Chemistry of Zeolites and Related Porous Materials: Synthesis and Structure

Chemistry of Zeolites and Related Porous Materials......Page 1
Contents......Page 7
Preface......Page 13
1. Introduction......Page 17
1.1.1 From Natural Zeolites to Synthesized Zeolites......Page 18
1.1.2 From Low-silica to High-silica Zeolites......Page 19
1.1.3 From Zeolites to Aluminophosphate Molecular Sieves and Other Microporous Phosphates......Page 20
1.1.4 From 12-Membered-ring Micropores to Extra-large Micropores......Page 21
1.1.5 From Extra-large Micropores to Mesopores......Page 22
1.1.6 Emergence of Macroporous Materials......Page 23
1.1.7 From Inorganic Porous Frameworks to Porous Metal-organic Frameworks (MOFs)......Page 24
1.2.1 The Traditional Fields of Application and Prospects of Microporous Molecular Sieves......Page 25
1.2.2 Prospects in the Application Fields of Novel, High-tech, and Advanced Materials......Page 26
1.2.3 The Main Application Fields and Prospects for Mesoporous Materials......Page 27
1.3.1 The Development from Synthesis Chemistry to Molecular Engineering of Porous Materials......Page 29
1.3.2 Developments in the Catalysis Study of Porous Materials......Page 30
2.1 Introduction......Page 35
2.2.1 Primary Building Units......Page 39
2.2.2 Secondary Building Units (SBUs)......Page 40
2.2.3 Characteristic Cage-building Units......Page 41
2.2.4 Characteristic Chain- and Layer-building Units......Page 45
2.2.5 Periodic Building Units (PBUs)......Page 48
2.3.1 Framework Composition......Page 49
2.3.2 Distribution and Position of Cations in the Structure......Page 50
2.3.3 Organic Templates......Page 55
2.4.1 Loop Configuration and Coordination Sequences......Page 57
2.4.2 Ring Number of Pore Opening and Channel Dimension in Zeolites......Page 59
2.4.4 Selected Zeolite Framework Structures......Page 63
2.5.1 Anionic Framework Aluminophosphates with Al/P <=1......Page 88
2.5.2 Open-framework Gallophosphates with Extra-large Pores......Page 104
2.5.3 Indium Phosphates with Extra-large Pores and Chiral Open Frameworks......Page 108
2.5.4 Zinc Phosphates with Extra-large Pores and Chiral Open Frameworks......Page 109
2.5.5 Iron and Nickel Phosphates with Extra-large Pores......Page 111
2.5.6 Vanadium Phosphates with Extra-large Pores and Chiral Open Frameworks......Page 113
2.5.7 Germanates with Extra-large Pores......Page 116
2.5.8 Indium Sulfides with Extra-large-pore Open Frameworks......Page 117
2.6 Summary......Page 120
3.1.1 Features of Hydro(solvo)thermal Synthetic Reactions......Page 133
3.1.2 Basic Types of Hydro(solvo)thermal Reactions......Page 135
3.1.3 Properties of Reaction Media......Page 136
3.1.4 Hydro(solvo)thermal Synthesis Techniques......Page 138
3.2 Synthetic Approaches and Basic Synthetic Laws for Microporous Compounds......Page 139
3.2.1 Hydrothermal Synthesis Approach to Zeolites......Page 140
3.2.2 Solvothermal Synthesis Approach to Aluminophosphates......Page 160
3.2.3 Crystallization of Zeolites under Microwave Irradiation......Page 173
3.2.4 Hydrothermal Synthesis Approach in the Presence of Fluoride Source......Page 177
3.2.5 Special Synthesis Approaches and Recent Progress......Page 180
3.2.6 Application of Combinatorial Synthesis Approach and Technology in the Preparation of Microporous Compounds......Page 184
3.3.1 Linde Type A (LTA)......Page 188
3.3.2 Faujasite (FAU)......Page 189
3.3.3 Mordenite (MOR)......Page 191
3.3.4 ZSM-5 (MFI)......Page 192
3.3.5 Zeolite Beta (BEA)......Page 193
3.3.7 AlPO4-5 (AFI)......Page 194
3.3.8 AlPO4-11 (AEL)......Page 195
3.3.9 SAPO-31......Page 196
3.3.11 TS-1 (Ti-ZSM-5)......Page 197
4. Synthetic Chemistry of Microporous Compounds (II) – Special Compositions, Structures, and Morphologies......Page 207
4.1.2 Microporous Transition Metal Phosphates......Page 208
4.1.3 Microporous Aluminoborates......Page 213
4.1.4 Microporous Sulfides, Chlorides, and Nitrides......Page 215
4.1.5 Extra-large Microporous Compounds......Page 217
4.1.6 Zeolite-like Molecular Sieves with Intersecting(or Interconnected) Channels......Page 228
4.1.7 Pillared Layered Microporous Materials......Page 231
4.1.8 Microporous Chiral Catalytic Materials......Page 234
4.2.1 Single Crystals and Perfect Crystals......Page 242
4.2.2 Nanocrystals and Ultrafine Particles......Page 251
4.2.3 The Preparation of Zeolite Membranes and Coatings......Page 257
4.2.4 Synthesis of Microporous Material with Special Aggregation Morphology in the Presence of Templates......Page 264
4.2.5 Applications of Zeolite Membranes and Films......Page 267
5. Crystallization of Microporous Compounds......Page 283
5.1.1 Structures and Preparation Methods for Commonly Used Silicon Sources......Page 284
5.1.2 Structure of Commonly Used Aluminum Sources......Page 300
5.2 Crystallization Process and Formation Mechanism of Zeolites......Page 301
5.2.1 Solid Hydrogel Transformation Mechanism......Page 303
5.2.2 Solution-mediated Transport Mechanism......Page 305
5.2.3 Important Issues Related to the Solution-mediated Transport Mechanism......Page 310
5.2.4 Dual-phase Transition Mechanism......Page 321
5.3.1 Roles of Guest Molecules (Ions) in the Creation of Pores......Page 323
5.3.2 Studies on the Interaction between Inorganic Host and Guest Molecules via Molecular Simulation......Page 340
5.3.3 Conclusions and Prospects......Page 341
5.4 Crystallization Kinetics of Zeolites......Page 342
6.1.1 High-temperature Calcination......Page 361
6.1.2 Chemical Detemplating......Page 363
6.1.3 Solvent-extraction Method......Page 364
6.2 Outline of Secondary Synthesis......Page 366
6.3.1 Ion-exchange Modification of Zeolite LTA......Page 367
6.3.2 Modification of FAU Zeolite through Ion-exchange......Page 373
6.4.1 Dealumination Routes and Methods for Zeolites......Page 377
6.4.2 High-temperature Dealumination and Ultra-stabilization......Page 378
6.4.3 Chemical Dealumination and Silicon Enrichment of Zeolites......Page 380
6.5 Isomorphous Substitution of Heteroatoms in Zeolite Frameworks......Page 389
6.5.1 Galliation of Zeolites – Liquid–Solid Isomorphous Substitution......Page 390
6.5.2 Secondary Synthesis of Titanium-containing Zeolites –

Gas–Solid Isomorphous Substitution Technique......Page 393
6.5.3 Demetallation of Heteroatom Zeolites through High-temperature Vapor-phase Treatment......Page 394
6.6 Channel and Surface Modification of Zeolites......Page 395
6.6.1 Cation-exchange Method......Page 396
6.6.2 Channel-modification Method......Page 397
6.6.3 External Surface-modification Method......Page 399
7.1 Introduction......Page 413
7.2 Structure-prediction Methods for Inorganic Microporous Crystals......Page 414
7.2.1 Determination of 4-Connected Framework Crystal Structures by Simulated Annealing Method......Page 415
7.2.2 Generation of 3-D Frameworks by Assembly of 2-D Nets......Page 417
7.2.3 Automated Assembly of Secondary Building Units (AASBU Method)......Page 422
7.2.4 Prediction of Open-framework Aluminophosphate Structures by using the AASBU Method with Lowenstein’s Constraints......Page 428
7.2.5 Design of Zeolite Frameworks with Defined Pore Geometry through Constrained Assembly of Atoms......Page 431
7.2.6 Design of 2-D 3.4-Connected Layered Aluminophosphates with Al3P4O163-Stoichiometry......Page 442
7.2.7 Hypothetical Zeolite Databases......Page 445
7.3.1 Data Mining-aided Synthetic Approach......Page 446
7.3.2 Template-directed Synthetic Approach......Page 449
7.3.4 Building-block Built-up Synthetic Route......Page 470
7.4 Prospects......Page 475
8. Synthesis, Structure, and Characterization of Mesoporous Materials......Page 483
8.1 Introduction......Page 484
8.2.1 Mesostructure Assembly System: Interaction Mechanisms between Organics and Inorganics......Page 488
8.2.2 Formation Mechanism of Mesostructure: Liquid-crystal Template and Cooperative Self-assembly......Page 494
8.2.3 Surfactant Effective Packing Parameter: g and Physical Chemistry of Assembly and Interface Considerations......Page 505
8.3.1 Structural Characteristics and Characterization Techniques for Mesoporous Silica......Page 510
8.3.2 2-D Hexagonal Structure: MCM-41, SBA-15, and SBA-3......Page 513
8.3.3 Cubic Channel Mesostructures: MCM-48, FDU-5, and Im3mMaterials......Page 521
8.3.4 Caged Mesostructures......Page 524
8.3.5 Deformed Mesophases, Low-order Mesostructures, and Other Possible Mesophases......Page 536
8.3.6 Phase Transformation and Control......Page 541
8.4.1 Pore-size and Window-size Control......Page 542
8.4.2 Macroporous Material Templating Synthesis......Page 545
8.4.3 The Synthesis of Hierarchical Porous Silica Materials......Page 547
8.5.1 Synthesis Methods......Page 549
8.5.2 Surfactant, its Effect on Product Structure and Removal from Solid Product, and Nonsurfactants template......Page 551
8.5.3 Stabilization of Silica Mesophases and Post-synthesis Hydrothermal Treatment......Page 557
8.5.4 Zeolite Seed as Precursor and Nanocasting with Mesoporous Inorganic Solids......Page 563
8.5.5 Synthesis Parameters and Extreme Synthesis Conditions......Page 566
8.6.1 Chemical Modification......Page 574
8.6.2 Synthesis Challenges for Nonsilica Mesoporous Materials......Page 577
8.6.3 Metal-containing Mesoporous Silica-based Materials......Page 578
8.6.4 Inorganic–Organic Hybrid Materials......Page 579
8.6.5 Metal Oxides, Phosphates, Semiconductors, Carbons,and Metallic Mesoporous Materials......Page 581
8.7 Morphology and Macroscopic Form of Mesoporous Material......Page 588
8.7.1 ‘Single Crystal’ and Morphologies of Mesoporous Silicas......Page 589
8.7.2 Macroscopic Forms......Page 591
8.8.1 Possible Applications......Page 599
8.8.2 Challenges and Outlook......Page 600
9. Porous Host–Guest Advanced Materials......Page 619
9.1.1 Definition of Metal Clusters......Page 620
9.1.2 Preparation Approaches to Metal Clusters......Page 621
9.1.3 Alkali Metal Clusters......Page 623
9.1.4 Metal Clusters of Silver......Page 628
9.1.5 Noble Metal (Platinum, Palladium, Rhodium, Ruthenium,Iridium, Osmium) Clusters......Page 629
9.1.6 Other Metal Clusters......Page 630
9.1.7 Clusters of Metal Oxides or Oxyhydroxide......Page 631
9.2 Dyes in Zeolites......Page 632
9.3.1 Polymers in Zeolites......Page 637
9.3.2 Preparation of Porous Carbon using Zeolites......Page 639
9.3.3 Fullerenes Assembled in Zeolites......Page 640
9.3.4 Carbon Nanotube Growth in Zeolites......Page 641
9.4 Semiconductor Nanoparticles in Zeolites......Page 647
9.5.1 Incorporation of Metal–Pyridine Ligand Complexes......Page 652
9.5.2 Incorporation of Metal–Schiff Base Complexes......Page 656
9.5.3 Incorporation of Porphyrin and Phthalocyanine Complexes......Page 658
9.5.4 Incorporation of Other Metal Complexes......Page 660
9.6.1 Transition Metal–Multicarboxylate Coordination Polymers......Page 663
9.6.2 Coordination Polymers with N-containing Multidentate Aromatic Ligands......Page 664
9.6.3 Coordination Polymers with N- and O-containing Multidentate Ligands......Page 666
9.6.4 Zinc-containing Porous Coordination Polymers......Page 667
9.6.5 Adsorption Properties and H2 Storage of MOFs......Page 668
Further Reading......Page 683
Index......Page 689