Metal-Organic Frameworks (MOFs) as Catalysts

✍ Scribed by Shikha Gulati

• Tongue: English
• Leaves: 785
• Category: Library

✦ Table of Contents

Foreword
Preface
Acknowledgements
About This Book
Contents
About the Editor
Abbreviations
MOFs as Catalysts: Introduction and Prospects
Introduction to Metal-Organic Frameworks (MOFs)
1 Introduction
2 Metal–organic Frameworks (MOFs): A Promising Class of Crystalline Heterogeneous Catalysts with Promising Properties
3 Structural Analysis of MOFs
4 Strategies for Synthesis of Metal–Organic Frameworks
4.1 Solvothermal Synthesis
4.2 Microwave(MW)-assisted Synthesis
4.3 Electrochemical Synthesis
4.4 Solvent-Free Synthesis
5 Post-Synthetic Modification (PSM) Approaches for Enhanced Functionality of Synthesized MOFs
6 Comparative Study of MOFs Catalysis with Traditional Heterogeneous Catalysts like Zeolites and Mesoporous Silica
7 Strategies for Incorporation of Specific Catalytic Activity into a MOF
8 Different Catalytic Applications of MOFs: Appropriate Properties and Opportunities
8.1 Heterogeneous Catalysis
8.2 Photocatalysis
8.3 Electrocatalysis
9 Some Examples of the Common MOFs-Catalyzed Reactions
9.1 CO/CO2 Hydrogenation
9.2 Alkyne Hydrogenation
9.3 Dehydrogenation
9.4 Epoxidation
9.5 Oligomerization
9.6 Hydrolysis, Dehydration, Esterification, and Condensation
9.7 Isomerization and Alkylation Reactions
9.8 Photocatalysis
10 Some Other Important Applications of MOFs
10.1 Luminescent Sensing
10.2 CO2 Capture and Photocatalytic Reduction
10.3 Biomedical Applications
11 Limitations in Catalytic Properties of MOFs
11.1 Transport Limitations in Catalysis by MOFs
11.2 Minority and Defect Structures in MOFs
11.3 Stability Limitations in MOFs
12 Conclusion and Future Outlook
References
Stability of MOFs and Kinetics of MOFs Catalyzed Reactions
Kinetic Stability of Robust Metal–Organic Frameworks (MOFs) in Catalytic Reactions
1 Introduction
2 Kinetic Factors Affecting MOFs Topology
2.1 The Rigidity of the Linker
2.2 Coordination Bond
2.3 Surface Hydrophobicity
2.4 Framework Interpenetration
3 Strategies for Stabilizing the Kinetics of Porous MOFs
3.1 Metal Ion Substitution Kinetics
3.2 Strengthening the Bonds for Stabilizing the Porous Phase in Contrast to the Transition State
3.3 Steric and Hydrophobicity
3.4 Linkers and Nodes Connectivity
4 MOFs Stability in Gases and Vapors Phase
4.1 Effect of Different Gases
4.2 Effect of Water and Vapors
5 Applications of Kinetically Stable MOFs
5.1 Adsorption and Separation
5.2 Fluorescence Sensing
5.3 Heterogeneous Catalysis
5.4 Biological and Pharmaceutical Application
6 Conclusion and Future Perspectives
References
Strategies for the Synthesis and Functionalization of MOFs
Strategies to Synthesize Diverse Metal–Organic Frameworks (MOFs)
1 Introduction
2 History of MOFs
3 Categories and Names of Metal–Organic Frameworks
4 Reticular Synthesis of MOFs
5 Properties and Parameters Considered During Synthesis of MOFs
6 Different Methods of Synthesis of MOFs
7 Microwave-Assisted MOF Synthesis
8 Electrochemical Synthesis
9 Mechanochemical Synthesis
10 Ultrasonic Synthesis
11 Conclusions and Future Perspectives
References
Functionalization Strategies of Metal–Organic Frameworks (MOFs): Diverse Ways to Versatile MOFs
1 Introduction
2 Metal–Organic Frameworks: General Characteristics, Structure and Synthesis
2.1 Synthetic Methods of MOFs
3 Functionalization of MOF Backbone (Internal-Surface Functionalization)
3.1 Inorganic Nodes
3.2 Organic Linkers
4 Strategies for Functionalization
4.1 In Situ Functionalization
4.2 Pre-Synthetic Functionalization
4.3 Post-Synthetic Modifications
5 Immobilization of Guest Species in MOF Matrices and Pores
6 Coating MOFs with Functional Materials
7 Applications of Functionalized MOFs
7.1 Chemical Sensing
7.2 Heterogeneous Catalysis
7.3 Gas Storage and Separation
7.4 Biomedical Applications
8 Conclusion and Future Outlook
References
Characterization Techniques of MOFs
Spectroscopic and Microscopic Techniques: Tools for Characterizing Nanoscale Metal–Organic Frameworks (NMOFs)
1 Introduction
2 Microscopic Characterizations
2.1 Visible Light Microscopy
2.2 Electron Microscopy
2.3 Scanning Probe Microscopy
2.4 Scanning Tunneling Microscopy (STM)
2.5 Atomic Force Microscopy (AFM)
3 Spectroscopic Characterizations
3.1 NMR Spectroscopy
3.2 UV–Visible Differential Reflectance Spectroscopy
3.3 Infrared and Raman Spectroscopy
3.4 Fluorescence Spectroscopy
3.5 Fluorescence Correlation Spectroscopy
3.6 Dynamic Light Scattering
3.7 Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)
3.8 Photoluminescence Spectroscopy
3.9 Powder X-Ray Diffraction (PXRD)
References
Metal–Organic Frameworks (MOFs) Characterization Using Different Analytical Methods
1 Introduction
2 Characterization Techniques
2.1 FE-SEM and EDX
2.2 TGA
2.3 XRD
2.4 DLS
2.5 FTIR
3 Characterizations of Some Prepared MOFs
3.1 ZIF-8
3.2 ZIF-67
3.3 CuBTC and GO@CuBTC
4 Conclusions
References
Reactions Catalyzed by MOFs and Prospects for Applications
7 Versatile Metal–Organic Frameworks: Perspectives on Contribution in Reaction Catalysis and Applications
Abstract
1 Introduction
2 Potential of Metal–Organic Frameworks (MOFs) Over Other Conventional Catalysts
3 Fundamental Properties of MOFs Contributing Towards Catalysis
4 MOFs as Robust Host for Various Nanoparticles in Heterogeneous Catalysis
5 Reactions Catalyzed by MOFs and Prospects for Applications
5.1 Polymerization Reactions
5.2 Oxidation Reactions
5.3 Coupling and Cross-Coupling Reactions
5.4 CO2 Conversion Reactions
Photoreduction
Electroreduction
Hydrogenation
6 Significance of MOFs as Lewis Acid Catalysts
6.1 In Condensation Reactions
6.2 In Cyanosilylation Reaction
6.3 In Friedel–Crafts Reaction
7 Conclusion and Future Perspectives
References
MOFs as Catalysts for CO2 Capture and Fixation
Metal–Organic Frameworks as Promising Catalysts for CO2 Capture and Fixation
1 Introduction
2 Metal–Organic Frameworks (MOFs) for Capturing CO2
2.1 Oxy-Fuel Combustion-Based CO2 Capture
2.2 CO2 Capture from the Air and Natural Gas
2.3 CO2 Separation by MOF-Based Membranes
2.4 Pre-combustion CO2 Capture
2.5 Post-combustion CO2 Capture
2.6 Photocatalytic Conversion of CO2
2.7 Electrochemical and Electrocatalytic Conversion of CO2
3 Factors Affecting the Efficiency of MOFs for CO2 Capture
3.1 Heteroatoms
3.2 Hydrophobicity
3.3 The Presence of Unsaturated Metal Sites
3.4 Interactions with Functional Groups of SBUs
4 Regeneration of MOFs
5 Summary
References
Theoretical Study on Catalytic Capture and Fixation of Carbon Dioxide by Metal–Organic Frameworks (MOFs)
1 Introduction
2 Metal–Organic Frameworks
3 Theoretical Studies on the Capture of CO2 by MOFs
4 Theoretical Studies on Fixation of CO2 by MOFs
5 Conclusion
References
Covalent Organic Frameworks as Catalysts
Covalent Organic Frameworks (COFs) as Catalysts: An Overview
1 Introduction
2 Chemistry and Design of COFs
3 Catalytic Applications of COFs
4 Engaging COF for Catalytic Splitting of Water Molecules Irradiated by Visible Light
5 COF Catalyzed Suzuki Coupling Reaction [22, 23]
6 Degradation of 4-Nitrophenol by the Ultra-Stable Covalent Organic Framework–Au Nanoparticles System [24]
7 Covalent Organic Frameworks Based on Azine as Metal-Free Photocatalysts for CO2 Reduction with H2O [26]
8 Imine-Based Covalent Organic Frameworks for Selective Olefin Oxidation [27]
9 A Novel Hybrid COF for Photocatalytic Removal of Organic Dye and Cr(VI) from Wastewater [28]
10 A Covalent Organic Framework–Cadmium Sulfide System for Visible Light-Initiated Hydrogen Gas Production [29]
11 Electrocatalytic Reduction of Carbon Dioxide on Active Sites of COF [30]
12 Ultra-Stable Covalent Organic Frameworks with Benzoxazole for Photocatalysis [31]
13 COF Efficiency in the Production of Solar Fuel from CO2 [32]
14 Covalent Organic Frameworks for Serotonin Detection Using Luminol Chemiluminescence [33]
15 Degradation of Organic Pollutants by Covalent Organic Framework-Silver Nanoparticles@Sand Hybrid [34]
16 CdS/COF Heterostructure for Enhanced Photocatalytic Decomposition of Bisphenol-A [36]
17 MnO2-loaded Ultrathin COF Nanosheets as Cathode Catalysts for Li-CO2 Batteries [37]
18 Magnetic COFs for Efficient Fenton-Like Degradation of Pharmaceutical Waste Sulfamethazine [38]
19 Triazine Functionalized Porous Covalent Organic Framework for Photo-Organocatalytic E−Z Isomerization of Olefins [39]
20 Conclusion
References
Recent Advances in the Synthesis of Covalent Organic Frameworks for Heterogeneous Catalysis
1 Introduction
2 Design of Building Blocks for the Synthesis of COFs
3 COF as a Support Material for Catalysis
4 Methods of Synthesis
4.1 Ionothermal Trimerization
4.2 Microwave-Assisted (MW) Synthesis
4.3 Sonochemical Synthesis
4.4 Mechanochemical Synthesis
4.5 Schiff’s Base Reaction
4.6 Synthesis of COFs via One-Pot Multi-component Reactions (MCRs)
4.7 Synthesis of Magnetic COFs
4.8 Friedel–Crafts Reaction
4.9 Coupling Reactions
5 Application of Covalent Organic Frameworks in Heterogeneous Catalysis
5.1 C–C Coupling Reactions
5.2 Nitrophenol Reduction
5.3 Asymmetric Catalysis
5.4 Cycloaddition of CO2 to Epoxides
5.5 Condensation and Multi-Component Reactions
5.6 Dye Degradation
5.7 Photocatalytic Applications
5.8 Electrocatalysis
5.9 Other Catalytic Applications
6 Conclusion
References
Designing, Synthesis, and Applications of Covalent Organic Frameworks (COFs) for Diverse Organic Reactions
1 Introduction
2 Diverse Strategies of Synthesis of COFs Using Alternate Energy Sources
3 Reticular Chemistry: Next Step in Chemistry
3.1 Types of Linkages in the Coupling Reactions for Synthesizing COFs
4 Post-Synthetic Modification
5 Application of COFs in Catalysis
6 Conclusion and Future Perspectives
References
MOFs as Heterogeneous Catalysts
Metal–Organic Frameworks (MOFs) as Heterogeneous Catalysts: An Overview
1 Introduction
2 Synthesis of Metal–Organic Frameworks
3 Conventional Solvothermal Synthesis of MOF
4 Catalysis by MOF
5 Photocatalytic Role of MOF-Based Heterogeneous Catalyst
5.1 Electrocatalysis by MOF-Based Molecules
6 Conclusion and Perspective
References
Recent Trends of Metal–Organic Frameworks in Heterogeneous Catalysis
1 Introduction
2 Designing MOFs with Intrinsic Catalytic Activity
2.1 MOFs Containing Open Metal Sites and Non-Decorated Structures
2.2 Catalysis Based on MOF Defects
2.3 Catalysis Based on Decorated MOFs
2.4 CO2 Activation
2.5 Carbon-Hydrogen Bond Functionalization
2.6 Other Reactions Catalyzed by MOFs
3 MOFs Containing Metal Nanoparticles
3.1 MOFs Synthesis
3.2 Catalysis
4 Outlook, Challenges, and Future Perspectives
References
MOFs as Sensors
Metal–Organic Frameworks (MOFs) as Sensors for Environmental Monitoring
1 Introduction
2 Water Sensors Based on MOFs
2.1 Luminescent Technology
2.2 Sensing of Heavy Metal Pollutants
2.3 Sensing of Organic Molecules Present as Contaminants
3 Electrochemical Sensors
4 Different Other Sensors in Aqueous Medium
5 Environmental Gas Sensors Based on MOF
6 Conclusion
References
Metal–Organic Frameworks for Pesticide Sensing: Trend in the Recent Years
1 Introduction
2 Synthetic Methodologies of MOFs
2.1 Diffusion-Based Synthesis
2.2 Conventional Solution-Based Method
2.3 Solvo/hydrothermal Method
2.4 Microwave-Assisted Synthesis
2.5 Sonochemical Method
2.6 Electrochemical Synthesis
2.7 Mechanochemical Method
3 Applications in Organophosphorus Pesticides Sensing
3.1 Luminescent Sensing Mechanism
3.2 Electrochemical Sensing System
4 Conclusion and Future Aspects
References
MOFs as Catalysts for the Capture and Degradation of Chemical Warfare Agents
Computational Approach Toward Identification and Catalytic Degradation of Chemical Warfare Agents Using MOFs
1 Introduction
2 Why Use MOFs for Adsorption and Detoxification of CWAs?
3 Detoxification of Nerve Agents and Their Simulants by Zirconium-Based MOFs
4 Other MOFs for Capturing and Catalytic Degradation of CWAs
5 How Good Are the Surrogate Molecules in Mimicking the Adsorption Behavior of Real CWAs?
6 Conclusions
References
Metal–Organic Frameworks (MOFs) as Versatile Detoxifiers for Chemical Warfare Agents (CWAs)
1 Introduction
2 Classification of CWAs and Their Characteristic Properties
2.1 Nerve Agents
2.2 Vesicants
2.3 Blood Agents
2.4 Choking Agents
2.5 Riot-Control Agents
2.6 Psychomimetic Agents
3 Toxic Effects of CWAs
3.1 Nerve Agents
3.2 Vesicants
3.3 Blood Agents
3.4 Riot-Control Agents
3.5 Psychomimetic Agents
4 Model CWA Simulants and Their Significance
5 Strategic Routes for Fabrication of MOFs for Effective Sequestration of CWAs
5.1 Tuning the Pore Properties and Surface Hydrophobicity
5.2 Partial Oxidation Approach
5.3 Post-Synthetic Functionalization with Amine Groups
5.4 Inducing Lewis Acidity Through Missing-Linker Defect
6 MOFs as Catalysts for Detoxification of CWAs
6.1 Degradation of Simulants of Real CWAs
6.2 Degradation of Real Nerve Agents
7 MOFs for Adsorption of CWAs
8 MOF-Modified Fabrics for CWA Adsorption
9 Conclusions and Future Aspects
References
Chiral MOFs for Asymmetric Catalysis
Chiral Metal-Organic Frameworks for Asymmetrical Catalysis
1 Introduction
2 Application of MOFs as Catalyst in Asymmetric Reactions
2.1 Chiral MOF Catalyzed Asymmetric Michael Addition
2.2 Enantioselective Ring-Opening of Epoxides/aziridines Using MOF Catalysts
2.3 Chiral MOFs -Catalyzed Alkene Functionalization
2.4 Asymmetric Dihydroxylation
2.5 Chiral MOF Catalyzed Asymmetric Carbonyl-ene Reactions
2.6 Asymmetric Aldol Reaction Using MOF Catalyst
2.7 Asymmetric Hydrosilation and Hydroboration of Carbonyl Using Chiral MOFs
2.8 Asymmetric Domino Reaction
2.9 Asymmetric Diels–Alder Reaction
2.10 Homochiral MOF-Mediated Asymmetric Cyanosilylation
2.11 Asymmetric Henry Reaction
2.12 Asymmetric Friedel–Crafts Reactions
2.13 Asymmetric Tandem Reactions
3 Conclusion
References
MOFs as Catalysts for the Storage of Methane
Metal–Organic Frameworks: Promising Materials for Methane Storage
1 Introduction
2 Basic Terminology Used in CH4 Storage
2.1 Excess, Absolute and Total Adsorption
2.2 Gravimetric and Volumetric Capacity
2.3 Working Capacity or Deliverable Capacity
3 CH4 Storage in MOFs
3.1 Requirements for MOFs as ANG Adsorbent
3.2 Characterizations Required for MOFs to Investigate Their CH4 Adsorption Capacity
4 Design and Synthesis of MOFs for CH4 Storage
4.1 Rigid MOFs for CH4 Storage
4.2 Flexible MOFs for CH4 Storage
5 Conclusion and Outlook
References
Photocatalysis by MOFs
Photocatalysis by Metal–Organic Frameworks (MOFs): An Overview
1 Introduction
2 MOF-Based Photocatalysis
2.1 Enhancing Light-Harvesting
2.2 Enhancing Electron–Hole Separation
3 MOFs as Photothermal Catalysis
3.1 Photothermal Effect of Plasmonic Metals
3.2 Photothermal Effect of Both MOFs and Plasmonic Metals
4 Conclusion
References
Metal Organic Frameworks as Photocatalyst for Water Purification
1 Introduction
2 Water Purification
2.1 Methods for Water Purification
3 Photocatalysis and Its Requirement for Water Purification
3.1 Mechanism of Photocatalysis
3.2 Factors Affecting Photocatalysis
3.3 Kinetics of Photocatalysis
4 Photocatalytic Reactors for Treatment of Water
5 General Photocatalytic Materials
6 Metal–Organic Frameworks (MOFs)
6.1 Synthesis of MOFs
6.2 Characterization of MOFs
7 MOFs as Photocatalyst
7.1 Metal–Organic Frameworks as Photocatalysts for Dye Degradation
7.2 Metal–Organic Frameworks as Photocatalysts for Primary Pollutants
7.3 Metal–Organic Frameworks as Photocatalysts for Photoreduction of Heavy Metals
8 Summary and Future perspectives
References
Metal-Organic Framework as a Photocatalyst: Recent Growth in Environmental Applications
1 Introduction
2 Possible Photocatalytic Applications of MOFs
2.1 Reduction of Carbon Dioxide (CO2) on MOFs
2.2 Hydrogen Production via Water Splitting on MOFs
2.3 Photoelectric Conversion/ Photoelectrochemical Applications
2.4 Reduction of N2 (Nitrogen Fixation) with MOFs
2.5 Photocatalytic Degradation of Organic Contaminants
2.6 Photocatalytic Application in Organic Synthesis and Transformation Reactions
2.7 Photocatalytic Reduction of Heavy Metal Ions for Detoxification
2.8 Photocatalytic Antibacterial Activity
2.9 Photocatalytic Removal of Toxic Gases
3 The Common Mechanism Involved in Photocatalysis by MOFs
4 Conclusion and Future Perspectives
References
Metal–Organic Frameworks (MOFs) Catalyzed Photodegradation of Organic Dyes: Syntheses, Designing Strategies, and Mechanism
1 Introduction
2 Synthetic Approaches, Designing, and Structures of Photosensitive MOFs
2.1 Synthetic Approaches
2.2 Designing
2.3 Structures and Photocatalyses of MOFs
3 Photocatalytic Mechanism
3.1 Direct Photodegradation Process
3.2 Sensitization-Mediated Degradation Process
4 Conclusions
References
Role of MOFs in Bio-catalysis
Multifaceted Metal–Organic Frameworks: An Emerging Platform for Biocatalytic Reactions
1 Introduction
2 Structural Morphology and Potential of Mofs Over Conventional Bio Catalysts
3 Fundamental Properties Contributing Towards Biocatalysis
4 Strategies for Enzyme Immobilization
4.1 Surface Immobilization
4.2 Covalent Binding
4.3 Cage Inclusion
4.4 In Situ MOF Formation and Enzyme Immobilization
5 Outlook to Applications of MOFs as Immobilized Biocatalysts
5.1 Biosensing and Detection
5.2 MOFs as Host for Biomimetic Catalysis
5.3 Enzyme-MOF for Digestion of Proteins
6 Conclusion and Future Outlook
Important Websites
References
MOFs Encapsulated Metal Nanoparticles as Catalysts
Metal–Organic Frameworks (MOFs) Encapsulated Nanoparticles: Potential Catalysts for Diverse Organic Reactions
1 Introduction
2 Encapsulation and Its Importance
3 Metal NPs Encapsulated in MOFs for Hydrogenation Reactions
4 MNPs@MOFs in C–C Cross-Coupling Reactions
References
Recent Progress in the Synthesis and Electrocatalytic Application of Metal–Organic Frameworks Encapsulated Nanoparticle Composites
1 Introduction
2 Challenges Associated with MOFs for Catalysis
2.1 Synthetic Challenge
2.2 Chemical and Thermal Stability
2.3 Electrical Conductivity
3 Synthesis of NP Encapsulated MOFs
3.1 Impregnation Approach
3.2 Encapsulation Approach
3.3 One-Pot Synthetic Approach
4 Reaction Mechanism of ORR, OER, and HER
4.1 Mechanism of Oxygen Reduction Reaction (ORR)
4.2 Mechanism of Oxygen Evolution Reaction (OER)
4.3 Mechanism of Hydrogen Evolution Reaction (HER)
5 Parameters to Evaluate the Electrochemical Performances
5.1 Parameters to Evaluate HER/OER Performance
5.2 Parameters to Evaluate ORR Performance
6 MOF and MOF-Based Electrocatalysts
6.1 MOF as Electrocatalyst
6.2 MOF Encapsulated Nanostructures for Electrocatalysis
6.3 MOF-Derived Electrocatalysts for ORR, OER, and HER
7 Summary and Future Perspectives
References
Concluding Remarks and Future Perspectives of MOFs as Catalysts
Concluding Remarks About Metal–Organic Frameworks (MOFs): From Properties to Potential Applications
1 Introduction
2 Structural Properties of Metal–Organic Frameworks (MOFs)
2.1 Stability of MOFs
2.2 Pore Characteristics and Surface Area Properties of MOFs
3 Emphasis on the Functionalization of MOFs
3.1 Synthesis Strategies for Functionalization
3.2 Applications of Functionalized MOFs
4 Catalytic Role of MOFs in Chemical Reactions and Their Implications
4.1 Metal or Metal Clusters as Lewis Acids or Bronsted Acids
4.2 Metal Catalyzed CO2 Conversions
4.3 Metal Catalyzed Oxidation
4.4 Metal Catalyzed Reduction
4.5 Metal Catalyzed Cross-Coupling Reactions
5 Future Application Potential of MOFs
5.1 Multivariate MOFs
5.2 Defective MOFs
5.3 2-dimensional MOFs
5.4 Composites Based on MOFs
5.5 Nanomaterials Based on MOFs
6 Challenges and Future Opportunities
7 Conclusion
References