ISBN-13: 9783527325146 / Angielski / Twarda / 2010 / 918 str.
ISBN-13: 9783527325146 / Angielski / Twarda / 2010 / 918 str.
This indispensable two-volume handbook covers everything on this hot research field. The first part deals with the synthesis, modification, characterization and application of catalytic active zeolites, while the second focuses on such reaction types as cracking, hydrocracking, isomerization, reforming and other industrially important topics.
Edited by a highly experienced and internationally renowned team with chapters written by the -Who's Who- of zeolite research.
It is accessible to both experienced and inexperienced researchers in the field of micro– and mesoporous silicate materials. It has excellent micrographs of zeolite crystals, figures of processes and timelines of scientific discovery in the zeolite world. Taking all these points into account, I highly recommend this text to both experienced and early–stage researchers in the field. (Applied Organometallic Chemistry, 6 March 2015)
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
1.4.2 Solution Chemistry Oligomers and Nanoparticles 17
1.4.3 Modeling 21
1.5 Case Studies 23
1.5.1 Zeolite A 23
1.5.2 Silicalite 28
1.5.3 LTL 33
1.5.4 STA–7 35
1.5.5 Zincophosphates 43
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
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 Pérez–Pariente, Raquel García, Luis Gómez–Hortigüela, and Ana Belén 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 ?¿m) 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
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(NO3)3 Solution under Acidic Conditions 158
6.3.2 Synthesis of Hydrophobic Zeolites by Hydrothermal Treatment with Acetic Acid 162
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
7.3.4 The Current Limits of Structural Complexity in Zeolites 193
7.3.5 Chirality and Mesoporosity 195
7.3.6 Ordered Vacancies and Growth Defects 197
7.3.7 Zeolites from Layered Precursors 198
7.3.8 Substitution of Framework Oxygen Atoms 199
7.4 Summary and Outlook 201
7.4.1 Summary 201
7.4.2 Outlook 202
References 204
8 Vibrational Spectroscopy and Related In situ Studies of Catalytic Reactions Within Molecular Sieves 209
Eli Stavitski and Bert M. Weckhuysen
8.1 Introduction 209
8.2 Acidity Determination with IR Spectroscopy of Probe Molecules 211
8.3 Zeolite Synthesis Processes 218
8.4 Selection of Zeolite–Based Catalytic Reactions 221
8.4.1 Catalytic Decomposition of Nitric Oxides 221
8.4.2 Methanol–to–Olefin Conversion 225
8.5 IR Microspectroscopy 231
8.6 Concluding Remarks and Look into the Future 232
Acknowledgment 234
References 234
9 Textural Characterization of Mesoporous Zeolites 237
Lei Zhang, Adri N.C. van Laak, Petra E. de Jongh, and Krijn P. de Jong
9.1 Introduction 237
9.2 Methods for Generating Meso– and Macropores in Zeolites 239
9.2.1 Postsynthesis Modification 239
9.2.2 Templating Method 243
9.2.3 Other Methods 245
9.3 Characterization of Textural Properties of Mesoporous Zeolites 246
9.3.1 Gas Physisorption 246
9.3.2 Thermoporometry 251
9.3.3 Mercury Porosimetry 255
9.3.4 Electron Microscopy 256
9.3.5 NMR Techniques 266
9.3.6 In situ Optical and Fluorescence Microscopy 271
9.4 Summary and Outlook 273
Acknowledgments 274
References 274
10 Aluminum in Zeolites: Where is it and What is its Structure? 283
Jeroen A. van Bokhoven and Nadiya Danilina
10.1 Introduction 283
10.2 Structure of Aluminum Species in Zeolites 284
10.2.1 Reversible versus Irreversible Structural Changes 285
10.2.2 Cautionary Note 286
10.2.3 Development of Activity and Changing Aluminum Coordination 286
10.3 Where is the Aluminum in Zeolite Crystals? 289
10.3.1 Aluminum Zoning 289
10.3.2 Aluminum Distribution Over the Crystallographic T Sites 292
10.4 Summary and Outlook 296
Acknowledgment 298
References 298
11 Theoretical Chemistry of Zeolite Reactivity 301
Evgeny A. Pidko and Rutger A. van Santen
11.1 Introduction 301
11.2 Methodology 302
11.2.1 Ab initio Methods 303
11.2.2 DFT Methods 303
11.2.3 Basis Sets 304
11.2.4 Zeolite Models 306
11.3 Activation of Hydrocarbons in Zeolites: The Role of Dispersion Interactions 307
11.4 Molecular–Level Understanding of Complex Catalytic Reactions: MTO Process 316
11.5 Molecular Recognition and Confinement–Driven Reactivity 321
11.6 Structural Properties of Zeolites: Framework Al Distribution and Structure and Charge Compensation of Extra–framework Cations 326
11.7 Summary and Outlook 330
References 331
12 Modeling of Transport and Accessibility in Zeolites 335
Sofía Calero Diaz
12.1 Introduction 335
12.2 Molecular Models 336
12.2.1 Modeling Zeolites and Nonframework Cations 336
12.2.2 Modeling Guest Molecules 337
12.3 Simulation Methods 338
12.3.1 Computing Adsorption 339
12.3.2 Computing Free Energy Barriers 341
12.3.3 Computing Volume–Rendered Pictures, Zeolite Surface Areas, and Zeolite Pore Volumes 343
12.3.4 Computing Diffusion 344
12.4 Molecular Modeling Applied to Processes Involving Zeolites 346
12.4.1 Applications in Technological Processes 346
12.4.2 Applications in Green Chemistry 351
12.5 Summary and Outlook 353
Acknowledgments 354
References 354
13 Diffusion in Zeolites Impact on Catalysis 361
Johan van den Bergh, Jorge Gascon, and Freek Kapteijn
13.1 Introduction 361
13.2 Diffusion and Reaction in Zeolites: Basic Concepts 362
13.2.1 Importance of Adsorption 364
13.2.2 Self–Diffusivity 364
13.2.3 Mixture Diffusion 365
13.2.4 Diffusion Measurement Techniques 365
13.2.5 Relating Diffusion and Catalysis 366
13.3 Diffusion in Zeolites: Potential Issues 368
13.3.1 Concentration Dependence of Diffusion 368
13.3.2 Single–File Diffusion 370
13.3.3 Surface Barriers 372
13.3.4 The Thiele Concept: A Useful Approach in Zeolite Catalysis? 374
13.4 Pore Structure, Diffusion, and Activity at the Subcrystal Level 375
13.5 Improving Transport through Zeolite Crystals 379
13.6 Concluding Remarks and Future Outlook 382
References 383
Contents to Volume 2
14 Special Applications of Zeolites 389
Víctor Sebastián, Clara Casado, and Joaquín Coronas
15 Organization of Zeolite Microcrystals 411
Kyung Byung Yoon
16 Industrial Potential of Zeolites 449
Giuseppe Bellussi, Angela Carati, and Roberto Millini
17 Catalytically Active Sites: Generation and Characterization 493
Michael Hunger
18 Cracking and Hydrocracking 547
Marcello Rigutto
19 Reforming and Upgrading of Diesel Fractions 585
Carlo Perego, Vincenzo Calemma, and Paolo Pollesel
20 Recent Development in Transformations of Aromatic Hydrocarbons over Zeolites 623
Sulaiman Al–Khattaf, Mohammad Ashraf Ali, and Jirí Cejka
21 Advanced Catalysts Based on Micro– and Mesoporous Molecular Sieves for the Conversion of Natural Gas to Fuels and Chemicals 649
Agustín Martínez, Gonzalo Prieto, Andrés García–Trenco, and Ernest Peris
22 Methanol to Olefins (MTO) and Methanol to Gasoline (MTG) 687
Michael Stöcker
23 Metals in Zeolites for Oxidation Catalysis 713
Takashi Tatsumi
24 Environmental 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 827
King Lun Yeung and Wei Han
Index 863
Prof. AVELINO CORMA was born in Moncófar, Spain in 1951. He studied Chemistry at the Universidad de Valencia (1967–1973), and received his Ph.D. at the Universidad Complutense de Madrid in 1976. He was a Postdoctoral researcher in the Department of chemical engineering at the Queen?s University (Canada, 1977–79). Prof. Corma is the director of the Instituto de Tecnología Química (UPV–CSIC) at the Universidad Politécnica de Valencia since 1990. His current research field is catalysis, and molecular sieves covering aspects of synthesis, characterization and reactivity in acid–base and redox catalysis. Avelino Corma is co–author of more than 700 articles and 100 patents on these subjects.
Prof. JIRÍ CEJKA was born in Roudnice nad Labem, former Czechoslovakia, in 1960. He studied at the Institute of Chemical Technology in Prague and received his Ph.D. at the J. Heyrovsky Institute of Physical Chemistry and Electrochemistry in Prague in 1988. At present he is a head of the Department of Synthesis and Catalysis at J. Heyrovsky Institute of Physical Chemistry in Prague and lecturer at the Faculty of Natural Sciences of Charles University in Prague. In 2005 he chaired the 3rd FEZA Conference on Zeolites in Prague. His research interests comprise: synthesis of zeolites, mesoporous and novel nano–structured materials, physical chemistry of sorption and catalysis, and investigation of the role of porous catalysts in transformations of hydrocarbons and their derivatives. Jirí Cejka is co–author of about 200 research papers and co–editor of 5 books.
Dr. STACEY I. ZONES is a Research Fellow at Chevron′s Energy and Technology Center in Richmond, CA, USA. He is the senior researcher in a group which strives to invent and explore newer zeolites and then follow through in finding applications for their use, ways to tailor their properties and methods to develop more econmical routes to introduce them into the commercial world. The group also looks for novel applications of zeolites in emerging technologies. Dr. Zones has been a co–inventor on more than 100 patents and a co–author on more than 100 journal publications. He has also been a frequent speaker and participant in the zeolite conferences around the world, and is a mentoring collaborator for elements of zeolite research programs at several universities.
Microporous, aluminosilicate minerals with regularly structured pores offer access to a wide range of applications in both academia and industry. This indispensable two–volume handbook covery everything on the hot research field of zeolites.
With information spread over two volumes: Volume 1 deals with the synthesis, modification, characterization and application of catalytic active zeolites, while Volume 2 focuses on such reaction types as cracking, hydrocracking, isomerization, reforming and other industrially important topics.
Edited by a highly experienced and internationally renowned team with chapters written by the ¿Who¿s Who¿ of zeolite research, this set is valuable to catalytic, solid state, physical, and industrial chemists, chemical engineers, surface chemists and materials scientists.
1997-2024 DolnySlask.com Agencja Internetowa