Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications

✍ Scribed by Garcia H., Dhakshinamoorthy A. (ed.)

• Publisher: WILEY-VCH
• Year: 2024
• Tongue: English
• Leaves: 496
• Category: Library

✦ Synopsis

Understanding the synthesis and applications of porous solid catalysts.
Heterogeneous catalysis is a catalytic process in which catalysts and reactants exist in different phases. Heterogeneous catalysis with solid catalysts proceeds through the absorption of substrates and reagents which are liquid or gas, and this is largely dependent on the accessible surface area of the solid which can generate active reaction sites. The synthesis of porous solids is an increasingly productive approach to generating solid catalysts with larger accessible surface area, allowing more efficient catalysis.
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications provides a comprehensive overview of synthesis and use of porous solids as heterogeneous catalysts. It provides detailed analysis of pore engineering, a thorough characterization of the advantages and disadvantages of porous solids as heterogeneous catalysts, and an extensive discussion of applications. The result is a foundational introduction to a cutting-edge field.
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications readers will also find.
An editorial team comprised of international experts with extensive experience.
Detailed discussion of catalyst classes including zeolites, mesoporous aluminosilicates, and more.
A special focus on size selective catalysis.
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications is an essential reference for catalytic chemists, organic chemists, materials scientists, physical chemists, and any researchers or industry professionals working with heterogeneous catalysis.

✦ Table of Contents

Cover
Half Title
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications
Copyright
Contents
Preface
1. Engineering of Metal Active Sites in MOFs
1.1 Metal Node Engineering
1.1.1 Frameworks with Intrinsically Active Metal Nodes
1.1.1.1 Metal–Organic Frameworks with Only One Metal
1.1.1.2 Metal–Organic Frameworks with more than One Metal in its Cluster
1.1.2 Introducing Defectivity as a Powerful Tool to Tune Metal‐node Catalytic Properties in MOFs
1.1.3 Incorporating Metals to Already‐Synthetized Metal–Organic Frameworks: Isolating the Catalytic Site
1.1.4 Metal Exchange
1.1.5 Attaching Metallic Units to the MOF
1.1.6 Grafting of Organometallic Complexes into the MOF Nodes
1.2 Ligand Engineering
1.2.1 Ligands as Active Metal Sites
1.2.1.1 Creating Metal Sites in the Organic Linkers. Types of Ligands
1.2.1.2 Cooperation Between Single‐Metal Sites and Metalloligands
1.2.1.3 Ligand Accelerated Catalysis (LAC)
1.2.2 Introduction of Metals by Direct Synthesis
1.2.2.1 In‐situ Metalation
1.2.2.2 Premetalated Linker
1.2.2.3 Postgrafting Metal Complexes
1.2.3 Introduction of Metals by Post‐synthetic Modifications
1.2.3.1 Post‐synthetic Exchange or Solvent‐Assisted Linker Exchange (SALE)
1.2.3.2 Post‐synthetic Metalation
1.3 Metal‐Based Guest Pore Engineering
1.3.1 Encapsulation Methodologies in As‐Made Metal–Organic Frameworks
1.3.1.1 Incipient Wetness Impregnation
1.3.1.2 Ship‐in‐a‐Bottle
1.3.1.3 Metal–Organic Chemical Vapor Deposition (MOCVD)
1.3.1.4 Metal‐Ion Exchange
1.3.2 In Situ Guest Metal–Organic Framework Encapsulations
1.3.2.1 Solvothermal Encapsulation or One Pot
1.3.2.2 Co‐precipitation Methodologies
References
2. Engineering the Porosity and Active Sites in Metal–Organic Framework
2.1 Introduction
2.2 Active Sites in MOF
2.2.1 Active Sites Near Pores in MOF
2.2.2 Active Sites Near Metallic Nodes in MOF
2.2.3 Active Sites Near Ligand Center in MOF
2.3 Synthesis and Characterization
2.4 Engineering of Active Sites in MOF Structure for Catalytic Transformations
2.4.1 Pore Tunability
2.4.2 Metal Nodes
2.4.3 Ligand Centers
2.5 Conclusion
References
3. Characterization of Organic Linker‐Containing Porous Materials as New Emerging Heterogeneous Catalysts
3.1 Introduction
3.2 Microscopy Techniques
3.2.1 Scanning Electron Microscopy (SEM)
3.2.2 Transmission Electron Microscopy (TEM)
3.2.3 Atomic Force Microscopy (AFM)
3.3 Spectroscopy Techniques
3.3.1 X‐ray Spectroscopy
3.3.1.1 X‐ray Diffraction (XRD)
3.3.1.2 X‐ray Photoelectron Spectroscopy (XPS)
3.3.1.3 X‐ray Absorption Fine Structure (XAFS) Techniques
3.3.2 Nuclear Magnetic Resonance (NMR)
3.3.3 Electron Paramagnetic Resonance (EPR)
3.3.4 Ultraviolet‐Visible Diffuse Reflectance Spectroscopy (UV–Vis DRS)
3.3.5 Inductively Coupled Plasma (ICP) Analysis
3.4 Other Techniques
3.4.1 Thermogravimetric Analysis (TGA)
3.4.2 N2 Adsorption
3.4.3 Density Functional Theory (DFT) Calculations
3.5 Conclusions
Acknowledgments
References
4. Mixed Linker MOFs in Catalysis
4.1 Introduction
4.1.1 Introduction to Mixed Linker MOFs
4.2 Strategies for Synthesizing Mixed‐Linker MOFs
4.2.1 IML Frameworks
4.2.2 HML Frameworks
4.2.3 TML Frameworks
4.3 Types of Mixed‐Linker MOFs
4.3.1 Pillared‐Layer Mixed‐Linker MOFs
4.3.2 Cage‐Directed Mixed‐Linker MOFs
4.3.3 Cluster‐Based Mixed‐Linker MOFs
4.3.4 Structure Templated Mixed‐Linker MOFs
4.4 Introduction to Catalysis with MOFs
4.5 Mixed‐Linker MOFs as Heterogeneous Catalysts
4.5.1 Mixed‐Linker MOFs with Similar Size/Directionality Linkers
4.5.2 Mixed‐Linker MOFs with Structurally Independent Linkers
4.6 Conclusion
References
5. Acid‐Catalyzed Diastereoselective Reactions Inside MOF Pores
5.1 Introduction
5.2 Diastereoselective Reactions Catalyzed by MOFs
5.2.1 Meerwein–Ponndorf–Verley Reduction of Carbonyl Compounds
5.2.2 Aldol Addition Reactions
5.2.3 Diels–Alder Reaction
5.2.4 Isomerization Reactions
5.2.5 Cyclopropanation
5.3 Conclusions and Outlook
Acknowledgments
References
6. Chiral MOFs for Asymmetric Catalysis
6.1 Chiral Metal–Organic Frameworks (CMOFs)
6.2 Synthesis Methods of CMOFs with Achiral and Chiral Building Blocks
6.2.1 Spontaneous Resolution
6.2.2 Direct Synthesis
6.2.3 Indirect Synthesis
6.3 Chiral MOF Catalysts
6.3.1 Brief History of CMOF‐Based Catalysts
6.3.2 Designing CMOF Catalysts
6.4 Examples of Enantioselective Catalysis Using CMOF‐Based Catalysts
6.4.1 Type I: Chiral MOFs in Simple Asymmetric Reactions
6.4.2 Type II: Chiral MOFs in Complex Asymmetric Reactions
6.5 Conclusion
References
7. MOF‐Supported Metal Nanoparticles for Catalytic Applications
7.1 Introduction
7.2 Synergistic Catalysis by MNP@MOF Composites
7.2.1 The Inorganic Nodes of MOFs Cooperating with Metal NPs
7.2.2 The Organic Linkers of MOFs Cooperating with Metal NPs
7.2.3 The Nanostructures of MOFs Cooperating with Metal NPs
7.3 Electrocatalysis Applications
7.3.1 Hydrogen Evolution Reaction
7.3.2 Oxygen Evolution Reaction
7.3.3 Oxygen Reduction Reaction
7.3.4 CO2 Reduction Reaction
7.3.4.1 CO
7.3.4.2 HCOOH
7.3.4.3 C2H4
7.3.5 Nitrogen Reduction Reaction
7.3.6 Oxidation of Small Molecules
7.4 Photocatalytic Applications
7.4.1 Photocatalytic Hydrogen Production
7.4.2 Photocatalytic CO2 Reduction
7.4.2.1 CO2 Photoreduction to CO
7.4.2.2 CO2 Photoreduction to CH3OH
7.4.2.3 CO2 Photoreduction to HCOO−/HCOOH
7.4.3 Photocatalytic Organic Reactions
7.4.3.1 Photocatalytic Hydrogenation Reactions
7.4.3.2 Photocatalytic Oxidation Reactions
7.4.3.3 Photocatalytic Coupling Reaction
7.4.4 Photocatalytic Degradation of Organic Pollutants
7.4.4.1 Degradation of Pollutants in Wastewater
7.4.4.2 Degradation of Gas‐Phase Organic Compounds
7.5 Thermocatalytic Applications
7.5.1 Oxidation Reactions
7.5.1.1 Gas‐Phase Oxidation Reactions
7.5.1.2 Liquid‐Phase Oxidation Reactions
7.5.2 Hydrogenation Reactions
7.5.2.1 Hydrogenation of CC and C≡C Groups
7.5.2.2 The Reduction of −NO2 Group
7.5.2.3 The Reduction of C=O Groups
7.5.3 Coupling Reactions
7.5.3.1 Suzuki–Miyaura Coupling Reactions
7.5.3.2 Heck Coupling Reactions
7.5.3.3 Glaser Coupling Reactions
7.5.3.4 Knoevenagel Condensation Reaction
7.5.3.5 Three‐Component Coupling Reaction
7.5.4 CO2 Cycloaddition Reactions
7.5.5 Tandem Reactions
7.6 Conclusions and Outlooks
References
8. Confinement Effects in Catalysis with Molecular Complexes Immobilized into Porous Materials
8.1 Introduction
8.2 Immobilization of Molecular Complexes into Porous Materials
8.2.1 Confinement of Molecular Complexes in Mesoporous Silica
8.2.2 Confinement of Molecular Complexes in Zeolites
8.2.3 Confinement of Molecular Complexes in Covalent Organic Frameworks (COF)
8.2.4 Confinement of Molecular Complexes in Metal–Organic Frameworks (MOFs)
8.2.5 Confinement of Molecular Complexes in Carbon Materials
8.3 Characterization of Molecular Complexes Immobilized into Porous Materials
8.4 Catalysis with Molecular Complexes Immobilized into Porous Materials and Evidences of Confinement Effects
8.4.1 Hydrogenation Reactions
8.4.2 Hydroformylation Reactions
8.4.3 Oxidation Reactions
8.4.4 Ethylene Oligomerization and Polymerization Reactions
8.4.5 Metathesis Reactions
8.4.6 Miscellaneous Reactions on Various Supports
8.4.6.1 Zeolites
8.4.6.2 Mesoporous Silica
8.4.6.3 MOFs
8.4.7 Asymmetric Catalysis Reactions
8.5 Conclusion
References
9. Size‐Selective Catalysis by Metal–Organic Frameworks
9.1 Introduction
9.2 Friedel–Crafts Alkylation
9.3 Cycloaddition Reactions
9.4 Oxidation of Olefins
9.5 Hydrogenation Reactions
9.6 Aldehyde Cyanosilylation
9.7 Knoevenagel Condensation
9.8 Conclusions
References
10. Selective Oxidations in Confined Environment
10.1 Introduction
10.2 Transition‐Metal‐Substituted Molecular Sieves
10.2.1 Ti‐Substituted Zeolites and H2O2
10.2.2 Co‐Substituted Aluminophosphates and O2
10.3 Mesoporous Metal–Silicates
10.3.1 Mesoporous Ti‐Silicates in Oxidation of Hydrocarbons
10.3.2 Mesoporous Ti‐Silicates in Oxidation of Bulky Phenols
10.3.3 Alkene Epoxidation over Mesoporous Nb‐Silicates
10.4 Metal–Organic Frameworks
10.4.1 Selective Oxidations over Cr‐ and Fe‐Based MOFs
10.4.2 Selective Oxidations with H2O2 over Zr‐ and Ti‐Based MOFs
10.5 Polyoxometalates in Confined Environment
10.5.1 Silica‐Encapsulated POM
10.5.2 MOF‐Incorporated POM
10.5.3 POMs Supported on Carbon Nanotubes
10.6 Conclusion and Outlook
Acknowledgments
References
11. Tailoring the Porosity and Active Sites in Silicoaluminophosphate Zeolites and Their Catalytic Applications
11.1 Introduction
11.2 Synthesis of SAPO‐n Zeolites
11.3 Characterization of SAPO Zeolites
11.4 SAPO‐Based Catalysts in Organic Transformations
11.4.1 Acid Catalysis
11.4.2 Reductive Transformations
11.4.2.1 Selective Catalytic Reduction (SCR)
11.4.2.2 Hydroisomerization
11.4.2.3 Hydroprocessing
11.4.2.4 CO2 Hydrogenation
11.5 Conclusion
References
12. Heterogeneous Photocatalytic Degradation of Pharmaceutical Pollutants over Titania Nanoporous Architectures
12.1 Introduction
12.2 Advanced Oxidation Process
12.2.1 Ozonation
12.2.2 UV Irradiation (Photolysis)
12.2.3 Fenton and Photo‐Fenton Process
12.2.4 Need for Green Sustainable Heterogeneous AOP
12.2.5 Heterogeneous Photocatalysis
12.3 Semiconductor Photocatalysis Mechanism
12.4 Factors Affecting Photocatalytic Efficiency
12.5 Crystal Phases of TiO2
12.6 Semiconductor/Electrolyte Interface and Surface Reaction
12.7 Visible‐Light Harvesting
12.8 Photogenerated Charge Separation Strategies
12.8.1 TiO2/Carbon Heterojunction
12.8.2 TiO2/SC Coupled Heterojunction
12.8.3 TiO2/TiO2 Phase Junction
12.8.4 Metal/TiO2 Schottky Junction
12.9 Ordered Mesoporous Materials
12.10 Ordered Mesoporous Titania
12.10.1 Synthesis and Characterization
12.10.2 Photocatalytic Degradation Studies
12.10.3 Complete Mineralization Studies
12.10.4 Spent Catalyst
12.11 Conclusion
Acknowledgment
References
13. Catalytic Dehydration of Glycerol Over Silica and Alumina‐Supported Heteropoly Acid Catalysts
13.1 Introduction
13.2 Value Addition of Bioglycerol
13.3 Interaction Between HPA and Support
13.4 Bulk Heteropoly Acid
13.5 Silica‐Supported HPA
13.5.1 Effect of Textural Properties of Support on Product Selectivity
13.5.2 Effect of Catalyst Loading
13.5.3 Effect of Acid Sites
13.5.4 Effect of Type of Heteropoly Acids
13.6 Tuning the Acidity
13.7 Conclusions
Acknowledgments
References
14. Catalysis with Carbon Nanotubes
14.1 Introduction
14.1.1 Why CNT may be Suitable to be Used as Catalyst Supports?
14.1.1.1 From the Point of Structural Features
14.1.1.2 From the Point of Electronic Properties
14.1.1.3 From the Point of Adsorption Properties
14.1.1.4 From the Point of Mechanical and Thermal Properties
14.2 Catalytic Performances of CNT‐Supported Systems
14.2.1 Different Approaches for the Anchoring of Metal‐Containing Species on CNT
14.2.2 Different Approaches for the Confining NPs Inside CNTs and Their Characterization
14.2.2.1 Wet Chemistry Method
14.2.2.2 Production of CNTs Inside Anodic Alumina
14.2.2.3 Arc‐Discharge Synthesis
14.2.3 Hydrogenation Reactions
14.2.4 Dehydrogenation Reactions
14.2.5 Liquid‐Phase Hydroformylation Reactions
14.2.6 Liquid‐Phase Oxidation Reactions
14.2.7 Gas‐Phase Reactions
14.2.7.1 Syngas Conversion
14.2.7.2 Ammonia Synthesis and Ammonia Decomposition
14.2.7.3 Epoxidation of Propylene in DWCNTs
14.2.8 Fuel Cell Electro Catalyst
14.2.9 Catalytic Decomposition of Hydrocarbons
14.2.10 CNT as Heterogeneous Catalysts
14.2.11 Sulfur Catalysis
14.3 Metal‐Free Catalysts of CNTs
14.4 Conclusion
References
Index