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Zeolites and Catalysis: Synthesis, Reactions and Applications

Zeolites and Catalysis: Synthesis, Reactions and Applications

Jiri Cejka (Editor), Avelino Corma (Editor), Stacey Zones (Editor)

ISBN: 978-3-527-63030-1

May 2010

918 pages

$348.99

Description

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.

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

“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)