Chemistry of Zeolites and Related Porous Materials

Professor Ruren Xu is Professor of Chemistry at Jilin University, P. R. China and an elected member of the Chinese Academy of Sciences. With over 400 papers in international journals and 6 research monographs, he is known worldwide for contributions in the synthesis of new families of microporous materials, establishment of solvothermal synthetic route, and pioneering work in the rational micropore-synthesis. Prof. Xu has served as a main editor or on the editorial board for 12 journals in the field. He was a councilor of International Zeolite Association from 1998 to 2004 and is the current President of Chinese Zeolite Association. Between 2005 and 2007, he is also the Chairman for the 15th International Zeolite Conference. Prof. Wenqin Pang is Professor of Chemistry at Jilin University, with research interest on synthetic chemistry of micro- and mesoporous compounds, especially on hetro-atom containing porous materials. She has published over 300 papers and 5 books. Prof. Jihong Yu is Professor of Chemistry at Jilin University. Her research interest is design and synthesis of inorganic open-framework materials, with over 100 papers. She is a member of editorial boards of Microporous and Mesoporous Materials and Current Chemical Biology. Dr. Qisheng Huo is a Staff Member, Fundamental Science Directorate, Pacific Northwest National Laboratory, USA. His current research interests include the design and synthesis of multi-functional nano-structured catalyst. Prof. Jiesheng Chen is Professor of Chemistry, Jilin University. His research interests are host-guest chemistry and physics, and synthesis of solid compounds with new structures and functions. He has published over 120 papers.

Preface. 1. Introduction.

1.1 The Evolution and Development of Porous Materials.

1.1.1 From Natural Zeolites to Synthesized Zeolites.

1.1.2 From Low-silica to High-silica Zeolites.

1.1.3 From Zeolites to Aluminophosphate Molecular Sieves and Other Microporous Phosphates.

1.1.4 From 12-Membered-ring Micropores to Extra-large Micropores.

1.1.5 From Extra-large Micropores to Mesopores.

1.1.6 Emergence of Macroporous Materials.

1.1.7 From Inorganic Porous Frameworks to Porous Metal-organic Frameworks (MOFs).

1.2 Main Applications and Prospects.

1.2.1 The Traditional Fields of Application and Prospects of Microporous Molecular Sieves.

1.2.2 Prospects in the Application Fields of Novel, High-tech, and Advanced Materials.

1.2.3 The Main Application Fields and Prospects for Mesoporous Materials.

1.3 The Development of Chemistry for Molecular Sieves and Porous Materials.

1.3.1 The Development from Synthesis Chemistry to Molecular Engineering of Porous Materials.

1.3.2 Developments in the Catalysis Study of Porous Materials.

2. Structural Chemistry of Microporous Materials.

2.1 Introduction.

2.2 Structural Building Units of Zeolites.

2.2.1 Primary Building Units.

2.2.2 Secondary Building Units (SBUs).

2.2.3 Characteristic Cage-building Units.

2.2.4 Characteristic Chain- and Layer-building Units.

2.2.5 Periodic Building Units (PBUs).

2.3 Composition of Zeolites.

2.3.1 Framework Composition.

2.3.2 Distribution and Position of Cations in the Structure.

2.3.3 Organic Templates.

2.4 Framework Structures of Zeolites.

2.4.1 Loop Configuration and Coordination Sequences.

2.4.2 Ring Number of Pore Opening and Channel Dimension in Zeolites.

2.4.3 Framework Densities (FDs).

2.4.4 Selected Zeolite Framework Structures.

2.5 Zeolitic Open-framework Structures.

2.5.1 Anionic Framework Aluminophosphates with Al/P (less than or equal to) 1.

2.5.2 Open-framework Gallophosphates with Extra-large Pores.

2.5.3 Indium Phosphates with Extra-large Pores and Chiral Open Frameworks.

2.5.4 Zinc Phosphates with Extra-large Pores and Chiral Open Frameworks.

2.5.5 Iron and Nickel Phosphates with Extra-large Pores.

2.5.6 Vanadium Phosphates with Extra-large Pores and Chiral Open Frameworks.

2.5.7 Germanates with Extra-large Pores.

2.5.8 Indium Sulfides with Extra-large-pore Open Frameworks.

2.6 Summary.

3. Synthetic Chemistry of Microporous Compounds (I) – Fundamentals and Synthetic Routes.

3.1 Introduction to Hydro(solvo)thermal Synthesis.

3.1.1 Features of Hydro(solvo)thermal Synthetic Reactions.

3.1.2 Basic Types of Hydro(solvo)thermal Reactions.

3.1.3 Properties of Reaction Media.

3.1.4 Hydro(solvo)thermal Synthesis Techniques.

3.1.5 Survey of the Applications of Hydro(solvo)thermal Synthetic Routes in the Synthesis of Microporous Crystals and the Preparation of Porous Materials.

3.2 Synthetic Approaches and Basic Synthetic Laws for Microporous Compounds.

3.2.1 Hydrothermal Synthesis Approach to Zeolites.

3.2.2 Solvothermal Synthesis Approach to Aluminophosphates.

3.2.3 Crystallization of Zeolites under Microwave Irradiation.

3.2.4 Hydrothermal Synthesis Approach in the Presence of Fluoride Source.

3.2.5 Special Synthesis Approaches and Recent Progresses.

3.2.6 Application of Combinatorial Synthesis Approach and Technology in the Preparation of Microporous Compounds.

3.3 Typical Synthetic Procedures for some Important Molecular Sieves.

3.3.1 Linde Type A (LTA).

3.3.2 Faujasite (FAU).

3.3.3 Mordenite (MOR).

3.3.4 ZSM-5 (MFI).

3.3.5 Zeolite Beta (BEA).

3.3.6 Linde Type L (LTL).

3.3.7 AlPO4-5 (AFI).

3.3.8 AlPO4-11 (AEL).

3.3.9 SAPO-31.

3.3.10 SAPO-34 (CHA).

3.3.11 TS-1 (Ti-ZSM-5).

4. Synthetic Chemistry of Microporous Compounds (II) – Special Compositions, Structures, and Morphologies.

4.1 Synthetic Chemistry of Microporous Compounds with Special Compositions and Structures.

4.1.1 M(III)X(V)O4-type Microporous Compounds.

4.1.2 Microporous Transition Metal Phosphates.

4.1.3 Microporous Aluminoborates.

4.1.4 Microporous Sulfides, Chlorides, and Nitrides.

4.1.5 Extra-large Microporous Compounds.

4.1.6 Zeolite-like Molecular Sieves with Intersecting (or Interconnected) Channels.

4.1.7 Pillared Layered Microporous Materials.

4.1.8 Microporous Chiral Catalytic Materials.

4.2 Synthetic Chemistry of Microporous Compounds with Special Morphologies.

4.2.1 Single Crystals and Perfect Crystals.

4.2.2 Nanocrystals and Ultrafine Particles.

4.2.3 The Preparation of Zeolite Membranes and Coatings.

4.2.4 Synthesis of Microporous Material with Special Aggregation Morphology in the Presence of Templates.

4.2.5 Applications of Zeolite Membranes and Films.

5. Crystallization of Microporous Compounds.

5.1 Starting Materials of Zeolite Crystallization.

5.1.1 Structures and Preparation Methods for Commonly Used Silicon Sources.

5.1.2 Structure of Commonly Used Aluminum Sources.

5.2 Crystallization Process and Formation Mechanism of Zeolites.

5.2.1 Solid Hydrogel Transformation Mechanism.

5.2.2 Solution-mediated Transport Mechanism.

5.2.3 Important Issues Related to the Solution-mediated Transport Mechanism.

5.2.4 Dual-phase Transition Mechanism.

5.3 Structure-directing Effect and Templating in the Crystallization Process of Microporous Compounds.

5.3.1 Roles of Guest Molecules (Ions) in the Creation of Pores.

5.3.2 Studies on the Interaction between Inorganic Host and Guest Molecules via Molecular Simulation.

5.3.3 Conclusions and Prospects.

5.4 Crystallization Kinetics of Zeolites.

6. Preparation, Secondary Synthesis, and Modification of Zeolites.

6.1 Preparation of Zeolites – Detemplating of Microporous Compounds.

6.1.1 High-temperature Calcination.

6.1.2 Chemical Detemplating.

6.1.3 Solvent-extraction Method.

6.2 Outline of Secondary Synthesis.

6.3 Cation-exchange and Modification of Zeolites.

6.3.1 Ion-exchange Modification of Zeolite LTA.

6.3.2 Modification of FAU Zeolite through Ion-exchange.

6.4 Modification of Zeolites through Dealumination.

6.4.1 Dealumination Routes and Methods for Zeolites.

6.4.2 High-temperature Dealumination and Ultra-stabilization.

6.4.3 Chemical Dealumination and Silicon Enrichment of Zeolites.

6.5 Isomorphous Substitution of Heteroatoms in Zeolite Frameworks.

6.5.1 Galliation of Zeolites – Liquid–Solid Isomorphous Substitution.

6.5.2 Secondary Synthesis of Titanium-containing Zeolites – Gas–Solid Isomorphous Substitution Technique.

6.5.3 Demetallation of Heteroatom Zeolites through High-temperature Vapor-phase Treatment.

6.6 Channel and Surface Modification of Zeolites.

6.6.1 Cation-exchange Method.

6.6.2 Channel-modification Method.

6.6.3 External Surface-modification Method.

7. Towards Rational Design and Synthesis of Inorganic Microporous Materials.

7.1 Introduction.

7.2 Structure-prediction Methods for Inorganic Microporous Crystals.

7.2.1 Determination of 4-Connected Framework Crystal Structures by Simulated Annealing Method.

7.2.2 Generation of 3-D Frameworks by Assembly of 2-D Nets.

7.2.3 Automated Assembly of Secondary Building Units (AASBU Method).

7.2.4 Prediction of Open-framework Aluminophosphate Structures by using the AASBU Method with Lowenstein’s Constraints.

7.2.5 Design of Zeolite Frameworks with Defined Pore Geometry through Constrained Assembly of Atoms.

7.2.6 Design of 2-D 3.4-Connected Layered Aluminophosphates with Al3P4O163- Stoichiometry.

7.2.7 Hypothetical Zeolite Databases.

7.3 Towards Rational Synthesis of Inorganic Microporous Materials.

7.3.1 Data Mining-aided Synthetic Approach.

7.3.2 Template-directed Synthetic Approach.

7.3.3 Rational Synthesis through Combinatorial Synthetic Route.

7.3.4 Building-block Built-up Synthetic Route.

7.4 Prospects.

8. Synthesis, Structure, and Characterization of Mesoporous Materials.

8.1 Introduction.

8.2 Synthesis Characteristics and Formation Mechanism of Ordered Mesoporous Materials.

8.2.1 Mesostructure Assembly System: Interaction Mechanisms between Organics and Inorganics.

8.2.2 Formation Mechanism of Mesostructure: Liquid-crystal Template and Cooperative Self-assembly.

8.2.3 Surfactant Effective Packing Parameter: g and Physical Chemistry of Assembly and Interface Considerations.

8.3 Mesoporous Silica: Structure and Synthesis.

8.3.1 Structural Characteristics and Characterization Techniques for Mesoporous Silica.

8.3.2 2-D Hexagonal Structure: MCM-41, SBA-15, and SBA-3.

8.3.3 Cubic Channel Mesostructures: MCM-48, FDU-5, and Im3m Materials.

8.3.4 Caged Mesostructures.

8.3.5 Deformed Mesophases, Low-order Mesostructures, and Other Possible Mesophases.

8.3.6 Phase Transformation and Control.

8.4 Pore Control.

8.4.1 Pore-size and Window-size Control.

8.4.2 Macroporous Material Templating Synthesis.

8.4.3 The Synthesis of Hierarchical Porous Silica Materials.

8.5 Synthesis Strategies.

8.5.1 Synthesis Methods.

8.5.2 Surfactant, its Effect on Product Structure and Removal from Solid Product, and Nonsurfactants template.

8.5.3 Stabilization of Silica Mesophases and Post-synthesis Hydrothermal Treatment.

8.5.4 Zeolite Seed as Precursor and Nanocasting with Mesoporous Inorganic Solids.

8.5.5 Synthesis Parameters and Extreme Synthesis Conditions.

8.6 Composition Extension of Mesoporous Materials.

8.6.1 Chemical Modification.

8.6.2 Synthesis Challenges for Nonsilica Mesoporous Materials.

8.6.3 Metal-containing Mesoporous Silica-based Materials.

8.6.4 Inorganic–Organic Hybrid Materials.

8.6.5 Metal Oxides, Phosphates, Semiconductors, Carbons, and Metallic Mesoporous Materials.

8.7 Morphology and Macroscopic Form of Mesoporous Material.

8.7.1 ‘Single Crystal’ and Morphologies of Mesoporous Silicas.

8.7.2 Macroscopic Forms.

8.8 Possible Applications, Challenges, and Outlook.

8.8.1 Possible Applications.

8.8.2 Challenges and Outlook.

9. Porous Host–Guest Advanced Materials.

9.1 Metal Clusters in Zeolites.

9.1.1 Definition of Metal Clusters.

9.1.2 Preparation Approaches to Metal Clusters.

9.1.3 Alkali Metal Clusters.

9.1.4 Metal Clusters of Silver.

9.1.5 Noble Metal (Platinum, Palladium, Rhodium, Ruthenium, Iridium, Osmium) Clusters.

9.1.6 Other Metal Clusters.

9.1.7 Clusters of Metal Oxides or Oxyhydroxide.

9.2 Dyes in Zeolites.

9.3 Polymers and Carbon Materials in Zeolites.

9.3.1 Polymers in Zeolites.

9.3.2 Preparation of Porous Carbon using Zeolites.

9.3.3 Fullerenes Assembled in Zeolites.

9.3.4 Carbon Nanotube Growth in Zeolites.

9.4 Semiconductor Nanoparticles in Zeolites.

9.5 Metal Complexes in Molecular Sieves.

9.5.1 Incorporation of Metal–Pyridine Ligand Complexes.

9.5.2 Incorporation of Metal–Schiff Base Complexes.

9.5.3 Incorporation of Porphyrin and Phthalocyanine Complexes.

9.5.4 Incorporation of Other Metal Complexes.

9.6 Metal–Organic Porous Coordination Polymers.

9.6.1 Transition Metal–Multicarboxylate Coordination Polymers.

9.6.2 Coordination Polymers with N-containing Multidentate Aromatic Ligands.

9.6.3 Coordination Polymers with N- and O-containing Multidentate Ligands.

9.6.4 Zinc-containing Porous Coordination Polymers.

9.6.5 Adsorption Properties and H2 Storage of MOFs.

Further Reading.