Micro-Mesoporous Metallosilicates: Synthesis, Characterization, and Catalytic Applications

✍ Scribed by Wu P., Xu H. (ed.)

• Publisher: Wiley-VCH
• Year: 2024
• Tongue: English
• Leaves: 488
• Category: Library

✦ Synopsis

Up-to-date and in-depth text bridging the technology gap between fundamental research and industry-scale applications of porous materials for catalysis
Micro-Mesoporous Metallosilicates: Synthesis, Characterization, and Catalytic Applications comprehensively introduces the chemistry and catalytic technologies of metallosilicates, an important family of microporous crystalline zeolite and heteroatom-containing mesoporous materials, with a primary focus on design synthesis, characterization, theoretical studies, and catalytic applications of titanosilicates, tin-silicates, germanosilicates and Ti-mesosilica, and more.
The text covers recent advances in the synthesis of titanosilicates, including hydrothermal synthesis, dry-gel conversion, fluoride-assisted synthesis, and post-synthesis methods, along with the synthesis of metallosilicates with two-dimensional lamellar structures and their structural modifications as well as applications in selective oxidation reactions.
The text also discusses synthesis of germanosilicates with specially designed organic structure-directing agents, synthesis and catalytic applications of heteroatom-containing mesoporous silica, and dendritic mesoporous silica nanoparticles with unique wrinkled center-radial structures.
Overall, every important porous metallosilicate and its synthesis, characterization, pore engineering, catalytic application, and industrial technique and process are covered.
Specific sample topics discussed in Micro-Mesoporous Metallosilicates include:
Chemical post-modifications of titanosilicates, in terms of the effects on transfer, adsorption/desorption, and surface reactions.
X-Ray based techniques, ultraviolet-visible-near infrared spectroscopy, Raman spectroscopy, and solid-state NMR spectroscopy.
Theoretical calculation as an effective tool and supplement to understand the catalytic active center, structural character, and Brønsted/Lewis acidity.
Titanosilicates in the liquid-phase epoxidation reaction of propylene and propylene chloride to corresponding epoxides.
Effects of particle sizes, oxidation state, and location sites of Au nanoparticles, and epoxidation performance of Ti-containing materials.
Delivering cutting-edge research and bridging the technology gap between fundamental research and industrial applications, Micro-Mesoporous Metallosilicates is a valuable resource for chemists, materials scientists, chemical engineers, and experienced researchers in related fields.

✦ Table of Contents

Cover
Half Title
Micro‐Mesoporous Metallosilicates. Synthesis, Characterization, and Catalytic Applications
Copyright
Contents
Preface
1. Synthesis of Titanosilicates
1.1 Introduction
1.2 Synthesis of Medium‐Pore Titanosilicates
1.2.1 TS‐1 Synthesis
1.2.2 Ti‐MWW Synthesis
1.2.3 TS‐2 Synthesis
1.2.4 Synthesis of Other Medium‐Pore Titanosilicates
1.3 Synthesis of Large‐Pore Titanosilicates
1.3.1 Ti‐Beta Synthesis
1.3.2 Ti‐MOR Synthesis
1.3.3 Ti‐MSE Synthesis
1.3.4 Synthesis of Other Large‐Pore Titanosilicates
1.4 Synthesis of Extra‐Large‐Pore Titanosilicates
1.5 Synthesis of Mesoporous Titanosilicates
1.6 Synthesis of ETSs
1.7 Conclusions
References
2. Layered Heteroatom-Containing Zeolites
2.1 Introduction
2.2 Traditional Layered Heteroatom‐Containing Zeolites
2.2.1 Heteroatom‐Containing MWW‐Type Layered Zeolites and Their Derivative Zeolitic Materials
2.2.2 Heteroatom‐Containing Layered Zeolites Built from fer‐Layers
2.3 Novel Layered Heteroatom‐Containing Zeolites
2.3.1 Heteroatom‐Containing MFI‐Type Layered Zeolites
2.3.2 Germanosilicate‐Derived Heteroatom‐Containing Zeolites
2.4 Conclusions
Acknowledgments
References
3. Synthesis and Catalytic Applications of Sn- and Zr-Zeolites
3.1 Introduction
3.2 Synthesis of Sn‐ and Zr‐Zeolites
3.2.1 Bottom‐up Approaches
3.2.1.1 Hydrothermal Synthesis
3.2.1.2 Dry‐Gel Conversion Methods
3.2.1.3 Interzeolite Transformation
3.2.1.4 Structural Reconstruction Strategy
3.2.2 Top‐Down Approaches
3.2.2.1 Direct Metalation
3.2.2.2 Demetallation–Metalation
3.3 General Remarks
3.4 Catalytic Applications of Sn‐ and Zr‐Zeolites
3.4.1 Redox Catalysis
3.4.1.1 Baeyer–Villiger Oxidation
3.4.1.2 Meerwein–Ponndorf–Verley Redox
3.4.2 Lewis Acid Catalysis
3.4.2.1 Ring Opening of Epoxides
3.4.2.2 Aldol Reaction
3.4.2.3 Propane Dehydrogenation
3.4.3 Biomass Conversion
3.4.3.1 Sugar Isomerization
3.4.3.2 5‐(Hydroxymethyl)Furfural (HMF) Synthesis
3.4.3.3 Synthesis of Lactic Acid or Alkyl Lactates
3.4.3.4 γ‐Valerolactone Synthesis
3.5 General Remarks
References
4. Synthesis of Germanosilicates
4.1 Introduction
4.1.1 General Property of Ge/Si Oxides
4.1.2 Germanosilicate Glass
4.2 Isomorphous Substitution in Germanosilicates
4.2.1 Isomorphous Substitution Si in Germanate
4.2.2 Isomorphous Substitution Ge in Silicates
4.3 Inorganic Structure‐Directing Effects
4.3.1 Structure‐Directing Effects of Ge
4.3.2 Structure‐Directing Effects of F−
4.4 Organic Structure‐Directing Agents in Germanosilicate Synthesis
4.4.1 Organic Structure‐Directing Agent Types and Revolutions
4.4.2 Two Important Families of OSDA
4.5 Structure Diversity of Germanosilicates/Silicogermanates
4.5.1 Relationship Between Composition and Structure
4.5.2 Pore Opening
4.6 Possibility of Elimination of Ge and Catalytic Research of Germanosilicates
4.6.1 The Price Concern of Ge
4.6.2 Removal of Ge in Zeolite Synthesis
4.6.3 Removal of Ge with Post‐synthesis
4.6.4 Catalytic Research of Germanosilicates
4.7 Conclusions and Outlook
References
5. Structural Modifications on Germanosilicates
5.1 Introduction
5.2 Germanosilicates to Layered Precursors
5.2.1 UTL to IPC‐1P
5.3 ADOR Strategy for Developing New Zeolite Structures
5.3.1 Assembly
5.3.2 Disassembly
5.3.3 Organization
5.3.4 Reassembly
5.3.5 Liquid‐phase ADOR
5.3.5.1 The UTL Case
5.3.5.2 The CIT‐13 Case
5.3.5.3 The UOV Case
5.3.5.4 The IWW Case
5.3.6 Vapor‐phase ADOR
5.3.7 Reductive Degermanation
5.3.8 Solid‐state Transformations
5.4 Structure Stabilization
5.4.1 Degermanation
5.4.2 Functionalization With Catalytic Sites
5.4.3 Slow Disassembly
5.4.4 Reverse ADOR
5.5 Germanosilicate‐Derived Catalysts
5.5.1 Summary and Perspectives
Acknowledgements
References
6. Heteroatom-Containing Dendritic Mesoporous Silica Nanoparticles
6.1 Introduction
6.2 Main Synthetic Methods and Formation Mechanism of Pure Silica‐Based Dendritic Mesoporous Silica Nanoparticles (DMSNs)
6.2.1 Main Synthetic Methods of Dendritic Mesoporous Silica Nanoparticles (DMSNs)
6.2.2 Unified Formation Mechanism of Dendritic Mesoporous Silica Nanoparticles
6.3 Synthesis of Heteroatom‐Containing DMSNs and Their Catalytic Applications
6.3.1 One‐Pot Doping Strategy for DMSNs Containing Heteroatoms (Al/Ti/V/Sn/Mn/Fe/Co)
6.3.2 Post‐grafting for Surface Metal Complexes
6.3.3 Loading of Metal and/or Metal Oxide Nanoparticles Within the Nanopores
6.4 Summary and Perspectives
Acknowledgments
References
7. Chemical Post-Modifications of Titanosilicates
7.1 Introduction
7.2 Diffusion and Adsorption/Desorption
7.2.1 Hierarchical Titanosilicates
7.2.2 Surface Hydrophilicity and Hydrophobicity
7.3 Surface Reaction
7.3.1 Ti Active Sites Content
7.3.2 Ti Active Sites Distribution
7.3.3 Ti Active Sites Properties
7.3.3.1 Electrophilicity of Ti Active Sites
7.3.3.2 Coordinate State of Ti Active Sites
7.3.3.3 Adjacent Silanol Groups of Ti Active Sites
7.4 Solvent Effect
7.4.1 Effect of Solvent on Diffusion
7.4.2 Effect of Solvent on Adsorption/Desorption
7.4.3 Effect of Solvent on Surface Reactions
7.4.3.1 Effect on the Formation on TiOOH
7.4.3.2 Effect on the Stability of TiOOH
7.4.3.3 Effect on the Transfer of TiOOH
7.5 Conclusions and Prospects
References
8. Spectroscopic Characterization of Heteroatom-Containing Zeolites
8.1 X‐Ray Technique
8.1.1 XRD Determination of Framework Structure and Heteroatoms in Zeolites
8.1.2 XAS Characterization of Metals in Zeolite
8.1.3 XPS Analysis of the Chemical State of Metal Species
8.2 Ultraviolet–Visible‐Near Infrared (UV–VIS–NIR) Spectroscopy
8.2.1 UV–VIS–NIR Characterization of Framework and Non‐Framework Metal Species
8.2.2 UV–VIS–NIR Characterization of Metal Species on Ion Exchange Sites of Zeolites
8.3 Raman Spectroscopy
8.3.1 Raman Study of Synthesis Mechanism and Assembly of Metal‐Zeolites
8.3.2 Raman Characterization of Active Metal‐Oxygen Species in Zeolites
8.4 Solid‐State NMR Spectroscopy
8.4.1 Solid‐State NMR Characterization of Metal Elements in Zeolites
8.4.2 Solid‐State Correlation NMR Measurement of Active Site Proximity and Host–Guest Interactions
8.4.3 In Situ Solid‐State NMR for the Study of Reaction Mechanisms
8.5 Conclusions
Acknowledgments
References
9. Theoretical Calculations of Heteroatom Substituted Zeolites
9.1 Introduction
9.2 Ti‐Doped Zeolites
9.2.1 Preferred Tetrahedral (T) Sites for Substitution
9.2.2 Lewis Acid
9.2.3 Active Site with H2O2
9.2.4 Reaction Mechanism
9.2.4.1 Epoxidation of Olefins
9.2.4.2 Ammoximation and Oxidation of Cyclohexanone
9.2.4.3 Oxidation Desulfurization Reactions
9.3 Sn‐Doped Zeolites
9.3.1 Preferred Substitution T Sites and Acidity
9.3.2 Reaction Mechanism
9.3.2.1 Glucose Isomerization to Fructose and Epimerization to Mannose
9.3.3 Other Catalytic Reactions
9.4 Other Metal‐Substituted Zeolites
9.5 Summary and Outlook
Acknowledgments
References
10. Catalytic Ammoximation of Ketones or Aldehydes Using Titanosilicates
10.1 Introduction
10.2 The Development of Titanosilicates in Ammoximation of Ketones and Aldehydes
10.3 Ammoximation Mechanism and Product Distributions of Representative Ketones and Aldehydes
10.3.1 Titanosilicate‐Catalyzed Ammoximation Mechanism
10.3.2 Product Distributions for Ammoximation of Representative Carbonyl Compounds
10.4 Enhancing Ammoximation Performances in Titanosilicate/H2O2 System
10.4.1 Improvement of Catalytic Ammoximation Activity
10.4.1.1 Regulation of Ti Active Sites
10.4.1.2 Enhancement of Diffusion Properties
10.4.1.3 Improvement of Hydrophobicity
10.4.1.4 Regulation of Acid Sites
10.4.2 Improvement of Catalytic Ammoximation Stability
10.5 Ketone Ammoximation Technology for Industrial Processes
10.6 Titanosilicate‐Based Bifunctional Catalysts for Process Intensified or Tandem Ammoximation Reactions
10.7 Conclusions and Perspectives
Acknowledgments
References
11. Titanosilicate-Based Alkene Epoxidation Catalysis
11.1 Introduction
11.2 Reaction Chemistry of Alkene Epoxidation Catalyzed by Titanosilicate Zeolites
11.3 Typical Alkene Epoxidation Cases
11.3.1 Propylene Epoxidation for PO Production
11.3.2 Propylene Chloride Epoxidation
11.3.3 Ethylene Epoxidation to EO, EG, and Ethers
11.4 Industrial Propylene Epoxidation Techniques and Processes
11.5 Conclusion and Outlook
Acknowledgments
References
12. Propylene Epoxidation with Cumene Hydroperoxide/Titanosilicates
12.1 Introduction
12.2 Traditional Route for PO Production (Chlorohydrin Process)
12.3 Co‐production Route for PO Production (PO/TBA and PO/SM Processes)
12.4 PO‐Only Production Routes (HPPO and CMHPPO Routes)
12.5 Catalyst Design for PO‐Only Routes
12.5.1 Mesoporous Ti‐Doped Catalysts for CMHPPO Process
12.5.2 Hierarchical Titanosilicates for CMHPPO Process
12.6 Industrial CMHPPO Process
12.7 Conclusions and Outlooks
References
13. Hydroxylation of Benzene and Phenol on Zeolite Catalysts
13.1 Introduction
13.2 Hydroxylation of Benzene to Phenol
13.2.1 Gas‐Phase Reactions
13.2.1.1 Heteroatomic Molecular Sieves as Catalysts
13.2.1.2 Fe‐Containing Molecular Sieves as Catalysts
13.2.1.3 Other Methods for Benzene Hydroxylation to Phenol
13.2.2 Liquid‐Phase Reactions
13.2.2.1 Fe‐Containing Molecular Sieves as Catalysts
13.2.2.2 Microporous Crystalline Titanosilicates as Catalysts
13.2.2.3 Catalytic Recyclability of Fe‐ and Ti‐Containing Zeolites
13.3 Hydroxylation of Phenol to DHB
13.3.1 Fe‐Containing Molecular Sieves as Catalysts
13.3.1.1 Effect of Reaction Conditions
13.3.1.2 Catalytic Recyclability
13.3.1.3 Improving Catalytic Performance by Developing Hierarchically Porous Structure
13.3.1.4 Catalytic Mechanism
13.3.2 Titanosilicate Molecular Sieves as Catalysts
13.3.2.1 Effect of Pore Structure
13.3.2.2 Effect of Solvent
13.3.2.3 Effect of Reaction Conditions
13.3.2.4 Stability of Ti Species
13.3.3 Transition Metal Complexes Encapsulated in Zeolite Y as Catalysts
13.4 Summary
Acknowledgments
References
14. Bifunctional Titanosilicate Systems for the Gas-Phase Catalytic Propylene Epoxidation with Hydrogen and Oxygen
14.1 Introduction
14.2 Advances in the Catalytic Propylene Epoxidation with H2 and O2
14.2.1 Mechanistic Insights into Au‐Ti Synergy
14.2.2 Effects of Au Particle Properties
14.2.2.1 Au Particle Sizes
14.2.2.2 Au Oxidation States
14.2.2.3 Au Sites Location
14.2.3 Effects of Materials' Properties for Immobilizing Au Particles
14.2.3.1 Ti‐SiO2 Materials
14.2.3.2 Mesoporous Ti‐Containing Materials
14.2.3.3 Microporous Ti‐Containing Materials
14.2.3.4 Effects of Hydrophobicity
14.2.4 Effect of Promoters
14.3 Conclusions and Outlook
Conflicts of Interest
References
15. Zeolites Containing Heteroatoms/Metal Nanoparticles for Catalytic Conversion of Light Alkanes
15.1 Introduction
15.2 Metal Nanoclusters and Heteroatoms in Zeolite for Propane Dehydrogenation
15.2.1 Zeolite‐Based Catalysts for Non‐Oxidative PDH
15.2.2 Zeolite‐Based Catalysts for Oxidative PDH
15.3 Metallosilicates for Ethane Dehydrogenation
15.3.1 Metallosilicates for Non‐Oxidative Dehydrogenation of Ethane
15.3.2 Metallosilicates for Oxidative Dehydrogenation of Ethane
15.4 Zeolite Catalysts for Selective Oxidation of Methane
15.4.1 Bionic Catalysis of Methane to Methanol Using Metallosilicates
15.4.2 In situ Synthesizing Hydrogen Peroxide for Low‐Temperature Methane Oxidation Using Metal@zeolite
15.4.3 Direct Metal Oxidation with Oxygen by Zeolite‐Supported Nanoparticle Catalysts
15.5 Summary and Outlook
Acknowledgments
References
16. Design and Applications of Single-Site Photocatalysis Using Metallosilicates
16.1 Introduction
16.2 Ti‐Based Single‐Site Photocatalysis Within Zeolites and Mesoporous Silica
16.3 Single‐Site Photocatalysis Based Thin Films
16.3.1 Thin Films with Ti‐Oxide Species
16.3.2 Thin Films with Various Metal Oxide Species (Mo, V, Cr, and W)
16.4 Visible‐Light Sensitive Single‐Site Photocatalysis
16.5 Nano‐Sized Metal Preparation Using Single‐Site Photocatalyst
16.5.1 Preparation of Monometallic NPs
16.5.2 Preparation of Bimetallic Metal NPs
16.6 Conclusions
Acknowledgments
References
Index