Zeolites and Catalysis Synthesis, Reactions and Applications Edited by Ji ˇ r ´ ı ˇ Cejka, Avelino Corma, and Stacey Zones Zeolites and Catalysis Edited by Ji ˇ r ´ ı ˇ Cejka, Avelino Corma, and Stacey Zones Related Titles Blaser, H U., Federsel, H J. (eds.) Asymmetric Catalysis on Industrial Scale Challenges, Approaches and Solutions 2010 ISBN: 978-3-527-32489-7 Mizuno, N. (ed.) Modern Heterogeneous Oxidation Catalysis Design, Reactions and Characterization 2009 ISBN: 978-3-527-31859-9 Barbaro, P., Bianchini, C. (eds.) Catalysis for Sustainable Energy Production 2009 ISBN: 978-3-527-32095-0 Crabtree, R. H. (ed.) Handbook of Green Chemistry - Green Catalysis Three Volumes 2009 ISBN: 978-3-527-31577-2 Ozkan, U. S. (ed.) Design of Heterogeneous Catalysts New Approaches based on Synthesis, Characterization and Modeling 2009 ISBN: 978-3-527-32079-0 Swiegers, G. Mechanical Catalysis Methods of Enzymatic, Homogeneous, and Heterogeneous Catalysis Hardcover ISBN: 978-0-470-26202-3 Jackson, S. D., Hargreaves, J. S. J. (eds.) Metal Oxide Catalysis 2009 ISBN: 978-3-527-31815-5 Ding, K., Uozumi, Y. (eds.) Handbook of Asymmetric Heterogeneous Catalysis 2008 ISBN: 978-3-527-31913-8 Ertl, G., Kn¨ozinger, H., Sch¨uth, F., Weitkamp, J. (eds.) Handbook of Heterogeneous Catalysis Eight Volumes 2008 ISBN: 978-3-527-31241-2 Zeolites and Catalysis Synthesis, Reactions and Applications Edited by Ji ˇ r ´ ı ˇ Cejka, Avelino Corma, and Stacey Zones The Editor Prof. Dr. Jiˇr ´ ı ˇ Cejka Academy of Sciences of the Czech Republic Heyrovsk ´ y Institute of Physical Chemistry Dokj ˇ skova Dolejskova 3 182 23 Prague 8 Czech Republic Prof. Dr. Avelino Corma University Politecnica de Valencia InstitutedeTecnologiaQuimica Avenida de los Naranjos s/n 46022 Valencia Spain Prof. Dr. Stacey I. Zones Chevron Texaco Energy Research and Technology Company 100 Chevron Road Richmond, CA 94802 USA All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbib- liografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de.  2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Composition Laserwords Private Limited, Chennai Printing and Bookbinding strauss GmbH, M ¨ orlenbach Cover Design Formgeber, Eppelheim Printed in the Federal Republic of Germany Printed on acid-free paper ISBN: 978-3-527-32514-6 V Contents to Volume 1 Preface XIII List of Contributors XVII 1 Synthesis Mechanism: Crystal Growth and Nucleation 1 Pablo Cubillas and Michael W. Anderson 1.1 Introduction 1 1.2 Theory of Nucleation and Growth 3 1.2.1 Nucleation 3 1.2.2 Supersaturation 3 1.2.3 Energetics 4 1.2.4 Nucleation Rate 5 1.2.5 Heterogeneous and Secondary Nucleation 5 1.2.6 Induction Time 6 1.2.7 Crystal Growth 6 1.2.8 Crystal Surface Structure 6 1.2.9 2D Nucleation Energetics 8 1.2.10 Spiral Growth 9 1.2.11 Interlaced Spirals 10 1.2.12 Growth Mechanisms: Rough and Smooth Surfaces 10 1.3 Nucleation and Growth in Zeolites 11 1.3.1 Overview 11 1.3.2 Zeolite Nucleation 13 1.3.3 Crystal Growth on Zeolites and Zeotypes 14 1.4 Techniques 15 1.4.1 The Solid Crystal 15 1.4.1.1 AFM 15 1.4.1.2 HRSEM 16 1.4.1.3 Confocal Microscopy 16 1.4.2 Solution Chemistry – Oligomers and Nanoparticles 17 1.4.2.1 Nuclear Magnetic Resonance 17 1.4.2.2 Mass Spectrometry 19 Zeolites and Catalysis, Synthesis, Reactions and Applications. Vol. 1. Edited by Ji ˇ r ´ ı ˇ Cejka, Avelino Corma, and Stacey Zones Copyright  2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32514-6 VI Contents 1.4.2.3 Cryo-TEM 20 1.4.3 Modeling 21 1.4.3.1 Monte Carlo Modeling of Crystal Growth 21 1.5 Case Studies 23 1.5.1 Zeolite A 23 1.5.1.1 Thompson Synthesis 24 1.5.1.2 Petranovskii Synthesis 26 1.5.2 Silicalite 28 1.5.3 LTL 33 1.5.4 STA-7 35 1.5.4.1 {001} Faces 38 1.5.4.2 {001} Faces 38 1.5.5 Zincophosphates 43 1.5.5.1 ZnPO 4 -Sodalite 43 1.5.5.2 ZnPO 4 -Faujasite 47 1.5.6 Metal Organic Frameworks 47 1.6 Conclusions and Outlook 49 References 50 2 Synthesis Approaches 57 Karl G. Strohmaier 2.1 Introduction 57 2.2 Aluminophosphates 58 2.3 Mineralizers 59 2.4 Dry Gel Conversion Syntheses 61 2.5 Low Water Syntheses 62 2.6 Germanium Zeolites 63 2.7 Isomorphous Substitution 65 2.8 Structure-Directing Agents 67 2.9 SDA Modeling 70 2.10 Co-templating 72 2.11 Layered Precursors 73 2.12 Nonaqueous Solvents 77 2.13 Summary and Outlook 79 Acknowledgments 80 References 80 3 Ionothermal Synthesis of Zeolites and Other Porous Materials 87 Russell E. Morris 3.1 Introduction 87 3.2 Hydrothermal, Solvothermal, and Ionothermal Synthesis 89 3.3 Ionothermal Aluminophosphate Synthesis 90 3.4 Ionothermal Synthesis of Silica-Based Zeolites 92 Contents VII 3.5 Ionothermal Synthesis of Metal Organic Frameworks and Coordination Polymers 92 3.6 Ambient Pressure Ionothermal Synthesis 93 3.7 The Role of Cation-Templating, Co-Templating, or No Templating 95 3.8 The Role of the Anion – Structure Induction 97 3.9 The Role of Water and Other Mineralizers 99 3.10 Unstable Ionic Liquids 101 3.11 Summary and Outlook 101 References 102 4 Co-Templates in Synthesis of Zeolites 107 Joaquin P´erez-Pariente, Raquel Garc´ıa, Luis G´omez-Hortig¨uela, and Ana Bel´en Pinar 4.1 Introduction 107 4.2 Templating of Dual-Void Structures 108 4.3 Crystallization of Aluminophosphate-Type Materials 113 4.4 Combined Use of Templating and Pore-Filling Agents 116 4.5 Cooperative Structure-Directing Effects of Organic Molecules and Mineralizing Anions 117 4.6 Cooperative Structure-Directing Effect of Organic Molecules and Water 119 4.7 Control of Crystal Size and Morphology 122 4.8 Membrane Systems 123 4.9 Use of Co-Templates for Tailoring the Catalytic Activity of Microporous Materials 123 4.10 Summary and Outlook 125 Acknowledgments 127 References 127 5 Morphological Synthesis of Zeolites 131 Sang-Eon Park and Nanzhe Jiang 5.1 Introduction 131 5.2 Morphology of Large Zeolite Crystals 132 5.2.1 Large Crystals of Natural Zeolites 132 5.2.2 Synthesis of Large Zeolite Crystals 133 5.3 Morphology Control of MFI Zeolite Particles (of Size Less than 100 µm) 138 5.3.1 Dependence of Structure-Directing Agents (SDAs) 139 5.3.2 Dependence on Alkali-Metal Cations 141 5.4 Morphological Synthesis by MW 142 5.4.1 Examples of MW Dependency 142 5.4.2 Morphological Fabrication by MW 143 5.4.3 Formation Scheme of Stacked Morphology 146 5.5 Summary and Outlook 149 VIII Contents Acknowledgments 150 References 150 6 Post-synthetic Treatment and Modification of Zeolites 155 Cong-Yan Chen and Stacey I. Zones 6.1 Introduction 155 6.2 Direct Synthesis of Zeolites 155 6.3 Post-synthetic Treatment and Modification of Zeolites 157 6.3.1 Aluminum Reinsertion into Zeolite Framework Using Aqueous Al(NO 3 ) 3 Solution under Acidic Conditions 158 6.3.1.1 Experimental Procedures 158 6.3.1.2 One-Step Method versus Two-Step Method 159 6.3.1.3 Effects of the Ratio of Al(NO 3 ) 3 to Zeolite 160 6.3.1.4 Effects of pH, Time, Temperature, and Other Factors 161 6.3.1.5 Applicable to Medium Pore Zeolite? 161 6.3.2 Synthesis of Hydrophobic Zeolites by Hydrothermal Treatment with Acetic Acid 162 6.3.2.1 Experimental Procedures 162 6.3.2.2 Highly Crystalline Pure-Silica Zeolites Prepared via This Technique 163 6.3.2.3 Effects of Type of Acid, pH, Temperature, and Other Factors 163 6.3.2.4 Experimental Results from Our Lab 164 6.4 Summary and Outlook 166 Acknowledgments 167 References 167 7 Structural Chemistry of Zeolites 171 Paul A. Wright and Gordon M. Pearce 7.1 Introduction 171 7.2 Zeolite Structure Types Exemplified by Those Based on the Sodalite Cage 172 7.2.1 Introduction 172 7.2.2 The Framework: Secondary Building Units in Zeolite Structural Chemistry 175 7.2.3 Assembling Sodalite Cages: Sodalite, A, Faujasites X and Y, and EMC-2 177 7.2.4 Faujasitic Zeolites X and Y as Typical Examples 178 7.2.5 Key Inorganic Cation-Only Zeolites Pre-1990 179 7.2.6 Structures Templated by Simple Alkylammonium Ions 182 7.2.7 Lessons from Nature 184 7.3 The Expanding Library of Zeolite Structures: Novel Structures, Novel Features 185 7.3.1 Introduction 185 7.3.2 Novel Structures and Pore Geometries 187 7.3.3 Expansion of the Coordination Sphere of Framework Atoms 191 [...]... Zeolites and Catalysis, Synthesis, Reactions and Applications Vol 2 Edited by Jiˇ´ Cejka, Avelino Corma, and Stacey Zones rı ˇ Copyright  2010 WILEY- VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 97 8-3 -5 2 7-3 251 4-6 283 VI Contents 11 Theoretical Chemistry of Zeolite Reactivity 301 Evgeny A Pidko and Rutger A van Santen 12 Modeling of Transport and Accessibility in Zeolites Sof´a Calero Diaz ı 13 Diffusion in Zeolites. .. Synthesis of Zeolites and Other Porous Materials 87 Russell E Morris 4 Co-Templates in Synthesis of Zeolites 107 Joaquin P´rez-Pariente, Raquel Garc´a, Luis G´ mez-Hortig¨ ela, and Ana e ı o u Bel´n Pinar e 5 Morphological Synthesis of Zeolites Sang-Eon Park and Nanzhe Jiang 6 Post-synthetic Treatment and Modification of Zeolites 155 Cong-Yan Chen and Stacey I Zones 7 Structural Chemistry of Zeolites 171... but also in the Zeolites and Catalysis, Synthesis, Reactions and Applications Vol 1 Edited by Jiˇ´ Cejka, Avelino Corma, and Stacey Zones rı ˇ Copyright  2010 WILEY- VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 97 8-3 -5 2 7-3 251 4-6 XIV Preface postsynthesis steps as highlighted for deboronation followed by realumination as described by C.Y Chen and S.I Zones (Chapter 6) P.A Wright and G.M Pearce show how... incorporation of intergrowth and twin structures Such defects are introduced during the crystal growth stage usually as a result of competing crystallization pathways that are near Zeolites and Catalysis, Synthesis, Reactions and Applications Vol 1 Edited by Jiˇ´ Cejka, Avelino Corma, and Stacey Zones rı ˇ Copyright  2010 WILEY- VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 97 8-3 -5 2 7-3 251 4-6 2 1 Synthesis Mechanism:... Olefin-to-Gasoline and Distillate Process (MOGD) 706 Catalyst and Process Operation 706 Thermodynamic Considerations 706 Technical Process 707 Contents 22.8 22.9 Summary and Outlook 707 Outlook 708 References 708 23 Metals in Zeolites for Oxidation Catalysis 713 Takashi Tatsumi Introduction 713 Titanium-Containing Zeolites 715 TS-1 715 Ti-Beta 722 Ti-MWW 724 Other Titanium-Containing Zeolites 731 Solvent Effects and. .. Isomerization Reactions: Isomerization of α-Pinene and α-Pinene Oxide 792 Oxidation and Reduction Reactions 795 Epoxidation Reactions 795 Baeyer–Villiger Oxidations 799 Meerwein–Ponndorf Verley Reduction and Oppenauer Oxidation (MPVO) 803 Base-Catalyzed Reactions 808 The Knoevenagel Condensation 809 Michael Addition 813 Aldol Condensations 816 XI XII Contents 25.4 Summary and Outlook 819 References 819 26 Zeolites. .. Ali, and Jiˇ ´ Cejka rı ˇ 21 Advanced Catalysts Based on Micro- and Mesoporous Molecular Sieves for the Conversion of Natural Gas to Fuels and Chemicals 649 Agust´n Mart´nez, Gonzalo Prieto, Andr´s Garc´a-Trenco, ı ı e ı and Ernest Peris 22 Methanol to Olefins (MTO) and Methanol to Gasoline (MTG) 687 Michael St¨cker o 23 Metals in Zeolites for Oxidation Catalysis 713 Takashi Tatsumi 24 Environmental Catalysis. .. Catalysis over Zeolites 745 Gabriele Centi and Siglinda Perathoner 25 Zeolites as Catalysts for the Synthesis of Fine Chemicals 775 Maria J Climent, Avelino Corma, and Sara Iborra 26 Zeolites and Molecular Sieves in Fuel Cell Applications King Lun Yeung and Wei Han Index 863 827 V Contents to Volume 1 1 Synthesis Mechanism: Crystal Growth and Nucleation Pablo Cubillas and Michael W Anderson 1 2 Synthesis... Summary and Outlook 353 Acknowledgments 354 References 354 Diffusion in Zeolites – Impact on Catalysis 361 Johan van den Bergh, Jorge Gascon, and Freek Kapteijn Introduction 361 Diffusion and Reaction in Zeolites: Basic Concepts 362 Importance of Adsorption 364 Self-Diffusivity 364 Mixture Diffusion 365 Diffusion Measurement Techniques 365 Relating Diffusion and Catalysis 366 Diffusion in Zeolites: ... the synthesis of zeolites, characterization of their properties, and applications of zeolites in adsorption and catalysis that have revolutionized the petrochemical industry In addition, based on the knowledge of zeolites several other areas of porous materials have recently emerged including mesoporous materials, hierarchic systems, metal-organic frameworks (cationic-periodic polymers) and mesoporous . (eds.) Handbook of Heterogeneous Catalysis Eight Volumes 2008 ISBN: 97 8-3 -5 2 7-3 124 1-2 Zeolites and Catalysis Synthesis, Reactions and Applications Edited by Ji ˇ r ´ ı ˇ Cejka, Avelino Corma, and. Synthesis, Characterization and Modeling 2009 ISBN: 97 8-3 -5 2 7-3 207 9-0 Swiegers, G. Mechanical Catalysis Methods of Enzymatic, Homogeneous, and Heterogeneous Catalysis Hardcover ISBN: 97 8-0 -4 7 0-2 620 2-3 Jackson,. Heterogeneous Oxidation Catalysis Design, Reactions and Characterization 2009 ISBN: 97 8-3 -5 2 7-3 185 9-9 Barbaro, P., Bianchini, C. (eds.) Catalysis for Sustainable Energy Production 2009 ISBN: 97 8-3 -5 2 7-3 209 5-0 Crabtree,