Chemistry of Zeolites and Related Porous Materials: Synthesis and Structure RUREN XU Jilin University, China WENQIN PANG Jilin University, China JIHONG YU Jilin University, China QISHENG HUO Pacific Northwest National Laboratory, USA JIESHENG CHEN Jilin University, China John Wiley & Sons (Asia) Pte Ltd Chemistry of Zeolites and Related Porous Materials Chemistry of Zeolites and Related Porous Materials: Synthesis and Structure RUREN XU Jilin University, China WENQIN PANG Jilin University, China JIHONG YU Jilin University, China QISHENG HUO Pacific Northwest National Laboratory, USA JIESHENG CHEN Jilin University, China John Wiley & Sons (Asia) Pte Ltd Copyright # 2007 John Wiley & Sons (Asia) Pte Ltd Clementi Loop #02-01, Singapore 129809 Visit our Home Page on www.wiley.com All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as expressly permitted by law, without either the prior written permission of the Publisher, or authorization through payment of the appropriate photocopy fee to the Copyright Clearance Center Requests for permission should be addressed to the Publisher, John Wiley & Sons (Asia) Pte Ltd, Clementi Loop, #02-01, Singapore 129809, tel: 65-64632400, fax: 65-64646912, email: enquiry@wiley.com.sg Designations used by companies to distinguish their products are often claimed as trademarks All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners The Publisher is not associated with any product or vendor mentioned in this book This publication is designed to provide accurate and authoritative information in regard to the subject matter covered It is sold on the understanding that the Publisher is not engaged in rendering professional services If professional advice or other expert assistance is required, the services of a competent professional should be sought Other Wiley Editorial Offices John Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA Jossey-Bass, 989 Market Street, San Francisco, CA 94103-1741, USA Wiley-VCH Verlag GmbH, Boschstr 12, D-69469 Weinheim, Germany John Wiley & Sons Australia Ltd, 42 McDougall Street, Milton, Queensland 4064, Australia John Wiley & Sons Canada Ltd, 6045 Freemont Blvd, Mississauga, ONT, L5R 4J3, Canada Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic books Anniversary Logo Design: Richard J Pacifico Library of Congress Cataloging-in-Publication Data Chemistry of zeolites and related porous materials synthesis and structure / Ruren Xu [et al] p cm ISBN 978-0-470-82233-3 (cloth) Zeolites Porosity–Congresses I Xu, Ruren TP245.S5C52 2007 2007015329 6660 86–dc22 ISBN 978-0-470-82233-3 (HB) Typeset in 10/12 pt Times by Thomson Digital, India Printed and bound in Singapore by Markono Print Media Pte Ltd, Singapore This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production Contents Preface xi Introduction 1.1 The Evolution and Development of Porous Materials 1.1.1 From Natural Zeolites to Synthesized Zeolites 1.1.2 From Low-silica to High-silica Zeolites 1.1.3 From Zeolites to Aluminophosphate Molecular Sieves and Other Microporous Phosphates 1.1.4 From 12-Membered-ring Micropores to Extra-large Micropores 1.1.5 From Extra-large Micropores to Mesopores 1.1.6 Emergence of Macroporous Materials 1.1.7 From Inorganic Porous Frameworks to Porous Metal-organic Frameworks (MOFs) 1.2 Main Applications and Prospects 1.2.1 The Traditional Fields of Application and Prospects of Microporous Molecular Sieves 1.2.2 Prospects in the Application Fields of Novel, High-tech, and Advanced Materials 1.2.3 The Main Application Fields and Prospects for Mesoporous Materials 1.3 The Development of Chemistry for Molecular Sieves and Porous Materials 1.3.1 The Development from Synthesis Chemistry to Molecular Engineering of Porous Materials 1.3.2 Developments in the Catalysis Study of Porous Materials 2 Structural Chemistry of Microporous Materials 2.1 Introduction 2.2 Structural Building Units of Zeolites 2.2.1 Primary Building Units 2.2.2 Secondary Building Units (SBUs) 2.2.3 Characteristic Cage-building Units 9 10 11 13 13 14 19 19 23 23 24 25 vi Contents 2.3 2.4 2.5 2.6 2.2.4 Characteristic Chain- and Layer-building Units 2.2.5 Periodic Building Units (PBUs) Composition of Zeolites 2.3.1 Framework Composition 2.3.2 Distribution and Position of Cations in the Structure 2.3.3 Organic Templates Framework Structures of Zeolites 2.4.1 Loop Configuration and Coordination Sequences 2.4.2 Ring Number of Pore Opening and Channel Dimension in Zeolites 2.4.3 Framework Densities (FDs) 2.4.4 Selected Zeolite Framework Structures Zeolitic Open-framework Structures 2.5.1 Anionic Framework Aluminophosphates with Al/P 2.5.2 Open-framework Gallophosphates with Extra-large Pores 2.5.3 Indium Phosphates with Extra-large Pores and Chiral Open Frameworks 2.5.4 Zinc Phosphates with Extra-large Pores and Chiral Open Frameworks 2.5.5 Iron and Nickel Phosphates with Extra-large Pores 2.5.6 Vanadium Phosphates with Extra-large Pores and Chiral Open Frameworks 2.5.7 Germanates with Extra-large Pores 2.5.8 Indium Sulfides with Extra-large-pore Open Frameworks Summary Synthetic Chemistry of Microporous Compounds (I) – Fundamentals and Synthetic Routes 3.1 Introduction to Hydro(solvo)thermal Synthesis 3.1.1 Features of Hydro(solvo)thermal Synthetic Reactions 3.1.2 Basic Types of Hydro(solvo)thermal Reactions 3.1.3 Properties of Reaction Media 3.1.4 Hydro(solvo)thermal Synthesis Techniques 3.1.5 Survey of the Applications of Hydro(solvo)thermal Synthetic Routes in the Synthesis of Microporous Crystals and the Preparation of Porous Materials 3.2 Synthetic Approaches and Basic Synthetic Laws for Microporous Compounds 3.2.1 Hydrothermal Synthesis Approach to Zeolites 3.2.2 Solvothermal Synthesis Approach to Aluminophosphates 3.2.3 Crystallization of Zeolites under Microwave Irradiation 3.2.4 Hydrothermal Synthesis Approach in the Presence of Fluoride Source 3.2.5 Special Synthesis Approaches and Recent Progress 3.2.6 Application of Combinatorial Synthesis Approach and Technology in the Preparation of Microporous Compounds 29 32 33 33 34 39 41 41 43 47 47 72 72 88 92 93 95 97 100 101 104 117 117 117 119 120 122 123 123 124 144 157 161 164 168 Contents 3.3 Typical Synthetic Procedures for some Important Molecular Sieves 3.3.1 Linde Type A (LTA) 3.3.2 Faujasite (FAU) 3.3.3 Mordenite (MOR) 3.3.4 ZSM-5 (MFI) 3.3.5 Zeolite Beta (BEA) 3.3.6 Linde Type L (LTL) 3.3.7 AlPO4-5 (AFI) 3.3.8 AlPO4-11 (AEL) 3.3.9 SAPO-31 3.3.10 SAPO-34 (CHA) 3.3.11 TS-1 (Ti-ZSM-5) Synthetic Chemistry of Microporous Compounds (II) – Special Compositions, Structures, and Morphologies 4.1 Synthetic Chemistry of Microporous Compounds with Special Compositions and Structures 4.1.1 M(III)X(V)O4-type Microporous Compounds 4.1.2 Microporous Transition Metal Phosphates 4.1.3 Microporous Aluminoborates 4.1.4 Microporous Sulfides, Chlorides, and Nitrides 4.1.5 Extra-large Microporous Compounds 4.1.6 Zeolite-like Molecular Sieves with Intersecting (or Interconnected) Channels 4.1.7 Pillared Layered Microporous Materials 4.1.8 Microporous Chiral Catalytic Materials 4.2 Synthetic Chemistry of Microporous Compounds with Special Morphologies 4.2.1 Single Crystals and Perfect Crystals 4.2.2 Nanocrystals and Ultrafine Particles 4.2.3 The Preparation of Zeolite Membranes and Coatings 4.2.4 Synthesis of Microporous Material with Special Aggregation Morphology in the Presence of Templates 4.2.5 Applications of Zeolite Membranes and Films Crystallization of Microporous Compounds 5.1 Starting Materials of Zeolite Crystallization 5.1.1 Structures and Preparation Methods for Commonly Used Silicon Sources 5.1.2 Structure of Commonly Used Aluminum Sources 5.2 Crystallization Process and Formation Mechanism of Zeolites 5.2.1 Solid Hydrogel Transformation Mechanism 5.2.2 Solution-mediated Transport Mechanism 5.2.3 Important Issues Related to the Solution-mediated Transport Mechanism 5.2.4 Dual-phase Transition Mechanism vii 172 172 173 175 176 177 178 178 179 180 181 181 191 192 192 194 197 199 201 212 215 218 226 226 235 241 248 251 267 268 268 284 285 287 289 294 305 Porous Host–Guest Advanced Materials 665 [183] M Alvaro, V Forues, S Garcia, H Garcia, and J.C Scaiano, Intrazeolite Photochemistry 20 Characterization of Highly Luminescent Europium Complexes Inside Zeolites J Phys Chem B, 1998, 102, 8744–8750 [184] A Stein, Advances in Microporous and Mesoporous solids – Hightlights of Recent Progress Adv Mater., 2003, 15, 763–775 [185] S.L James, Metal-organic Frameworks Chem Soc Rev., 2003, 32, 276–288 [186] S.S.Y Chui, S.M F Lo, J.P.H Charmant, A.G Orpen, and I.D Williams, A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n Science, 1999, 283, 1148–1150 [187] O.M Yaghi, G Li, and H Li, Selective Binding and Removal of Guests in a Microporous Metal-organic Framework Nature (London), 1995, 378, 703–706 [188] H.J Choi and M.P Suh, Self-assembly of Molecular Brick wall and Molecular Honeycomb from Nickel(II) Macrocycle and 1,3,5-Benzenetricarboxylate: Guest-dependent Host Structures J Am Chem Soc., 1998, 120, 10622–10628 [189] B.L Chen, M Eddaoudi, T.M Reineke, J.W Kampf, M O’Keeffe, and O.M Yaghi, Cu2(ATC) Á 6H2O: Design of Open Metal Sites in Porous Metal-organic Crystals (ATC: 1,3,5,7-Adamantane tetracarboxylate) J Am Chem Soc., 2000, 122, 11559–11560 [190] B.L Chen, M Eddaoudi, S.T Hyde, M O’Keeffe, and O.M Yaghi, Interwoven Metalorganic Framework on a Periodic Minimal Surface with Extra-large Pores Science, 2001, 291, 1021–1023 [191] S Noro, R Kitaura, M Kondo, S Kitagawa, T Ishii, H Matsuzaka, and M Yamashita, Framework Engineering by Anions and Porous Functionalities of Cu(II)/4,40 -bpy Coordination Polymers J Am Chem Soc., 2002, 124, 2568–2583 [192] K Biradha and M Fujita, A Springlike 3D-Coordination Network that Shrinks or Swells in a Crystal-to-crystal Manner upon Guest Removal or Readsorption Angew Chem., Int Ed., 2002, 41, 3392–3395 [193] G.J Halder, C.J Kepert, B Moubaraki, K.S Murray, and J.D Cashion, Guest-dependent Spin Crossover in a Nanoporous Molecular Framework Material Science, 2002, 298, 1762–1765 [194] C.D Wu, A Hu, L Zhang, and W Lin, A Homochiral Porous Metal-organic Framework for Highly Enantioselective Heterogeneous Asymmetric Catalysis, J Am Chem Soc., 2005, 127, 8940–8941 [195] B Zhao, P Cheng, Y Dai, C Cheng, D.Z Liao, S.P Yan, Z.H Jiang, and G.L Wang, A Nanotubular 3D Coordination Polymer Based on a 3d-4f Heterometallic Assembly Angew Chem., Int Ed., 2003, 42, 934–936 [196] W Chen, Q Yue, C Chen, H.M Yuan, W Xu, J.S Chen, and S.N Wang, Assembly of a Manganese(II) Pyridine-3,4-dicarboxylate Polymeric Network Based on Infinite Mn–O–C Chains Dalton Trans., 2003, 28–30 [197] C.Y Su, X.P Yang, B.S Kang, and T.C W Mak, Th-Symmetric Nanoporous Network Built of Hexameric Metallamacrocycles with Disparate Cavities for Guest Inclusion Angew Chem., Int Ed., 2001, 40, 1725–1728 [198] R.G Xiong, X.Z You, B.F Abrahams, Z.L Xue, and C.M Che, Enantioseparation of Racemic Organic Molecules by a Zeolite Analogue Angew Chem., Int Ed., 2001, 40, 4422–4425 [199] N.G Pschirer, D.M Ciurtin, M.D Smith, U.H.F Bunz, and H.C zur Loye, Noninterpene˚ Prepared by using trating Square-grid Coordination Polymers with Dimensions of 25 Â 25 A N,N -type Ligands: the First Chiral Square-grid Coordination Polymer Angew Chem., Int Ed., 2002, 41, 583–585 [200] C.J Kepert, T.J Prior, and M.J Rosseinsky, A Versatile Family of Interconvertible Microporous Chiral Molecular Frameworks: the First Example of Ligand Control of Network Chirality J Am Chem., Soc., 2000, 122, 5158–5168 666 Chemistry of Zeolites and Related Porous Materials [201] L Pan, H Liu, X Lei, X Huang, D.H Olson, N.J Turro, and J Li., IRPM-1: A Recyclable Nanoporous Material Suitable for Ship-in-bottle Synthesis and Large Hydrocarbon Sorption Angew Chem., Int Ed., 2003, 42, 542–546 [202] R Kitaura, K Seki, G Akiyama, and S Kitagawa, Porous Coordination-polymer Crystals with Gated Channels Specific for Supercritical Gases Angew Chem., Int Ed., 2003, 42, 428–431 [203] M Eddaoudi, H Li, and O.M Yaghi, Highly Porous and Stable Metal-Organic Frameworks: Structure Design and Sorption Properties J Am Chem Soc., 2000, 122, 1391–1397 [204] L.N Rosi, M Eddaoudi, J Kim, M O’Keeffe, and O.M Yaghi, Infinite Secondary Building Units and Forbidden Catenation in Metal-organic Frameworks Angew Chem., Int Ed., 2002, 41, 284–287 [205] N.L Rosi, J Eckert, M Eddaoudi, D.T Vodak, J Kim, M O’Keeffe, and O.M Yaghi, Hydrogen Storage in Microporous Metal-organic Frameworks Science, 2003, 300, 1127–1129 [206] M Eddaoudi, J Kim, N Rosi, D Vodak, J Wachter, M O’Keefe, and O.M Yaghi, Systematic Design of Pore Size and Functionality in Isoreticular MOFs and their Application in Methane Storage Science, 2002, 295, 469–472 [207] J.S Seo, D Whang, H Lee, S.I Jun, J Oh, Y.J Jeon, and K Kim, A Homochiral Metalorganic Porous Material for Enantioselective Separation and Catalysis Nature (London), 2000, 404, 982–986 [208] W Chen, J.Y Wang, C Chen, Q Yue, H.M Yuan, J.S Chen, and S.N Wang, Photoluminescent Metal-organic Polymer Constructed from Trimetallic Clusters and Mixed Carboxylates Inorg Chem., 2003, 42, 944–946 [209] J Sun, L Weng, Y Zhou, J Chen, Z Chen, Z Liu, and D Zhao, QMOF-1 and QMOF-2: Three-dimensional Metal-organic Open Frameworks with a Quartzlike Topology Angew Chem., Int Ed., 2002, 41, 4471–4473 [210] B Panella, M Hirscher, H Pu¨tter, and U Muller, Hydrogen Adsorption in Metal–organic Frameworks: Cu-MOFs and Zn-MOFs Compared Adv Funct Mater., 2006, 16, 520–524 [211] X Lin, A.J Blake, C Wilson, X.Z Sun, N.R Champness, M.W George, P Hubberstey, R Mokaya, and M Schroder, A Porous Framework Polymer Based on a zinc(II) 4,40 Bipyridine-2,20 ,6,60 -tetracarboxylate: Synthesis, Structure, and ‘Zeolite-Like’ Behaviors J Am Chem Soc., 2006, 128, 10745–10753 [212] A.G Wong-Foy, A.J Matzger, and O.M Yaghi, Exceptional H2 Saturation Uptake in Microporous Metal-organic Frameworks J Am Chem Soc., 2006, 128, 3494–3495 [213] G Garberoglio, A.I Skoulidas, and J.K Johnson, Adsorption of Gases in Metal Organic Materials: Comparison of Simulations and Experiments J Phys Chem B, 2005, 109, 13094–13103 [214] Q Yang and C Zhong, Understanding Hydrogen Adsorption in Metal-organic Frameworks with Open Metal Sites: a Computational Study J Phys Chem B, 2006, 110, 655–658 [215] D.F Sun, S.Q Ma, Y.X Ke, D.J Collins, and H.C Zhou, An Interweaving MOF with High Hydrogen Uptake J Am Chem Soc., 2006, 128, 3896–3897 Further Reading Important monographs, proceedings, and journals on molecular sieves and porous materials Important monographs [1] D.W Breck, Zeolite Molecular Sieves, Structure, Chemistry and Use John Wiley & Sons, New York, London, Sydney, Toronto, 1974 [2] Dalian Institute of Chemical Physics, Chinese Academy of Sciences Zeolite Molecular Sieves Science Press, Beijing, 1978 (Chinese) [3] A Dyer, An Introduction to Zeolite Molecular Sieves John Wiley & Sons Ltd, Chichester, 1988 [4] R Szostak, Handbook of Molecular Sieves Van Nostrand Reinhold, New York, 1992 [5] R Szostak, Molecular Sieves, Principles of Synthesis and Identification Blackie Academic & Professional, London, 1998 [6] R Szostak, Handbook of Molecular Sieves – Structures Springer, New York, 2006 [7] F Schu¨th, S.W.S Kenneth, and J Weitkamp, Handbook of Porous Solids John Wiley & Sons, New York, 2002 [8] H.G Karge and J Weitkamp, Molecular Sieves Vol 1, Synthesis Springer, Berlin, Heidelberg, New York, Tokyo, 1998 [9] H.G Karge and J Weitkarp, Molecular Sieves Vol 2, Structures and Structure Determination Springer, Berlin, Heidelberg, 1999 [10] H.G Karge and J Weitkarp, Molecular Sieves Vol 3, Post-Synthesis Modification I Springer, 2002 [11] H.G Karge and J Weitkarp, Molecular Sieves Vol 4, Characterization I Springer, 2004 [12] H.G Karge and J Weitkarp, Molecular Sieves Vol 5, Characterization II Springer, 2006 [13] R.M Barrer, Hydrothermal Chemistry of Zeolites Academic Press, London, New York, 1982 [14] P.A Jacobs and J.A Martens, Synthesis of High-silicon Aluminosilicate Zeolites Stud Surf Sci Catal., 33, 1987 Chemistry of Zeolites and Related Porous Material – Synthesis and Structure Ruren Xu, Wenqin Pang, Jihong Yu, Qisheng Huo and Jiesheng Chen # 2007 John Wiley & Sons, (Asia) Pte Ltd 668 Chemistry of Zeolites and Related Porous Materials [15] H.K Beyer, H.G Karge, I Kirics, and J.B Nagy, (Eds) Catalysis by Microporous Materials Stud Surf Sci Catal 94, 1994 [16] R.R Xu, Z Gao, and Y Xu, Progress in Zeolite Science – A China Perspective World Scientific Press, Singapore, New Jersey, London, Hong Kong, 1995 [17] H Chon, S.I Woo, and S.E Park, Recent Advance and New Horizons in Zeolite Science and Technology Elsevier, Amsterdam, 1996 [18] J Weitkamp and L Puppe, Catalysis and Zeolites, Fundamentals and Applications Springer, Berlin, 1999 [19] H Van Bekkum, P.A Jacobs, E.M Flanigen, and J.C Jansen, Introduction to Zeolite Science and Techology, Elsevier, Amsterdam, 137 2001 [20] H Ghobarkar, O Scha¨f, Y Massiani, and P Knauth, The Reconstruction of Natural Zeolites, A New Approach to Announce Old Materials by Their Synthesis Springer, New York, 2004 [21] C.R.A Catlow, R.A van Santen, and B Smit, Computer Modelling of Microporous Materials, Elsevier, 2004 Manuals and Atlases [1] Verified Synthesis of Zeolitic Materials Synthesis Commission of the International Zeolite Association, 2nd Edn, ed H Robson, Elsevier, 2001 [2] Atlas of Zeolite Framework Types Structure Commission of the International Zeolite Association, 5th Edn, eds Ch Baerlocher, W.M Meier, and D.H Olson, Elsevier, 2001 [3] Collection of Simulated XRD Powder Patterns for Zeolites Structure Commission of the International Zeolite Association, 4th Edn, ed M.M.J Treacy and J.B Higgins, Elsevier, 2001 Proceedings of International Zeolite Conferences (IZC) [1] Molecular Sieves Proceedings of the lst IZC, London, U.K., 1967, Society of Chemical Industry London, 1968 [2] Molecular Sieves I and II Proceedings of the 2nd IZC, Worcester, U.S.A., 1970, Adv Chem Ser., 101 and 102, 1971 [3] Molecular Sieves Proceedings of the 3rd IZC, Zu¨rich, Switzerland, 1973, ed W.M Meier and J.B Uytterhoeven, Adv Chem Ser., 121, 1973 [4] Molecular Sieves - II Proceedings of the 4th IZC, Chicago, U.S.A., 1977, ed J.R Katzer, ACS Symp Ser., 40, 1977 [5] Proceedings of the 5th Intenational Conference on Zeolites Proceedings of the 5th IZC, Naples, ltaly, 1980, ed L.V.C Rees, Heyden, London, Philadelphia, Rheine, 1980 [6] Proceedings of the 6th International Conference on Zeolites Proceedings of the 6th IZC, Reno, U.S.A., 1983, ed D Olson and A Bisio, Butterworths, Guildford, 1984 [7] New Developments in Zeolites Science and Technology Proceedings of the 7th IZC, Tokyo, Japan, 1986, ed Y Murakami, A Iijima, and J.W Ward, Stud Surf Sci Catal., 28, 1986 [8] Zeolites: Facts, Figures, Future Proceedings of the 8th IZC, Amsterdam, Netherlands, 1989, ed P.A Jacobs and R.A Van Santen, Stud Surf Sci Catal., 49, 1989 [9] Proceedings from the 9th IZC, Montreal, Canada, 1992, ed R von Ballmoos, J.B Higgins, and M.M.J Treacy, Butterworth-Heinemann, Boston, London, 1992 [10] Zeolites and Related Microporous Materials State of the Art 1994, Proceedings of the 10th IZC, Garmisch-Partenkirchen, Germany, 1994, ed J Weitkamp, H.G Karge, H Pfeifer, and W Holderich, Stud Surf Sci Catal., 84 1994 Further Reading 669 [11] Progress in Zeolite and Microporous Materials Proceedings of the 11th IZC, Seoul, Korea, 1996, ed Chon Hakze, Ihm Son-ki and Uh Young Sun, Stud Surf Sci Catal., 105, 1996 [12] Proceedings of the 12th IZC, ed M.M.J Treacy, B.K Marcus, M.E Bisher, and J.B Higgins, MRS, Baltimore, U.S.A., 1998 [13] Zeolite and Mesoporous Materials of the Dawn of the 21st Century Proceedings of the 13th IZC, Montpellier, France, 2001, ed A Galarneau, F Di Renzo, F Fajula, and J Verdrine, Stud Surf Sci Catal., 135, 2001 [14] Recent Advances in the Science and Technology of Zeolites and Related Materials Proceedings of the 14th IZC, Cape Town, South Africa, 2004, ed E Sreen, L.H Callanan, and M Claeys, Stud Surf Sci Catal., 154, 2004 Proceedings of important international symposiums on different topics (1) Synthesis [1] [2] [3] [4] Zeolites, Synthesis, Structure, Technology and Application Stud Surf Sci Catal., 24B, 1985 Synthesis of High-silicon Aluminosilicate Zeolites Stud Surf Sci Catal., 33, 1986 Innovation in Zeolite Materials Science Stud Surf Sci Catal., 37, 1988 Zeolite Synthesis ACS Symp Ser., 398, 1989 (2) Characterization [1] Characterization of Porous Solids Proceedings of the IUPAC Symposium (COPS I), 1987 Stud Surf Sci Catal 39, 1987 [2] Characterization of Porous Solids II Proceedings of the IUPAC Symposium (COPS II), 1990 Stud Surf Sci Catal., 62, 1990 [3] Characterization of Porous Solids III Proceedings of the IUPAC Symposium (COPS III), 1993 Stud Surf Sci Catal., 87, 1993 [4] Characterisation of Porous Solids V Proceedings of the 5th International Symposium on the Characterisation of Porous Solids (COPS-V), Heidelberg, Germany, 1999 Stud Surf Sci Catal 128, 1999 [5] Characterization of Porous Solids VI Proceedings of the 6th International Symposium on the Characterization of Porous Solids (COPS-VI), Allicante, Spain, 2002 Stud Surf Sci Catal., 144, 2002 [6] Characterization of Porous Solids VII Proceedings of the 7th International Symposium on the Characterization of Porous Solids (COPS-VII), Aix-en-Provence, France, 2005 Stud Surf Sci Catal., 160, 2005 (3) Structure [1] Structure and Reactivity of Modified Zeolites Proceedings of an International Conference, Prague, 1984 Stud Surf Sci Catal., 18, 1984 (4) Catalysis and adsorption [1] Catalysis by Zeolites Proceedings of an International Symposium, 1980 Stud Surf Sci Catal., 5, 1980 [2] Zeolites as Catalysts, Sorbents and Detergent Builders Applications and Innovations Proceedings of an International Symposium, Wu¨zburg, 1988 Stud Surf Sci Catal., 46, 1988 670 Chemistry of Zeolites and Related Porous Materials [3] Catalysis and Adsorption by Zeolites Proceedings of ZEOCAT 90, Leipzig, 1990 Stud Surf Sci Catal., 65, 1990 [4] Zeolite Chemistry and Catalysis Proceedings of an International Symposium, Czechoslovakia, 1991 Stud Surf Sci Catal., 69, 1991 [5] Catalysis by Microporous Materials Proceedings of ZEOCAT’95, Hungary, 1995 Stud Surf Sci Catal., 94, 1995 [6] Zeolites: A Refined Tool for Designing Catalytic Sites Proceedings of the International Symposium, Canada, 1995 Stud Surf Sci Catal., 97, 1995 (5) Mesoporous materials [1] Mesoporous Molecular Sieves 1998 Proceedings of the 1st International Symposium, USA, 1998 Stud Surf Sci Catal., 117, 1998 [2] Nanoporous Materials II Proceedings of the 2nd Conference on Access in Nanoporous Materials, Canada, 2000 Stud Surf Sci Catal., 129, 2000 [3] Proceedings of the 2nd International Symposium on Mesoporous Molecular Sieves (ISMMS), Microporous and Mesoporous Materials, 44–45, ed L Bonneviot, S Giasson, S Kaliaguine, and M Sto¨cker, Elsevier, Amsterdam, 2001 [4] Nanoporous Materials III Proceedings of the 3rd International Symposium on Nanoporous Materials, Canada, 2002 Stud Surf Sci Catal., 141, 2002 [5] Nanotechnology in Mesostructured Materials Proceedings of the 3rd International Mesostructured Materials Symposium, Korea, 2002 Stud Surf Sci Catal., 146, 2000 [6] Mesoporous Crystals and Related Nano-Structured Materials Proceedings of the Meeting on Mesoporous Crystals and Related Nano-Structured Materials, Stockholm, Sweden, 2004 Stud Surf Sci Catal., 148, 2000 [7] Nanoporous Materials IV Proceedings of the 4th International Symposium on Nanoporous Materials, Niagara Falls, Ontario, Canada, 2005, Stud Surf Sci Catal., 156, 2005 (6) Advanced materials [1] Innovation in Zeolite Materials Science Proceedings of an International Symposium, Nieuwpoort, 1987 Stud Surf Sci Catal., 37, 1987 [2] Advanced Zeolite Science and Applications Stud Surf Sci Catal., 85, 1993 [3] Porous Materials in Environmentally Friendly Processes Proceedings of the 1st International FEZA Conference, Hungary, 1999 Stud Surf Sci Catal., 125, 1999 (7) ZMPC (Japan) [1] Chemistry of Microporous Crystals Proceedings of the International Symposium on Chemistry of Microporous Crystals, Tokyo, 1990 Stud Surf Sci Catal., 60, 1990 [2] Zeolites and Microporous Crystals Proceedings of the International Symposium on Zeolites and Microporous Crystals, Japan, 1993 Stud, Surf Sci Catal., 83, 1993 [3] Zeolite and Microporous Crystals Proceedings of the International Symposium on ZMPC, 1997 Microporous Mesoporous Mater., 21/4–6, 1998 [4] Zeolite and Microporous Crystals Proceedings of the International Symposium on ZMPC, 2001 Microporous Mesoporous Mater., 48, 2001 [5] Zeolite and Microporous Crystals Proceedings of the International Symposium on ZMPC, 2006, Microporous Mesoporous Mater., in press, 2007 Further Reading 671 (8) Proceedings of FEZA (Federation of the European Zeolite Associations) [1] Porous Materials in Environmentally Friendly Processes Proceedings of the 1st International FEZA Conference, Eger, Hungary, 1999 Stud Surf Sci Catal., 125, 1999 [2] Zeolites and Ordered Mesoporous Materials: Progress and Prospects The 1st FEZA School on Zeolites, Prague, Czech Republic, 2005 Stud Surf Sci Catal., 157, 2005 [3] Impact of Zeolites and Other Porous Materials on the New Technologies at the Beginning of the New Millennium Proceedings of the 2nd International FEZA Conference, Taormina, Italy, 2002 Stud Surf Sci Catal., 142, 2002 [4] Proceedings of the 3rd International FEZA Conference, Prague, Czech Republic, 2005 Stud Surf Sci Catal., 158, 2005 Important international journals [1] Zeolites, ed L.V.C Rees and R von Ballmoos, Butterworth, [2] Heinemann, Stoneham, MA, USA, 1981–1993 [3] Microporous Materials, ed J Weitkamp, Elsevier, Amsterdam, London, New York, Tokyo, 1993–1997 [4] Microporous and Mesoporous Materials, Ed-in-chief M Sto¨cker, Founding ed J Weitkamp; Regional ed S.L Suib, R.W Thompson, and K Kuroda, Elsevier, Amsterdam, London, New York, Tokyo, as from 1998 The above three are the official publications of the International Zeolite Association Besides, lots of papers on molecular sieves and porous materials have been frequently published in some journals on inorganic chemistry (Inorg Chem., J Chem Soc., Dalton Trans., etc.), physical chemistry (J Phys Chem and Langmuir, etc.), material chemistry (Chem Mater and J Mater Chem etc.), solid-state chemistry (J Solid State Chem and Solid, State, Sci., etc.), catalytic chemistry (J Catal Appl Catal., A, Curr Opin Colloid Interface Sci., etc.), and some famous communication journals, such as Chem Commun and Angew Chem., etc Some important creative letters and reviews have also been published in Nature, Science, Chem Rev., Chem Soc Rev., and Acc Chem Res., etc Index 2-D hexagonal mesophase 498–505 3-D hexagonal mesophase 482, 491, 577 AASBUs 406–14 Adsorption isotherms 354, 355 Adsorption of hydrogen 655 Adsorption properties 352, 381 Aging 130–5, 296–300 Aging temperature 136–7 AlPO4-11 (AEL) synthesis 179–80 AlPO4-5 (AFI) rational synthesis 432–3 structure 66–7 synthesis 178–9 with encapsulated dye molecules 617 AlPO-CJ11 structure 78, 79 AlPO-CJ19 structure 80 AlPO-CJ4 structure 74–5 AlPO-CJB1 structure 78–80 AlPO-CSC structure 87–8, 455–7 AlPO-DETA structure 75–6 AlPO-ESC structure 87–8 AlPO-HDA structure 76, 77 synthesis 441–3 AlPO-PDA synthesis 442 Aluminoarsenates synthesis 193 Aluminoborates anionic framework 198 positive framework 198–9 Aluminophosphates anionic framework 72–88 composition 33 structure design 412–4, 426–8 structural construction regularity 153–7 Aluminosilicates gel primary gel 131 secondary gel 131–5 structure and aging 296–300 Aluminosilicates composition 33 Aluminium source 125 Ammonolysis 347 Amorphous SiO2 preparation 283 structure 279–80 AMS-n 508 Anionic surfactants 537 Chemistry of Zeolites and Related Porous Material – Synthesis and Structure Ruren Xu, Wenqin Pang, Jihong Yu, Qisheng Huo and Jiesheng Chen # 2007 John Wiley & Sons, (Asia) Pte Ltd 674 Index Application of zeolite coatings corrosion-resistant coatings 253 for pervaporation 255–7 hydrophilic and antimicrobial coatings 254 Assembly of 2-D nets allowed operators 404 enumeration of structures 404–6 operators 402–3 sheet conformation 403–4 ASU-16 structure 100–1 synthesis 210 ASU-31 structure 101 ASU-32 structure 101–2 BEC structure 56 synthesis 458 Beta (BEA) structure 54–6 synthesis 177–8, 213–4 Block copolymer surfactants 477, 490, 538 Building units cage 25, 27–9 chain 29–30 layer 30–2, 401–2 periodic building units 32–3 primary building units 23–4 secondary building unites (SBUs) 24–6 Building-block built-up approach AlPO-CSC 455–7 C60 624 Caged mesostructures 508–20 Cancrinite (CAN) structure 51–2 Carbon nanotube growth in zeolites 625–31 Cationic surfactants 535–7 Cations distribution and position in framework 34 templating effect in crystallization 139–44 Chabazite (CHA) structure 52 Channel and surface modification cation exchange method 380–1 channel modification method 381–3 external surface modification 383–91 internal surface modification 383 Channel dimension 43–6 Charge density matching 151–3 Charge-balancing effect 318 Chelating dealumination 365, 366 Chemical dealumination 364, 371 Chemical modification of mesoporous silica 558–61 Chemical-liquid deposition (CLD) 387–91 Chemical-vapor deposition (CVD) 633–8, 241, 384–5, 387 Chiral building blocks 225 Chiral catalytic centers 218–219 Chiral catalytic materials 221–6 assembly of chiral catalytic centers 218–9 coordination and condensation of chiral building blocks 225–6 germanates 219–21 phosphates 222–3 silicates 218–26 uranyl molybdates 221–2 Chiral mesoporous silica 581–2 Chiral metal complexes 443–54 Chiral open frameworks 92, 93, 97 Chiral porous coordination polymer 651–2, 654 Chirality transfer 443–54 CIT-1(CON) structure 60, 62 synthesis 458 CIT-5 (CFI) synthesis 203 structure 56–7 CLD-modified HZSM-5 387, 389, 390 Cloverite (-CLO) synthesis 204 structure 69–71 Cluster crystal 610–1 CMK-n 568–71 Co-condensation 560–1 Combinatorial synthesis 168–72, 454–5 Condensation reaction of silicate and aluminate ions 294–6 Coordination polymer 647–55 Coordination sequences (CSQ) 42 Critical micelle concentration (CMC) 480 Crystal transition 165–6 Crystallization field 125–8 Crystallization kinetics 326–37 Crystallization process 285–7 Crystallization temperature 137–8 Index Cubic channel mesostructures 505–8 Cubic-hexagonal intergrowth 508–511 CVD-modified SiHM catalyst 386 CZP structure 71 Data mining 430–3 De novo molecular design 434–5 Dealumination liquid phase method 364 hydrothermal and chemical methods 371–3 high-temperature 362–3 vapor phase method 370–1 Decision tree 431 Deformed mesophases 520–5 Degree of polarization (DOP) 629 Detemplating 345, 347, 348 extraction 348–50 Dry gel conversion 166 Dual-phase transition mechanism 305–6 Dyes in zeolites 616–20 ECR-34(ETR) structure 62, 63 EMT structure 50–1 Energy minimization 437 Evaporation-induced self-assembly (EISA) 534–5 Extra-large pore materials structure 88, 92–3, 95, 97, 100 synthesis 201–11 Faujasite (FAU) structure 50 synthesis of Linde-Y type 173–5 synthesis of Low-silica type X (LSX) FDU-1 synthesis 511–2 FDU-12 synthesis 518–20 FDU-4 structure 100 synthesis 209 FDU-5 synthesis 508 FJ-1 synthesis 209 Fluoride ion 161–4 Forbidden zone 415–26 174 675 Formation mechanism mesoporous silica 478–489 charge density matching 485–7 cooperative formation mechanism 483–5 folding sheets mechanism 486–7 generalized liquid crystal templating mechanism 487 original liquid crystal templating (LCT) mechanism 482–3 true liquid crystal templating mechanism (LCT) 487–8 microporous zeolites 285–7 Framework density 47 FSM-16 synthesis 486–7 Fullerenes assembled in zeolites 624 Gallium-containing zeolites 374 Galloarsenates synthesis 193 Gallophosphates structure 88–92 synthesis 192 Gas separation membranes 242 LTA 242 MFI 242 Gelation of silica sol 280–2 Gemini surfactants 535–6 Genetic algorithm 428 Germanates 100–1 Grafting 559–60 Heteroatoms coating zeolites 373, 378 Hexagonal mesoporous silica materials 498–505 Hierarchical porous silica materials 531–3 High-resolution electron microscopy 627 High-temperature calcination 345, 346 High-temperature rapid crystallization 167 High-temperature vapor-phase treatment 378 Host-guest interaction energy 435–54, 620 Hydro(solvo)thermal synthesis 122–4 Hydrogen uptake 653–4 Hydrogen-bonding interaction 435–54 Hydrogen-storage 652–5 Hypothetical zeolite database 429–30 IM-12(UTL) structure 65–6 676 Index IM-12(UTL) synthesis 459 Indium phosphates structure 92–3 synthesis 194 Indium sulfides structure 101–2 Inorganic-organic hybrid materials 563–4 Interaction between organic and inorganic 475–478 Intersecting channel zeolites synthesis 212–5 Ion clusters location 609–10 Ion-exchange modification 351 Ion-exchange of zeolites under microwave irradiation 160–1 Ionic liquids 167 Iron phosphates structure 95–6 Isomorphous substitution 33, 368, 373–8 demetallation 378–9 gas-solid 377–8 liquid-solid 374–7 ITQ-15 (UTL) synthesis 459 ITQ-17 structure 56 ITQ-21 synthesis 458 ITQ-22 (IWW) synthesis 213, 458–9 structure 60, 61 ITQ-24(IWR) structure 65 ITQ-29 (LTA) synthesis 453–4 JDF-20 structure synthesis JLU-10 structure JLU-7 structure JLU-8 structure JLU-9 structure 76–8 205 450–2 444–7 447–8 448–50 KIT-6 506 KSW-2 522, 524–5 Loop configuration 41–2 Lowenstein’s Rule 33, 412 LTA structure 49–50 synthesis 172–3 LTL structure 51 synthesis 178 M41S materials 469–71 Macroporous material templating synthesis 529–31 MCM-41 498–500, 619 MCM-48 505–7 MCM-50 470, 479, 485 Mesopore size control 526–7 Mesoporous carbon 568 Mesoporous carbon as template 540 Mesoporous fiber 579–80 Mesoporous material synthesis through acid-base pair 555–6 Mesoporous metal oxides 565–7 Mesoporous metals 571–2 Mesoporous nanoparticles 575 Mesoporous phosphates 567 Mesoporous spheres and balls 577–9 Mesoporous thin film 576–7 Metal cluster in pore preparation approaches 605–7 alkali metal cluster 607 bimetallic cluster 606 cadmium 615 noble metal cluster 613–4 mercury 614 Metal cluster ion in pore alkali metal ion cluster 609–12 bifunctional catalyst 613 electrical conductivity 612 ESR spectra 609–13 metal-containing mesoporous silica-based materials 562–3 Na43þ 607–8 Metal complexes in pore catalytic performance of the loaded complex 636–7 epoxidatin reaction 644–6 Index nonaromatic macrocyclic ligand 645 redox pair 646 Metal-organic framework (MOF) 8–9, 651–5 Coordination polymer 647–9 Metal-Schiff base hydrogenation of alkenes 641 phthalocyanine complex 642–3 salen 641 selective hydrogenation catalyst 641 silylation agent 643 Methylene blue 616 Microporous chlorides 200 Microporous nitrides 201 Microporous sulfides 200 Microwave radiation 346 Microwave synthesis AlPO4-5 159–60 NaA 158–9 MIL-31 structure 89 Mixed ligand system 652 Mixed surfactants 538–9 Molecular engineering 13–14 Molecular simulation 324–5, 654–5 Mordenite (MOR) structure 52–3 synthesis 175–6 Morphologies of mesoporous silicas 573 MSU-n 525, 542, 547 Multicarboxylate linker 652–3 Nanocrystals and ultrafine zeolite particles 235–41 controlled crystallization condition 238–9 controlled crystallization in microreactor 239–40 controlled crystallization of sol 236–7 nanozeolite catalytic materials 240 ND-1 structure 93 synthesis 207 Nickel phosphates structure 96–7 Non equilibrium thermodynamics 118 Non-ionic (neutral) surfactants 537 Non-silica mesoporous materials 561–2 NTHU-1 structure 90 synthesis 207 Nucleation 300–5 677 Si-ZSM-48 302–304 Si-ZSM-5 302–304 One-dimensional superconductor 631 Ordered mesoporous materials 468–71 Organic chelate of silicon 283 Outer space synthesis 167 Oxide-modified HZSM-5 zeolite 382 Oxidative detemplating 347 Periodic mesoporous organosilicas (PMOs) 564–5 Phase transformation and control in mesoporous materials 525–6 Physical chemistry of mesostructure assembly 491–4 Pillared layered microporous materials 215–7 Polymer in zeolites 621–23 Polymeric surfactant 538 Polymerization state 269–75, 284–5 aluminate 284–5 polysilicate ions 269–77 in potassium silicate solution 270–1 in sodium salt solution 269–70, 271 in tetrabutylammonium silicate (TBAS) aqueous solution 275–7 in tetraethylammonium silicate (TEAS) aqueous solution 274–5 in tetramethylammonium silicate (TMAS) aqueous solution 272–3 Preparation of porous carbon 623–4 Pseudo-boehmite 284 Quantum wire 612 Raman spectroscopy 627 Rational synthesis 430–59 Removal of surfactant from mesoporous silica 539–40 Ring number 43 SAPO-31 synthesis 180–1 SAPO-34(CHA) synthesis 181 composition 33–4 SBA-1 synthesis 512–3 SBA-15 synthesis 500–3 678 Index SBA-16 synthesis 517–8 SBA-2 synthesis 509–511 SBA-3 synthesis 503–5 SBA-6 synthesis 514–7 SBA-8 synthesis 520–3 SDA cleavage 168 Secondary synthesis 164–5, 350, 377 Semiconductor clusters in zeolites Cd4S4 633–4 HgI2 634 III-V semiconductor nanocluster 635 PbI2 634 Se, Te, Ge and Si 635 silver sulfide 634 Semiconductor nanoparticles blue-shift phenomenon 631 luminescence 632 metal-organic chemical-vapor deposition (MOCVD) 631 optoelectronic property 631 zero-dimensional semiconductor clusters 631 Sensor chemical-sensing material 613 water-vapor-sensing material 613 Shape-selective adsorption 384, 385 Shape-selective catalysis 651 Sharpless catalysts 219 Ship-in-bottle strategy 11 Si-addition 368, 370 Silica gel preparation 282–3 structure 279–280 Silica mesophases 541–2 Silica sol gelation 280 preparation 279 structure 277–80 Siliceous mesostructured cellular foams (MCFs) 531 Silicon enrichment 364 Silicon-addition 367 Silicon-enrich zeolites 366 Simulated annealing 399–401, 406–12 Single crystal mesoporous material bulk material dissolution 234–5 clear homogeneous system 234 FÀ ions systems 230–3 influence of nucleation suppressors 227 solvothermal conditions 228–30 two silica sources 233 Single-walled carbon nanotubes 627–31 Sodalite (SOD) structure 48–9 Sodalite cage 609–10 Solid hydrogel transformation 287–9 Solid laser 618 Solution-mediated transport mechanism 294–305 Solvent polarity (ETN) 121 Solvent-extraction method 348 Space-filling effect 39, 317–8 Special aggregation morphology AlPO4-5 fibers 250 silicate-1 microspheres 250 cellular structures 249–50 SSZ-23(STT) structure 57–9 SSZ-53(SFH) synthesis 452–3 structure 62, 63, 64–5 SSZ-59(SFN) synthesis 452–3 structure 63, 64–5 Structure-directing effect (SDE) 39, 307–26 Structure-type code 20–3 Supercage of Y zeolites 614 Surfactant effective packing parameter: g 489–491 Surfactant micelle and lyotropic liquid crystal 479–481 Synthesis of mesoporous materials at high temperatures 556–7 parameters 550–555 Systematic enumeration 401–6 Template for zeolites anions 322–4 cations 307–8 FÀ ion 320–1 metal complex 321–2 organic compounds 308–20 salts 322–4 water 322–4 Index Titanium-containing zeolites 181–2, 377 True templating effect 40–1, 311–3 Two-step calcination 346 Type material 20 UCSB-6(SBS) structure 71–2 ULM-16 synthesis 206 ULM-5 structure 89 synthesis 206 Ultra-stabilization 361, 362, 363 USY (ultra-stable Y zeolite) 363–73 UTD-1 (DON) synthesis 201, 203 structure 59–60 Vanadium phosphates 97–9 Vertex symbol 42 VPI-5 (VFI) synthesis 203 structure 67–8, 69 VSB-1 synthesis 208 VSB-5 structure 96–7 synthesis 208 Window size for caged mesostructures 527–9 679 Xe-adsorption-dynamic curves 382 Zeolite extra-large micropore 5–6 high-silica low-silica 3–4 macropore 7–8 mesopore 6–7 natural 2–3 Zeolite films on stable supports 241–8 layer-by-layer (LBL) 243 a-axis oriented MFI zeolite films 245 b-axis oriented MFI zeolite films 244–5 patterned zeolite films 247–8 spin-on zeolite films 245–7 self-supporting zeolitic crystalline 241 low dielectric constant films 251 Zinc phosphates dimension build-up mechanism 197 structure 93–5 structure characters 195 synthetic approach 196 ZnHPO-CJ1 synthesis 211 ZSM-11 (MEL) structure 54 ZSM-5 (MFI) structure 53 synthesis 176–7 [...]... Inorganic synthesis and preparative chemistry, hydrothermal and solvothermal chemistry, sol–gel chemistry, crystallization and 14 Chemistry of Zeolites and Related Porous Materials crystal–growth, host–guest chemistry, and combinatorial chemistry all help to paved the way for the progress of the synthetic chemistry of porous materials or the so-called ‘pore-construction’ synthetic chemistry On the other hand,... number of unique zeolites might be enormous The announcement of M41S compounds in 1992 by Mobil scientists has stimulated rapid growth of mesoporous materials, whereas the study of macroporous materials has just begun to burgeon, and their special structural features and properties Chemistry of Zeolites and Related Porous Material – Synthesis and Structure Ruren Xu, Wenqin Pang, Jihong Yu, Qisheng Huo and. .. John Wiley & Sons, (Asia) Pte Ltd 2 Chemistry of Zeolites and Related Porous Materials are very attractive From microporous to mesoporous to macroporous, the conventional framework compositions of molecular sieves and porous materials are purely inorganic However, in recent years, the appearance of porous metal-organic frameworks (MOFs) has greatly enhanced the diversity and compositional complexity of. .. the pool of porous materials that traditionally have their frameworks made of inorganic elements In addition, the MOF materials with their unique structural and functional characteristics have greatly diversified the existing porous materials Clearly, the rapid development of microporous compounds and the advent of mesoporous, macroporous, and MOF materials have expanded the already rich and complex... porous composite chemistry In particular, the overlap of molecular sieve science with other related sciences, including physics, mathematics, computer science, materials science, and biology, has promoted the in-depth development of the chemistry of molecular sieves and porous materials 16 Chemistry of Zeolites and Related Porous Materials References [1] M.E Davis, Ordered Porous Materials for Emerging... series of zeolites with low Si/Al ratios were hydrothermally synthesized through mimicking of the geothermal formation of natural zeolites The successful synthesis of zeolites laid the foundation for rapid development of zeolite industry in the 20th and 21st centuries Porous compounds or porous materials share the common feature of regular and uniform porous structures To describe a porous structure, ... engineering is the chemistry of rational design and synthesis The key impact of molecular engineering on chemistry is that it broadens the perspectives on function, structure, and synthesis, draws more attention to ‘function– structure synthesis , and promotes a better understanding of structure types and levels beyond molecular structures, rather than excessively focusing on the synthesis of individual... composite materials, it is believed that mesoporous materials will play more important roles in the 21st century as an increasing number of mesoporous materials with advanced functions are designed and synthesized 1.3 The Development of Chemistry for Molecular Sieves and Porous Materials In the past half century, with the expansion of structure types and compositions of porous materials, the number of application... structural chemistry of microporous and mesoporous materials as the core Five chapters (Chapters 3, 4, 5, 6, and 8) are allocated to cover the synthetic aspects of the topic Chapter 3 introduces the synthesis and related fundamental principles, synthetic strategies, and techniques for the major microporous materials such as zeolites and microporous aluminophosphates This Chapter serves as Part I of the... synthetic chemistry for pore construction, and to conduct an in-depth study on related scientific issues, such as the structures of intermediates and products, the polymerization of reactants, the structures and transformation of sols and gels, nucleation and crystallization, the templating and structure- directing effects, the metastable state and crystal transformation, and the growth of crystals and their