Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications

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Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications
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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