Ordered Porous Solids (eBook)

Front Cover 1
Ordered Porous Solids 2
Copyright Page 3
Contents 4
Contributions 8
Section I: Synthesis, Modification and Characterization of Ordered Porous Materials 14
Chapter 1: A New Family of Mesoporous Oxides-Synthesis, Characterisation and Applications of TUD-1 16
Abbreviations 17
1. Introduction 17
2. MCM-41 and FSM-16 18
3. TUD-1 19
4. Redox Metal Incorporation into Siliceous TUD-1 Framework 23
5. Al2O3-TUD-1 and Al-TUD-1 32
6. TUD-1 as Potential Drug Carriers 34
7. Particle Incorporation 35
8. Conclusion 41
References 42
Chapter 2: Organoclays: Preparation, Properties and Applications 44
1. Introduction 44
2. Preparation and Applications of Organoclays 46
3. Outlook 58
References 59
Chapter 3: Titanium-Based Nanoporous Materials 64
1. Introduction 65
2. Nanoporous Titanosilicates with Ti[4] Coordination 65
3. Nanoporous Titanosilicates with Ti[6] Coordination 77
4. Nanoporous Titania 80
5. Synthesis of Titanium-Based Nanoporous Materials 82
6. Summary and Outlook 85
References 86
Chapter 4: Porous Metal Organic Frameworks: From Synthesis to Applications 90
1. Introduction 91
2. Flexible MOFs 94
3. Synthesis 95
4. Thin Films 98
5. Adsorption 99
6. MOFs and Separation 102
7. Inclusion and Reaction in MOFs 102
8. Catalytic Applications 103
9. Redox Activity 104
10. Magnetism 104
11. Optical Properties 105
12. Bioapplications 105
13. Conclusions 106
Acknowledgements 107
References 107
Chapter 5: Functionalisation and Structure Characterisation of Porous Silicates and Aluminophosphates 114
1. Introduction 115
2. Hydrothermal Conventional and Microwave Synthesis of Nanoporous Silica- and Aluminophosphate-Based Materials 116
3. Determination of Structure Porosity and Acid Sites in Nanoporous Catalysts 118
4. Mn-, Fe- and Ti-Functionalised Microporous and Mesoporous Silicates and Aluminophosphates: Case Studies 125
5. Mesoporous Thin Films 132
6. Conclusions 133
Acknowledgements 133
References 134
Chapter 6: Theoretical and Practical Aspects of Zeolite Nucleation 140
1. Introduction 140
2. Nucleation of Zeolites: An Overview and Critical Evaluation 142
3. Summary and Outlook 188
References 191
Chapter 7: Modern Spectroscopic Methods Applied to Nanoscale Porous Materials 200
1. Introduction 201
2. Vibrational Spectroscopy: Fundamentals and Practical Hints 203
3. Application of Raman and IR Spectroscopy to Zeolite-Type Nano-Materials 209
4. Perspectives 219
References 220
Chapter 8: Computational Modelling of Nanoporous Materials 224
Glossary 225
1. Introduction 225
2. Quantum Chemical and Hybrid Methods for Modelling of Nanoporous Materials 225
3. Selected Areas and Research Problems 233
4. Outlook 248
Acknowledgements 249
References 249
Chapter 9: Intermolecular Forces in Zeolite Adsorption and Catalysis 252
1. Introduction 252
2. Basic Thermodynamic Conceptsa 253
3. Dispersion (London) Forces 255
4. Induced Dipole and Quadrupole-Charge Interactions 260
5. Dipole-Charge Interactions 265
6. Interactions of Adsorbed Molecules with Acid Sites 267
7. Hydrophobic Interactions in High-Silica Zeolites 272
8. Final Remarks 272
References 273
Chapter 10: Application of Isotopically Labelled IR Probe Molecules for Characterization of Porous Materials 276
Glossary 277
1. Introduction 277
2. Brief Background of the Vibrational Spectra of Isotopically Labelled Molecules 278
3. Chemical Composition and Structure of Surface Species 280
4. Identification of Polyligand Species 282
5. Use of D3-Acetonitrile for Determination of Surface Acidity 290
6. Use of Isotopic Exchange for Changing the Spectral Region 291
7. Conclusions 292
Acknowledgements 292
References 292
Chapter 11: Organically Modified Ordered Mesoporous Siliceous Solids 296
1. Introduction 297
2. Functionalization Methods 298
3. Characterization 301
4. Shape Modelling 305
5. Targeted Applications 305
6. Outlook and Prospects 313
References 314
Section II: Bi- and Three-Dimensional Organised Porous Constructs 322
Chapter 12: Hydrothermal Synthesis of Zeolitic Coatings for Applications in Micro-structured Reactors 324
Glossary 325
1. Introduction 325
2. Material Choice 328
3. Effect of Surface Roughness on Coverage 328
4. Effect of Surface Hydrophobicity on Coverage 330
5. Effect of Synthesis Conditions on Coverage 333
6. Microwave-Assisted Synthesis of Zeolitic Coatings 338
7. Large-Scale Synthesis of Zeolitic Coatings 339
8. Applications in Micro-structured Reactors 339
9. Summary and Outlook 343
Acknowledgements 343
References 344
Chapter 13: Pure-Silica-Zeolite Low-Dielectric Constant Materials 348
Glossary Entries 349
1. Introduction 349
2. Pure-Silica-Zeolite Film Synthesis and Characterization 351
3. Strategies to Reduce the Dielectric Constant 354
4. Hydrophobicity 359
5. Mechanical Properties 361
6. Hybrid Materials 370
7. Future Considerations and Conclusions 370
Acknowledgements 372
References 373
Chapter 14: Highly Selective Zeolite Membranes 378
1. Introduction to Zeolite Membranes 379
2. Zeolite Membrane Growth Methods 380
3. Permeation and Gas Transport 381
4. Defect-Sites Diffusion/Non-Zeolitic Pores 383
5. Thin Films 383
6. Zeolite Membrane Modification 383
7. Applications 385
8. Fabrication and Manufacturing 394
9. Conclusion 396
Acknowledgements 396
References 397
Chapter 15: Gas Sensing with Silicon-Based Nanoporous Solids 400
Abbreviations 400
1. Introduction 401
2. Porous Silicon 405
3. Si-Based Microporous Solids: Zeolites and Related Materials 409
4. Mesoporous Silica 416
5. Ordered Mesoporous Materials: M41S and PMOs Families 417
6. Conclusions and Outlook 420
References 420
Chapter 16: Mesostructuring of Metal Oxides Through EISA: Fundamentals and Applications 426
Glossary 426
1. Self-Assembly of Mesoporous Materials 427
2. Evaporation-Induced Self-Assembly Origins 430
3. Fundamentals 431
4. Preparation Methods of Mesoporous Films 434
5. Mesostructured Silicate Systems 435
6. Mesostructured Non-Silicate Systems 439
7. Emerging Applications 447
8. Concluding Remarks 448
References 449
Chapter 17: Zeolite Nanocrystals: Hierarchical Assembly and Applications 454
1. Introduction 455
2. Hierarchical Assemblies of Zeolite Nanocrystals 456
3. Emerging Applications of Zeolite Nanocrystals 463
4. Conclusions and Prospects 477
Acknowledgements 479
References 479
Chapter 18: Bioinspired Porous Materials 490
Glossary 490
1. Introduction 490
2. Hierarchical Porous Structures 492
3. Concluding Remarks 507
Acknowledgements 509
References 509
Chapter 19: Strategies Towards the Assembly of Preformed Zeolite Crystals into Supported Layers 514
1. Introduction 514
2. Methods for the Assembly of Preformed Zeolite Crystals 516
3. Applications of Supported Layers of Preformed Zeolite Crystals 527
4. Concluding Remarks 529
References 530
Section III: Applications and Prospects of Ordered Porous Materials 534
Chapter 20: Electrochemistry with Micro- and Mesoporous Silicates 536
1. Introduction 537
2. Confinement of Microporous Zeolites and Mesoporous Silica Materials onto Electrode Surfaces 538
3. Basic Electrochemical Behaviour 542
4. Applications 553
5. Conclusions 565
References 565
Chapter 21: Nanoparticle Doped Photopolymers for Holographic Applications 572
1. Introduction 573
2. Holographic Recording 575
3. Mechanism for the Holographic Redistribution of Nanoparticles 581
4. Holographic Applications 587
5. Summary 596
Acknowledgements 596
References 596
Chapter 22: Inorganic Sulphur Pigments Based on Nanoporous Materials 604
1. Introduction 605
2. Molecules Encapsulated in Zeolites 606
3. Sulphur Chromophores in Zeolite Matrices 607
4. Conclusions 630
Acknowledgements 631
References 631
Chapter 23: Advances in the Use of Carbon Nanomaterials in Catalysis 634
Glossary 635
1. Carbon Nanotubes and Carbon Nanofibres Properties: Towards Smart and Versatile Materials 635
2. Carbon Nanomaterials in Catalysis: A Laughing Choice? 641
3. Unidimensional Carbon Nanomaterials in Catalysis? 644
4. Carbon Nanomaterials with Controlled Macroscopic Shapes: Novel Versatile Structured Catalysts 650
5. Conclusions 658
Acknowledgements 659
References 659
Chapter 24: Strong Brlatin small letter o slashnsted Acidity in Alumina-Silicates: Influence of Pore Dimension, Steaming and Acid Site Density on Cracking of Alkanes 664
1. Introduction 665
2. Structure of the Active Site 665
3. Reacting Species 665
4. Determining Reaction Constants 666
5. Cracking of Alkanes Over ZSM5 668
6. Adsorption of Alkanes in Zeolite Pores 670
7. Cracking of Alkanes Over Different Zeolites 673
8. Cracking of Alkanes Over Steamed Zeolites and Amorphous Silica-Alumina 677
9. Concluding Remarks 678
References 679
Chapter 25: Catalysis by Mesoporous Molecular Sieves 682
1. Introduction to Mesoporous Molecular Sieves 683
2. Catalysis by Single Atoms 685
3. Transition Metal Oxides Supported on Mesoporous Molecular Sieves 695
4. Immobilized Organometallic Complexes 698
5. Conclusions 701
Acknowledgements 701
References 701
Chapter 26: Catalytic Phases Embedded in Mesostructured Matrices and Their Nanocasts: Effects of Spatial Dimension and Assembling Mode on Activity 706
Abbreviations 707
1. Introduction 707
2. Approximation of the CP Surface Area in CP/MHM Composites and Corresponding Nanocasts with a Geometric Model 710
3. Control of CP Assembling Mode in a Mesostructured Matrix 716
4. Evaluation of CP Assembling Mode in CP/MHM Composites and Their Nanocasts 726
5. Effect of CPs' Spatial Dimension and Assembling Mode on Their Catalytic Performance 729
6. Conclusions 732
Acknowledgements 733
References 733
Chapter 27: Nanoporous Materials-Catalysts for Green Chemistry 738
Glossary 739
1. Introduction 739
2. Metrics-Measurement and Comparison of Processes 740
3. Green Aspects in the Synthesis of Nanoporous Catalysts 742
4. Catalysis Using Mesoporous Materials 743
5. Towards One-Pot Multistage Syntheses 749
6. Enzyme Immobilization in Mesoporous Hosts 753
7. Incorporation of Nanoporous Solids in Flow Reactors 755
8. Conclusions 757
References 758
Chapter 28: The Fascinating Chemistry of Iron- and Copper-Containing Zeolites 762
1. Introduction 763
2. The Oxidation of Benzene to Phenol Over Iron Zeolites 764
3. The Decomposition of N2O by Iron Zeolites 773
4. Active Oxygen Atoms in Copper Zeolites 777
5. Conclusions-Iron Versus Copper Zeolites 780
References 781
Index 786
Color Plates Section 802