework structure
as the naturally occurring chabazite. The chabazite topology consists of a three-dimensional pore
system of ellipsoidal cages (6.8 x 10Ų) interconnected by eight membered windows (3.8 x 3.8Ų),
where each cage possessses six windows. Due to this small pore system and its catalytic properties,
SAPO-34 is a very interesting material for molecular sieve separations and selective catalysis. A lot
of attention has been given to the potential of SAPO-34 to separate small gaseous molecules and to
catalyze the MTO process. Recently we have shown that SAPO-34 could efficiently separate 1alcohols from each other, which was proven to be interesting for the purification of biobutanol.
However a study of the transport properties of alcohol molecules is missing. In this study, we present
results on the adsorption and diffusion of 1-alcohols and n-alkanes into SAPO-34 crystals from the
liquid phase and vapor phase, obtained by batch measurement, a gravimetric method and a zerolength column (ZLC) method.
3.5 Adsorption and separation
302
P-3.5-18
Hydrogen adsorption by Cu(I)-Y, -SSZ-13 and –ZK-5
B. Ipek1, C.M. Brown2, R.F. Lobo1
1Center for Catalytic Science and Technology, University of Delaware, Newark, DE, USA,
bhripek@udel.edu
2National Center for Neutron Research, National Institute of Standards and Technology,
Gaithersburg, MD, USA
Zeolites are promising in hydrogen storage with their low density and fast adsorption kinetics.
However, the weak interactions between hydrogen and the surface of zeolites render favorable storage
densities only at cryogenic temperatures at atmospheric pressures. We report better hydrogen
adsorption capacities on Cu(I)- Y, -ZK-5 and –SSZ-13 zeolites at 303 K when compared to Na+
exchanged Y, ZK-5 and SSZ-13 zeolites. On the other hand Cu(I) exchanged zeolites show smaller
adsorption capacities than those of to Na+ exchanged Y, ZK-5 and SSZ-13 at 77 K. Possible changes
in the location of Cu(I) cations inside the zeolite structure are being investigated by neutron and X-ray
diffraction studies as a function of temperature and as a function of the adsorbate concentrations.
P-3.5-19
Enhancing CCS performances of microporous materials by basic oxide coating
Jenny G. Vitillo1, Gabriele Ricchiardi1, Valentina Crocellà1, Silvia Bordiga1
1 Dipartimento di Chimica and NIS Centre of Excellence, Università di Torino, Via Quarello 15A,
10135 Torino and INSTM UdR Torino, Italia, jenny.vitillo@unito.it
Carbon dioxide separation and adsorption is the most urgent scientific challenge of our age.
Microporous materials as MOF and zeolites showed good CCS performances for both CO2 adsorption
and separation, although their optimal working temperatures are essentially close to RT. Nevertheless,
their potential in this field is limited by the fact that the involved processes maintain the molecular
nature of CO2. The presence of sites able to chemisorb CO2 by dissociating the molecule is typical of
metal oxides that, however, require high temperature for their regeneration.
In this study, the possibility to couple dissociative and not dissociative chemisorption of CO2 in a
controlled way has been realized by coating the internal pores of a zeolite and a MOF with an alkali
earth oxides layer and characterized by means of volumetric and FTIR techniques.
P-3.5-20
Titanosilicate desiccants for low temperature/energy input CO2 drying
S. Rezaei1, B. Tanchuk1, J.A. Sawada, S.M. Kuznicki1
1Dep. of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada,
Sabereh@ualberta.ca
In this work new titanosilicate-based desiccants for low temperature CO2 drying have been
developed. We are centering our work on cation-exchanged forms of a large-pored
octahedral/tetrahedral titanosilicate molecular sieve, which display unique water adsorption
characteristics due to the chemical composition of the sieve coupled with its microporous nature. The
energy requirement to remove the water adsorbed on this material is much lower than for the same
quantity of water adsorbed on a conventional molecular sieve. These attributes make this new
titanosilicate material a promising desiccant for CO2 drying, as it is capable of substantially drying a
gas stream to extremely low water concentration with reactivation under mild (low temperature/low
energy) conditions.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.5-21
Removal of Cr(III) from aqueous solution by zeolites sintetized from exhausted FCC catalysts.
Kinetics studies and effect of Cr(III) exchange on the zeolitic structure
M. R. Gonzalez1, A. M. Pereyra1,2, E. I. Basaldella1,2
1Centro de Investigación y Desarrollo en Ciencias Aplicadas Dr J.J. Ronco (CINDECA) (CONICETCIC-UNLP), calle 47 N°257, 1900- La Plata, Argentina. E-mail: eib@quimica.unlp.edu.ar
2Universidad Tecnológica Nacional, Regional La Plata, calle 60 y 124, 1900 La Plata, Argentina
The conversion of a spent FCC catalyst in a zeolitic mixture was carried out and the product obtained
was afterwards tested as trapping material for Cr(III) species frequently found in aqueous solutions.
The kinetic parameters of the Cr retention process were determined and the eventual changes in the
zeolite structure produced by the Cr incorporation were studied by different characterization
techniques: zeta potential measurements (PZC), X-ray Diffraction (XRD), scanning electron
microscopy (SEM) and infrared spectrometry (FTIR). DRX and FTIR analysis indicated that
chromium incorporation produces an amorphization of the zeolitic structure and PZC shows no
surface adsorption of charged chromium species. SEM micrographs clearly show that the initial
microspheres morphology is maintained and the presence of zeolite crystals covering the external
microsphere surface.
P-3.5-22
Surface concentrations of methanol/DME/C3H6/C3H8 mixtures
calculated by the Langmuir and ideal adsorbed solution theories
Yasukazu Kobayashi, Yuxin Li, Yao Wang, Dezheng Wang*
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China,
wangdezheng@tsinghua.edu.cn
In reaction kinetics, Langmuir theory is used to calculate the surface concentration or fractional
occupancy of each gas component on solid catalysts that are exposed to gas mixtures. However, this
theory is only consistent with thermodynamics when the monolayer capacity is the same for all
species. When this is not the case, to ensure thermodynamics consistency, the ideal adsorbed solution
theory (IAST) should be used. In this study, the surface concentrations on SAPO34 at 350°C due to a
mixture of methanol, DME, C3H6, and C3H8 were predicted by the Langmuir theory and IAST. The
Langmuir equation parameters at 350°C used for the predictions were extrapolated from pure
component adsorption isotherms at 25°C, 60°C, and 100°C. The predicted surface concentrations are
different enough that there would be a significant effect on the reaction kinetics. The predicted
surface concentrations of the two theories are tested with binary component adsorption isotherm
experiments.
P-3.5-23
Pore-expanded MCM-41 for CO2 adsorption
E.S. Sanz Pérez1, A. Arencibia2, G. Calleja2, R. Sanz2
1 Dep. of Chemical and Environmental Technology, Rey Juan Carlos University, Madrid, Spain
2 Dep. of Chemical and Energy Technology, Rey Juan Carlos University, Madrid, Spain,
raul.sanz@urjc.es
Pore-expanded MCM-41 mesostructured silica has been prepared and functionalized post-syntheses
by grafting with aminopropyl, AP (N), ethylenediamine, ED (NN) and diethylenetriamine,
DT (NNN), and by impregnation with tetraethylenepentamine, TEPA, pentaethylenehexamine,
PEHA, and polyethyleneimine, PEI.
Significant CO2 adsorption capacities up to 121 mg CO2/g (2.8 mmol CO2/g) and efficiencies up to
0.41 mol CO2/mol N have been obtained, turning these materials into promising adsorbents in largescale facilities for post-combustion CO2 capture.
3.5 Adsorption and separation
304
P-3.5-24
Adsorption of methyl tert-butyl ether on zeolites Y, Mordenite, and ZSM-5 used for the
decontamination of ground water
V. Sacchetto1,2, C. Bisio1,2, G. Gatti1,2, M. Cossi1,2, L. Marchese1,2, I. Braschi2,3
1Department of Advanced Science and Technologies, chiara.bisio@mfn.unipmn.it
2Interdisciplinary Nano-SiSTeMI Centre, University of Eastern Piedmont A. Avogadro, Alessandria
(Italy),
3Department of Agricultural l Science, University of Bologna, Bologna (Italy).
Methyl tertiary butyl ether (MTBE) is a fuel-based pollutant present in ground water coming from
areas where refinery plants and gas stations are located. To restrict downward movement of
contaminants, physical barriers made of zeolites can be used. In this study, the adsorption of MTBE
on high silica zeolites Y, mordenite, and ZSM-5 has been studied by FTIR spectroscopy,
thermogravimetric analysis and ab initio calculations. The type and strength of host-guest interactions
have been defined for each sorbents also under wet working conditions.
P-3.5-25
Adsorption of hexane isomers on MFI type zeolites: Understanding the aluminium content
effect
A. Ferreira1, M. Mittelmeijer-Hazeleger2, J. Bergh3, S. Aguado4, J.C. Jansen3, G. Rothenberg2, A.E.
Rodrigues1, F. Kapteijn2
1 LSRE, Faculty of Engineering, University of Porto, Porto, Portugal, aferreir@fe.up.pt
2HIMS, University of Amsterdam, Amsterdam, The Netherlands
3 CE, ChemE dept., Delft University of Technology, Delft, The Netherlands
4 Dept. of Chemical Engineering, University of Alcalá, Madrid, Spain.
The influence of the aluminium content on the adsorption of hexane isomers was studied at 293K on
MFI type zeolites (Si/Al ratios of 25, 100 and ∞). Adsorption isotherms were assessed with a
homemade volumetric system. Temporal up-take curves were recorded using a manometric set-up
combined with a Rubotherm suspension balance. All four isomers show dual site adsorption behavior
that is well described with a Dual Site Sips (DSS) model. The Si/Al ratio influences strongly the
adsorption equilibrium properties. Regardless of the isomer type, the sample with SAR = 100 shows
the highest saturation loadings. Generally, the Henry constant increases with aluminium content.
Clear diffusional limitations are observed for the di-branched hexane isomers on all three zeolite
samples. From an application point of view silicalite-1 is the most promising for enhancing gasoline
octane numbers at 293K, as it gives the highest equilibrium 2,3-DMB / 2-MP ratios.
17 IZC, 2013. POSTER COMMUNICATIONS
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P-3.5-26
Purification of catalytic cracking gasoline from sulfur by the hydroadsorption method
G.S. Mukhtarova, Z.A.Qasimova, H.C. Ibrahimov, V.M.Abbasov, M.I. Rustamov
Azerbaijan NAS Institute of Petrochemical Processes, Azerbaijan, Baku, gulermuxtarova@yahoo.com
In the done job for the purpose to improve the quality of catalytic cracking gasoline it has been
develop to treat it from sulfur with the process of hydroadsorption over the bentonite which modified
with Ni. For the treatment of catalytic cracking gasoline from sulfur with the hydroadsorption method
the process was conducted in the current Madjar plant at 240-3000C temperature, at 2.5 MPa pressure,
1500 l/l correlation of hydrogen to stuff and on 0.5-1.5 h-1 velocity space, it was investigate the
influence of condition parameters (temperature and space velocity) to the hydrotreatment process and
it was selected optimal regime parameters (temperature 2700C, pressure 2.5 MPa, space velocity 1h1).
P-3.5-27
Hydrogen adsorption onto MCM-48 carbon replica modified with metals
J. M. Juárez1, M. B. Gómez Costa1, J. Cussa1, O.A. Anunziata1
1 Centro de Investigación en Nanociencia y Nanotecnología (NANOTEC), Facultad Regional
Córdoba, Universidad Tecnológica Nacional, Córdoba, Argentina. oanunziata@scdt.frc.utn.edu.ar
CMK-1 ordered carbon was synthesized via a two step impregnation of the mesopores of MCM-48,
with a solution of sucrose using an incipient wetness method.
Ni-CMK-1, Zn-CMK-1 and Ir-CMK-1 were prepared by wet impregnation using NiCl2.6H2O,
Zn(NO3)2.6H2O and Iridium Acetylacetonate as source of Ni, Zn and Ir respectively. In order to
increase the amount of hydrogen adsorbed the Zn-CMK-1 sample was treated under H2 flow, at 1173
K.
Porous carbon CMK-1 and the samples modified with metals were characterized by XRD, FTIR,
XPS, BET and SEM.
Measurements of hydrogen adsorption at cryogenic temperatures and low pressures were performed.
Zn-CMK-1 and Ni-CMK-1 had a lower hydrogen storage capacity than the nanostructured CMK-1.
While the Zn-CMK-1 sample that was thermally treated under hydrogen flow showed a greater H2
than the sample CMK-1.
P-3.5-28
Adsorption of amino acids on ordered mesoporous sillicas modified with lanthanum
J. Goscianska, A. Olejnik, R. Pietrzak
Faculty of Chemistry, Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614 Poznań,
Poland, pietrob@amu.edu.pl
Amino acids such as L-phenylalanine and L-histidine were adsorbed on a series of mesoporous
ordered silicas KIT-6, SBA-16, SBA-15, SBA-3 modified with lanthanum. The structural and textural
properties of all obtained materials were characterized by XRD and nitrogen adsorption. The sillica
materials exhibited well-developed surface area and large pore volume. The occurrence of ordered
mesoporous structure of all the materials studied was also confirmed. The modification of silicas with
lanthanum leads to decrease in their surface area and pore volume. The adsorption process of amino
acids was carried out in potassium phosphate buffer solutions with adjustable amino acid
concentration, ion strength, and pH. The adsorption of amino acids on the mesoporous silicas follows
the Langmuir type isotherm with a maximum capacity at pH close to the isoelectric points of these
amino acids.
3.5 Adsorption and separation
306
P-3.5-29
Enhanced CO2 capture over CMK carbons functionalized with amino groups
R. Sanz1, D. Serrano1,2, P.Pizarro1,2, A. Arencibia1, A. L. López3, E. Esteban3, J.L. Domínguez3, I.
Moriña3
1Department of Energy and Chemical Technology, ESCET, Universidad Rey Juan Carlos,
Madrid, Spain, raul.sanz@urjc.es
2IMDEA Energía Institute, 28935