Metal-Organic Frameworks

Hermenegildo García is full Professor at the Instituto de Tecnologica Quimica of the Technical University of Valencia and Honorary Adjunct Professor at the Center of Excellence in Advanced Materials Research of King Abdulaziz University. He was a postdoctoral researcher at the University of Reading with Andrew Gilbert and had several sabbatical leaves in the group of J. C. Scaiano in Ottawa. His research centers on heterogeneous catalysis with porous catalysts and nanoparticles. He is Doctor Honoris Causa from the University of Bucharest and the recipient of the 2011 Janssen-Cilag award and the 2008 Alpha Gold award. Sergio Navalón is Associate Professor at the Department of Chemistry of the Technical University of Valencia (UPV). He graduated in Chemical Engineering in 2003 and obtained his PhD in 2010 at the UPV. His research focuses on the development of heterogeneous (photo)catalysts based on carbons, porous materials and nanoparticles. He has co-authored over fifty publications and two book chapters.

• Preface xiii1 The Stability of Metal–Organic Frameworks 1Georges Mouchaham, Sujing Wang, and Christian Serre1.1 Introduction 11.2 Chemical Stability 21.2.1 Strengthening the Coordination Bond 41.2.1.1 High-Valence Cations and Carboxylate-Based Ligands 41.2.1.2 Low-Valence Cations and Highly Complexing Ligands 91.2.1.3 High-Valence Cations and Highly Complexing Ligands 111.2.2 Protecting the Coordination Bond 121.2.2.1 Introducing Bulky and/or Hydrophobic Groups 121.2.2.2 Coating MOFs with Hydrophobic Matrices 131.3 Thermal Stability 141.4 Mechanical Stability 171.5 Concluding Remarks 19Acknowledgments 20References 202 Tuning the Properties of Metal–Organic Frameworks by Post-synthetic Modification 29Andrew D. Burrows, Laura K. Cadman, William J. Gee, Harina Amer Hamzah, Jane V. Knichal, and Sébastien Rochat2.1 Introduction 292.2 Post-synthetic Modification Reactions 302.2.1 Covalent Post-synthetic Modification 312.2.2 Inorganic Post-synthetic Modification 322.2.3 Extent of the Reaction 332.3 PSM for Enhanced Gas Adsorption and Separation 342.3.1 PSM for Carbon Dioxide Capture and Separation 342.3.2 PSM for Hydrogen Storage 352.4 PSM for Catalysis 372.4.1 Catalysis with MOFs Possessing Metal Active Sites 372.4.2 Catalysis with MOFs containing Reactive Organic Functional Groups 392.4.3 Catalysis with MOFs as Host Matrices 412.5 PSM for Sequestration and Solution Phase Separations 422.5.1 Metal Ion Sequestration 422.5.2 Anion Sequestration 432.5.3 Removal of Organic Molecules from Solution 432.6 PSM for Biomedical Applications 442.6.1 Therapeutic MOFs and Biosensors 442.6.2 PSM by Change of Physical Properties 462.7 Post-synthetic Cross-Linking of Ligands in MOF Materials 462.7.1 Pre-synthetically Cross-Linked Ligands 472.7.2 Post-synthetic Cross-Linking of MOF Linkers 472.7.3 Post-synthetically Modifying the Nature of Cross-Linked MOFs 492.8 Conclusions 51References 513 Synthesis of MOFs at the Industrial Scale 57Ana D. G. Firmino, Ricardo F. Mendes, João P.C. Tomé, and Filipe A. Almeida Paz3.1 Introduction 573.2 MOF Patents from Academia versus the Industrial Approach 583.3 Industrial Approach to MOF Scale-up 643.4 Examples of Scaled-up MOFs 663.5 Industrial Synthetic Routes toward MOFs 693.5.1 Electrochemical Synthesis 693.5.2 Continuous Flow 703.5.3 Mechanochemistry and Extrusion 723.6 Concluding Remarks 74Acknowledgments 75List of Abbreviations 75References 764 From Layered MOFs to Structuring at the Meso-/Macroscopic Scale 81David Rodríguez-San-Miguel, Pilar Amo-Ochoa, and Félix Zamora4.1 Introduction 814.2 Designing Bidimensional Networks 824.3 Methodological Notes Regarding Characterization of 2D Materials 844.3.1 Morphological and Structural Characterization 844.3.2 Spectroscopic and Diffractometric Characterization 884.4 Preparation and Characterization 924.4.1 Bottom-Up Approaches 924.4.1.1 On-Surface Synthesis 924.4.1.2 Synthesis at Water/Air or Solvent-to-Solvent Interface 924.4.1.3 Synthesis at the Liquid–Liquid Interface 1004.4.2 Miscellaneous 1044.4.2.1 Direct Colloidal Formation 1044.4.2.2 Surfactant Mediated 1044.4.3 Top-Down Approaches 1054.4.3.1 Liquid Phase Exfoliation (LPE) 1064.4.3.2 Micromechanical Exfoliation 1104.5 Properties and Potential Applications 1114.5.1 Gas Separation 1114.5.2 Electronic Devices 1124.5.3 Catalysis 1134.6 Conclusions and Perspectives 115Acknowledgments 116References 1165 Application of Metal–Organic Frameworks (MOFs) for CO2 Separation 123Mohanned Mohamedali, Hussameldin Ibrahim, and Amr Henni5.1 Introduction 1235.2 Factors Influencing the Applicability of MOFs for CO2 Capture 1245.2.1 Open Metal Sites 1255.2.2 Amine Grafting on MOFs 1325.2.3 Effects of Organic Ligand 1385.3 Current Trends in CO2 Separation Using MOFs 1395.3.1 Ionic Liquids/MOF Composites 1395.3.2 MOF Composites for CO2 Separation 1435.3.3 Water Stability of MOFs 1445.3.3.1 Effect of Water on MOFs with Open Metal Sites 1465.3.3.2 Effects of the Organic Ligand on Water Stability of MOFs 1475.4 Conclusion and Perspective 150References 1516 Current Status of Porous Metal–Organic Frameworks for Methane Storage 163Yabing He, Wei Zhou, and Banglin Chen6.1 Introduction 1636.2 Requirements for MOFs as ANG Adsorbents 1656.3 Brief History of MOF Materials for Methane Storage 1676.4 The Factors Influencing Methane Adsorption 1686.4.1 Surface Area 1696.4.2 Pore Size 1706.4.3 Adsorption Heat 1706.4.4 Open Metal Sites 1706.4.5 Ligand Functionalization 1716.5 Several Classes of MOFs for Methane Storage 1716.5.1 Dicopper Paddlewheel-Based MOFs 1716.5.2 Zn4O-Cluster Based MOFs 1806.5.3 Zr-Based MOFs 1826.5.4 Al-Based MOFs 1866.5.5 MAF Series 1896.5.6 Flexible MOFs for Methane Storage 1906.6 Conclusion and Outlook 192References 1957 MOFs for the Capture and Degradation of Chemical Warfare Agents 199Elisa Barea, Carmen R. Maldonado and Jorge A. R. Navarro7.1 Introduction to Chemical Warfare Agents (CWAs) 1997.2 Adsorption of CWAs 2017.3 Catalytic Degradation of CWAs 2067.3.1 Hydrolysis of Nerve Agents and Their Simulants 2067.3.2 Oxidation of Sulfur Mustard and Its Analogues 2117.3.3 Multiactive Catalysts for CWA Degradation 2127.4 MOF Advanced Materials for Protection against CWAs 2147.5 Summary and Future Prospects 218References 2198 Membranes Based on MOFs 223Pasquale F. Zito, Adele Brunetti, Alessio Caravella, Enrico Drioli and Giuseppe Barbieri8.1 Introduction 2238.2 Characteristics of MOFs 2248.3 MOF-Based Membranes for Gas Separation 2258.3.1 MOF in Mixed Matrix Membranes 2268.3.1.1 MOF-based MMMs: Experimental Results 2288.3.2 MOF Thin-Film Membranes 2328.3.2.1 Stability of Thin-Film MOF Membranes 2428.3.3 Modeling the Permeation through MOF-based MMMs 244Acknowledgments 246References 2469 Composites of Metal–Organic Frameworks (MOFs): Synthesis and Applications in Separation and Catalysis 251Devjyoti Nath, Mohanned Mohamedali, Amr Henni and Hussameldin Ibrahim9.1 Introduction 2519.2 Synthesis of MOF Composites 2529.2.1 MOF–Carbon Composites 2529.2.1.1 MOF–CNT Composites 2529.2.1.2 MOF–AC Composites 2559.2.1.3 MOF–GO Composites 2559.2.2 MOF Thin Films 2569.2.3 MOF–Metal Nanoparticle Composites 2629.2.3.1 Solution Infiltration Method 2639.2.3.2 Gas Infiltration Method 2669.2.3.3 Solid Grinding Method 2669.2.3.4 Template-Assisted Synthesis Method 2669.2.4 MOF–Metal Oxide Composites 2669.2.5 MOF–Silica Composites 2729.3 Applications of MOF Composites in Catalysis and Separation 2749.3.1 MOF Composites for Catalytic Application 2749.3.2 MOF Composites for Gas Adsorption and Storage Applications 2769.3.3 MOF Composites for Liquid Separation Applications 2859.4 Conclusions 286References 28610 Tuning of Metal–Organic Frameworks by Pre- and Post-synthetic Functionalization for Catalysis and Separations 297Christopher F. Cogswell, Zelong Xie, and Sunho Choi10.1 Introduction 29710.1.1 Terminology for Functionalization on MOFs 29710.1.2 General Design Parameters for Separations and Catalysis 29910.2 Pre-synthetic Functionalization 30310.2.1 Explanation of this Technique 30310.2.2 Separations Applications 30410.2.3 Catalytic Applications 30710.3 Type 1 or Physical Impregnation 30910.3.1 Explanation of this Technique 30910.3.2 Separations Applications 31010.3.3 Catalytic Applications 31210.4 Type 2 or Covalent Attachment 31310.4.1 Explanation of this Technique 31310.4.2 Separations Applications 31410.4.3 Catalytic Applications 31610.5 Type 3 or In Situ Reaction 31810.5.1 Explanation of this Technique 31810.5.2 Separations Applications 31910.5.3 Catalytic Applications 32110.6 Type 4 or Ligand Replacement 32110.7 Type 5 or Metal Addition 32210.7.1 Explanation of this Technique 32210.7.2 Separations Applications 32510.7.3 Catalytic Applications 32510.8 Conclusions 326References 32711 Role of Defects in Catalysis 341Zhenlan Fang and Qiang Ju11.1 Introduction 34111.2 Definition of MOF Defect 34211.3 Classification of MOF Defects 34311.3.1 Defects Classified by Defect Dimensions 34311.3.2 Defects Classified by Distribution, Size, and State 34311.3.3 Defects Classified by Location 34311.4 Formation of MOF Defects 34311.4.1 Inherent Defects of MOFs 34311.4.1.1 Inherent Surface Defect 34411.4.1.2 Inherent Internal Defect 34411.4.1.3 Post-crystallization Cleavage 34511.4.2 Intentionally Implanted Defects via Defect Engineering 34611.4.2.1 Defects Introduced during De Novo Synthesis 34711.4.2.2 Defects Formed by Post-synthetic Treatment 35111.5 Characterization of Defects 35211.5.1 Experimental Methods for Analyzing Defects 35211.5.1.1 Assessing Presence of Defects 35211.5.1.2 Imaging Defects 35511.5.1.3 Probing Chemical and Physical Environment of Defects 35711.5.1.4 Distinguish between Isolated Local and Correlated Defects 35811.5.2 Theoretical Methods 35911.6 The Role of Defect in Catalysis 36311.6.1 External Surface Linker Vacancy 36311.6.2 Inherent Linker Vacancy of Framework Interior 36611.6.3 Intentionally Implanted Defects 36711.6.3.1 Implanted Linker Vacancy by TML Strategy 36711.6.3.2 Implanted Linker Vacancy by LML Strategy 36811.6.3.3 Implanted Linker Vacancy by Post-synthetic Treatment 36911.6.3.4 Implanted Linker Vacancy by Fast Precipitation 37011.6.3.5 Implanted Linker Vacancy by MOF Partial Decomposition 37011.7 Conclusions and Perspectives 372Acknowledgment 372References 37212 MOFs as Heterogeneous Catalysts in Liquid Phase Reactions 379Maksym Opanasenko, Petr Nachtigall, and Jiří Čejka12.1 Introduction 37912.2 Synthesis of Different Classes of Organic Compounds over MOFs 38012.2.1 Alcohols 38012.2.2 Carbonyl and Hydroxy Carbonyl Compounds 38312.2.3 Carboxylic Acid Derivatives 38512.2.4 Acetals and Ethers 38912.2.5 Terpenoids 39012.3 Specific Aspects of Catalysis by MOFs 39212.3.1 Concept of Concerted Effect of MOF’s Active Sites: Friedländer Reaction 39212.3.2 Dynamically Formed Defects as Active Sites: Knoevenagel Condensation 39412.4 Concluding Remarks and Future Prospects 395References 39613 Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis 399Karen Leus, Himanshu Sekhar Jena, and Pascal Van Der Voort13.1 Introduction 39913.1.1 Impregnation Methods 40013.1.1.1 Liquid Phase Impregnation 40013.1.1.2 Solid Phase Impregnation 40113.1.1.3 Gas Phase Impregnation 40113.1.2 Assembly Methods 40213.2 Nanoparticles in MOFs for Gas and Liquid Phase Oxidation Catalysis 40513.3 Nanoparticles in MOFs in Hydrogenation Reactions 41113.4 Nanoparticles in MOFs in Dehydrogenation Reactions 42413.5 Nanoparticles in MOFs in C─C Cross-Coupling Reactions 43013.6 The Use of Nanoparticles in MOFs in Tandem Reactions 43313.7 Conclusions and Outlook 437References 43814 MOFs as Supports of Enzymes in Biocatalysis 447Sérgio M. F. Vilela and Patricia Horcajada14.1 Introduction 44714.2 MOFs as Biomimetic Catalysts 44914.3 Enzyme Immobilization Strategies 45414.3.1 Surface Immobilization 45514.3.2 Diffusion into the MOF Porosity 45614.3.3 In Situ Encapsulation/Entrapment 45714.4 Biocatalytic Reactions Using Enzyme–MOFs 45914.4.1 Esterification and Transesterification 46314.4.2 Hydrolysis 46414.4.3 Oxidation 46614.4.4 Synthesis of Warfarin 46814.4.5 Other Applications Based on the Catalytic Properties of Enzyme–MOFs 46814.5 Conclusions and Perspectives 469Acknowledgments 470References 47115 MOFs as Photocatalysts 477Sergio Navalón and Hermenegildo García15.1 Introduction 47715.2 Properties of MOFs 48215.3 Photophysical Pathways 48315.4 Photocatalytic H2 Evolution 49015.5 Photocatalytic CO2 Reduction 49315.6 Photooxidation Reactions 49415.7 Photocatalysis for Pollutant Degradation 49615.8 Summary and Future Prospects 497Acknowledgements 498References 498Index 503