Authored by a top-level team of both academic and industrial researchers in the field, this is an up-to-date review of mesoporous zeolites.
The leading experts cover novel preparation methods that allow for a purpose-oriented fine-tuning of zeolite properties, as well as the related materials, discussing the specific characterization methods and the applications in close relation to each individual preparation approach. The result is a self-contained treatment of the different classes of mesoporous zeolites.
With its academic insights and practical relevance this is a comprehensive handbook for researchers in the field and related areas, as well as for developers from the chemical industry.
Cuprins
Foreword XIII
Preface XVII
List of Contributors XXV
1 Strategies to Improve the Accessibility to the Intracrystalline Void of Zeolite Materials: Some Chemical Reflections 1
Joaquén Pérez-Pariente and Teresa Álvaro-Münoz
1.1 Introduction 1
1.2 Strategies to Obtain New Large-Pore Materials 5
1.3 Methodologies to Control the Crystallization Process of Zeolite Materials in the Absence of Pore-Forming Agents 9
1.3.1 Confined Nucleation and Growth 11
1.3.2 Use of Blocking Agents for Crystal Growth 13
1.3.2.1 Silanization Methods 13
1.3.2.2 Use of Surfactants in the Synthesis of Silicoaluminophosphates 16
1.3.3 Synthesis in the Presence of Pore-Forming Agents 18
1.4 Postsynthesis Methodologies 21
1.4.1 Materials with High Structural Anisotropy: Layered Zeolites 21
1.4.2 Removal/Reorganization of T Atoms in the Crystal Bulk 23
1.5 Conclusions 24
Acknowledgments 25
References 25
2 Zeolite Structures of Nanometer Morphology: Small Dimensions, New Possibilities 31
Heloise de Oliveira Pastore and Dilson Cardoso
2.1 The Structures of Zeolites 34
2.1.1 FAU and EMT Structures: Zeolites X and Y 34
2.1.2 LTA Structure 50
2.1.3 BEA Structure 52
2.1.4 Pentasil Zeolites, MFI, and MEL Structures: ZSM-5, ZSM-11, and S-1 56
2.2 The Structures of Zeotypes: Aluminophosphates and Silicoaluminophosphates 63
2.3 Lamellar Zeolites 66
2.4 Conclusions and Perspectives 71
References 75
3 Nanozeolites and Nanoporous Zeolitic Composites: Synthesis and Applications 79
Gia-Thanh Vuong and Trong-On Do
3.1 Introduction 79
3.2 Synthesis of Nanozeolites 81
3.2.1 Principles 81
3.2.2 Synthesis from Clear Solutions 87
3.2.2.1 Parameters Affecting the Crystal Size 87
3.2.3 Synthesis Using Growth Inhibitor 90
3.2.4 Confined Space Synthesis 91
3.2.5 Synthesis of Nanozeolites Using Organic Media 95
3.3 Nanozeolite Composites 98
3.4 Recent Advances in Application of Nanozeolites 106
3.5 Conclusions and Perspectives 109
References 110
4 Mesostructured and Mesoporous Aluminosilicates with Improved Stability and Catalytic Activities 115
Yu Liu
4.1 Introduction 115
4.2 Zeolite/Mesoporous Composite Aluminosilicates 116
4.2.1 Synthesis of Zeolite/Mesoporous Composite Material 116
4.2.2 Catalytic Evaluation of Zeolite/Mesoporous Composite Material 124
4.3 Posttreatment of Mesostructured Materials 128
4.3.1 Posttreatment of Mesoporous Materials by Zeolite Structure-Directing Agents or Zeolite Nanocrystals 128
4.3.2 Postsynthesis Grafting of Aluminum Salts on the Walls of Mesostructured Materials 133
4.4 Mesostructured and Mesoporous Aluminosilicates Assembled from Digested Zeolite Crystals 135
4.5 Mesostructured and Mesoporous Aluminosilicates Assembled from Zeolite Seeds/Nanoclusters 141
4.5.1 Assembly of Mesostructured Aluminosilicates from Zeolite Y Seeds 141
4.5.2 Assembly of Mesostructured Aluminosilicates from Pentasil Zeolite Seeds 145
4.6 Conclusions 152
References 153
5 Development of Hierarchical Porosity in Zeolites by Using Organosilane-Based Strategies 157
David P. Serrano, José M. Escola, and Patricia Pizarro
5.1 Introduction 157
5.2 Types of Silanization-Based Methods 159
5.2.1 Functionalization of Protozeolitic Units with Organosilanes 159
5.2.1.1 Fundamentals of the Method 159
5.2.1.2 Influence of the Organosilane Type 163
5.2.1.3 Application to Different Zeolites 166
5.2.1.4 Influence of the Silica Source 168
5.2.1.5 Reduction of the Gel Viscosity by Means of Alcohols 169
5.2.1.6 State of the Aluminum and Acidity 171
5.2.2 Use of Silylated Polymers 173
5.2.3 Use of Amphiphile Organosilanes 175
5.3 Catalytic Applications 180
5.3.1 Fine Chemistry 180
5.3.2 Oil Refining and Petrochemistry 185
5.3.3 Production of Advanced Fuels 189
5.4 Conclusions 193
5.5 New Trends and Future Perspectives 195
References 196
6 Mesoporous Zeolite Templated from Polymers 199
Xiangju Meng and Feng-Shou Xiao
6.1 Introduction 199
6.2 Cationic Polymer Templating 200
6.3 Nonionic Polymer Templating 203
6.4 Silane-Functionalized Polymer Templating 208
6.5 Polymer–Surfactant Complex Templating 210
6.6 Morphology Control of Mesoporous Zeolites Using Polymers 212
6.7 Zeolites with Oriented Mesoporous Channels 218
6.8 Microfluidic Synthesis of Mesoporous Zeolites 220
6.9 Nonsurfactant Cationic Polymer as a Dual-Function Template 220
6.10 Conclusions 224
References 224
7 Nanofabrication of Hierarchical Zeolites in Confined Space 227
Zhuopeng Wang and Wei Fan
7.1 Introduction of Confined Space Synthesis 227
7.2 General Principles of Confined Space Synthesis 228
7.3 Crystallization Mechanisms of Zeolite under Hydrothermal Conditions 228
7.4 Preparation of Synthesis Gel within the Confined Space of Inert Matrices 230
7.5 Crystallization of Zeolite within Confined Space 230
7.6 Synthesis of Hierarchical Zeolites in Carbon Blacks, Nanotubes, and Nanofibers by SAC Method 232
7.7 Synthesis of Hierarchical Zeolites within Ordered Mesoporous Carbons by SAC and VPTMethods 234
7.8 Synthesis of Hierarchical Zeolites within Carbon Aerogels, Polymer Aerogels, and other Carbon Materials 241
7.9 Synthesis of Hierarchical Zeolites within Carbon Materials Using Seeded Growth Method 243
7.10 Confined Synthesis of Zeolites in Polymer and Microemulsions 248
7.11 Conclusions 250
References 253
8 Development of Hierarchical Pore Systems for Zeolite Catalysts 259
Masaru Ogura and Masahiko Matsukata
8.1 Introduction 259
8.2 Alkali Treatment of ZSM-5: Effects of Alkaline Concentration, Treatment Temperature, and Treatment Duration 260
8.3 Desilication of ZSM-5: Effects of Temperature and Time 263
8.4 Alkali Treatment of ZSM-5 with Various Si/Al Molar Ratios: Effect of Si/Al on Mesopore Formation 263
8.5 Desilication of ZSM-5: Effects of Other Descriptors 272
8.6 Desilication of Silicalite-1 273
8.7 Desilication of Other Zeolites: Multidimensionalization of Low-Dimensional Microstructures 277
8.8 Desilicated Zeolites for Applications – Test Reactions 280
8.9 Desilicated Zeolites for Applications – Superior Diffusion 284
8.10 Desilicated Zeolites for Novel Applications 289
8.11 Summary 291
References 292
9 Design and Catalytic Implementation of Hierarchical Micro–Mesoporous Materials Obtained by Surfactant-Mediated Zeolite Recrystallization 295
Irina I. Ivanova, Elena E. Knyazeva, and Angelina A. Maerle
9.1 Introduction 295
9.2 Mechanism of Zeolite Recrystallization 296
9.3 Synthetic Strategies Leading to Different Types of Recrystallized Materials 301
9.4 Coated Mesoporous Zeolites (RZEO-1) 303
9.5 Micro–Mesoporous Nanocomposites (RZEO-2) 308
9.6 Mesoporous Materials with Zeolitic Fragments in the Walls (RZEO-3) 312
9.7 Conclusions 316
Acknowledgment 318
References 318
10 Surfactant-Templated Mesostructuring of Zeolites: From Discovery to Commercialization 321
Kunhao Li, Michael Beaver, Barry Speronello, and Javier García-Martínez
10.1 Introduction 321
10.2 Surfactant-Templated Mesostructuring of Zeolites 326
10.3 Mesostructured Zeolite Y for Fluid Catalytic Cracking Applications 334
10.4 Beyond Catalysis: Mesostructured Zeolite X for Adsorptive Separations 341
10.5 Concluding Remarks 344
References 345
11 Physical Adsorption Characterization of Mesoporous Zeolites 349
Matthias Thommes, Rémy Guillet-Nicolas, and Katie A. Cychosz
11.1 Introduction 349
11.2 Experimental Aspects 352
11.2.1 General 352
11.2.2 Choice of Adsorptive 354
11.3 Adsorption Mechanism 357
11.4 Surface Area, Pore Volume, and Pore Size Analysis 363
11.4.1 Surface Area 363
11.4.2 Pore Size Analysis 367
11.4.2.1 General Aspects 367
11.4.2.2 Pore Size Analysis: Hierarchically Structured Materials 370
11.5 Probing Hierarchy and Pore Connectivity in Mesoporous Zeolites 376
11.6 Summary and Conclusions 378
References 379
12 Measuring Mass Transport in Hierarchical Pore Systems 385
Jörg Kärger, Rustem Valiullin, Dirk Enke, and Roger Gläser
12.1 Types of Pore Space Hierarchies in Nanoporous Host Materials 385
12.2 Hierarchy of Mass Transfer Parameters and Options of Their Measurement Techniques 389
12.2.1 Diffusion Fundamentals 389
12.2.2 Techniques of Diffusion Measurement 392
12.2.2.1 Macroscopic Diffusion Studies: Uptake and Release 392
12.2.2.2 Microscopic Diffusion Measurement: Molecular Displacements 396
12.2.2.3 Microscopic Diffusion Measurement: Transient Concentration Profiles 399
12.3 Diffusion Measurement in Various Types of Pore Space Hierarchies 400
12.3.1 Macro/Meso 400
12.3.2 Macro/Micro 401
12.3.3 Meso/Meso 404
12.3.4 Meso/Micro 407
12.3.4.1 PFG NMR Diffusion Measurements in Y-Type Zeolites: A Case Study with FCC Catalysts 407
12.3.4.2 Mass Transfer in Mesoporous LTA-Type Zeolites: An In-Depth Study of Diffusion Phenomena in Mesoporous Zeolites 409
12.3.4.3 Diffusion Studies with Mesoporous Zeolite of Structure-Type CHA: Breakdown of the Fast-Exchange Model 414
12.3.4.4 The Impact of Hysteresis 415
12.4 Conclusions and Outlook 416
References 417
13 Structural Characterization of Zeolites and Mesoporous Zeolite Materials by Electron Microscopy 425
Wei Wan, Changhong Xiao, and Xiaodong Zou
13.1 Introduction 425
13.2 Characterization of Zeolites by Electron Diffraction 426
13.2.1 Geometry of Electron Diffraction 427
13.2.2 Conventional Electron Diffraction 428
13.2.3 Three-Dimensional (3D) Electron Diffraction 430
13.3 Characterization of Zeolite and Mesoporous Materials by High-Resolution Transmission Electron Microscopy 433
13.3.1 Introduction to HRTEM 433
13.3.2 Working with Electron-Beam-Sensitive Materials 434
13.3.3 Structure Projection Reconstruction from Through-Focus HRTEM Images 435
13.3.4 3D Reconstruction of HRTEM Images 437
13.4 Characterization of Zeolite and Mesoporous Materials by Electron Tomography (ET) 440
13.4.1 Basic Principles of Electron Tomography 440
13.4.2 Applications of Electron Tomography on Mesoporous Zeolites 443
13.4.2.1 Quantification of Mesopores in Zeolite Y 443
13.4.2.2 Quantification of Pt Nanoparticles in Mesoporous Zeolite Y 444
13.4.2.3 Orientation Relationship between the Intrinsic Micropores of Zeolite Y and Mesopore Structures 445
13.4.2.4 Single-Crystal Mesoporous Zeolite Beta Studied by Transmission Scanning Electron Microscopy (STEM) 448
13.5 Other Types of Mesoporous Zeolites Studied by EM 450
13.5.1 Aluminosilicate Zeolite ZSM-5 Single Crystals with b-Axis-Aligned Mesopores 450
13.5.2 Mesoporous Zeolite LTA 451
13.5.3 Ultrasmall EMT Crystals with Intercrystalline Mesopores from Organic Template-Free Synthesis 452
13.5.4 Self-Pillared Zeolites with Interconnected Micropores and Mesopores 452
13.6 Future Perspectives 454
13.7 Conclusions 455
Acknowledgments 456
References 456
14 Acidic Properties of Hierarchical Zeolites 461
Jerzy Datka, Karolina Tarach, and Kinga Góra-Marek
14.1 Short Overview of Experimental Methods Employed for Acidity Investigations 461
14.2 Hierarchical Zeolites Obtained by Templating and Dealumination of Composite Materials 463
14.2.1 Surfactant Templating Approach 465
14.2.2 Dealumination 470
14.3 Hierarchical Zeolites Obtained by Desilication 471
14.3.1 Studies of Desilicated Zeolites Acidity 471
14.3.1.1 Analysis of the Hydroxyl Groups Spectra 471
14.3.1.2 Concentration of Acid Sites 474
14.3.1.3 Studies of Acid Sites Strength 475
14.3.1.4 Realumination: Mesopore Surface Enrichment in Al Species 476
14.3.1.5 Nature and Origin of Lewis Acid Sites in Desilicated Zeolites 477
14.3.2 Accessibility of Acid Sites in Desilicated Zeolites 481
14.4 Conclusions and Future Perspectives 487
Acknowledgments 489
References 489
15 Mesoporous Zeolite Catalysts for Biomass Conversion to Fuels and Chemicals 497
Kostas S. Triantafyllidis, Eleni F. Iliopoulou, Stamatia A. Karakoulia, Christos K. Nitsos, and Angelos A. Lappas
15.1 Introduction to Mesoporous/Hierarchical Zeolites 497
15.2 Potential of Hierarchical Zeolites as Catalysts for the Production of Renewable/Biomass-Derived Fuels and Chemicals 503
15.3 Catalytic Fast Pyrolysis (CFP) of Lignocellulosic Biomass 508
15.4 Catalytic Cracking of Vegetable Oils 514
15.5 Hydroprocessing of Biomass-Derived Feeds 516
15.6 Methanol to Hydrocarbons 524
15.6.1 Methanol to Dimethyl Ether (DME) 525
15.6.2 Methanol to Gasoline (MTG)/Methanol to Olefins (MTO) 527
15.7 Other Processes 533
15.8 Summary and Outlook 535
References 536
16 Industrial Perspectives for Mesoporous Zeolites 541
Roberto Millini and Giuseppe Bellussi
16.1 Introduction 541
16.2 Enhancing the Effectiveness of the Zeolite Catalysts 543
16.2.1 Increasing the Pore Size 544
16.2.2 Hierarchical (Mesoporous) Zeolites 546
16.3 Industrial Assessment of Mesoporous Zeolite 555
16.4 Conclusions 560
References 561
Index 565
Despre autor
Javier Garcia-Martinez is the founder of and chief scientist at Rive Technology, Inc. in Boston, USA, a spin-off from MIT that commercializes mesostructured zeolites to the refining industry. He is also Professor of Inorganic Chemistry and the director of the Molecular Nanotechnology Lab at the University of Alicante, Spain. Since 2011 he is a member of the Bureau of IUPAC and Fellow of the Royal Society of Chemistry. His work has been honored with the European Young Chemist Award in 2006, MIT’s Technology Review Award (TR35) in 2007, and by the World Economic Forum, which selected him as a Young Global Leader in 2009. Professor Garcia-Martinez has published extensively in the areas of nanomaterials, catalysis, and energy, and also has over 25 patents to his name. His latest books are ‘Nanotechnology for the Energy Challenge’ (Wiley-VCH, 2014) and ‘The Chemical Element’ (Wiley-VCH, 2011).
Kunhao Li is a Project Leader at Rive Technology, Inc. since 2008. He has been heavily involved in the improvement of Rive’s core technology in zeolite mesostructuring processes, zeolites and catalysts characterization, testing, and evaluation, as well as extension of application areas of mesostructured zeolites to chemical separations and other catalytic processes. He obtained Ph D in chemistry at The George Washington University and did postdoctoral research at Rutgers University. His research work has resulted in many publications in the form of original papers and reviews, book chapters, technical reports, patent applications, and patents.
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