内容

目次

Preface xiii 1 The Stability of Metal–Organic Frameworks 1Georges Mouchaham, Sujing Wang, and Christian Serre 1.1 Introduction 1 1.2 Chemical Stability 2 1.2.1 Strengthening the Coordination Bond 4 1.2.1.1 High–Valence Cations and Carboxylate–Based Ligands 4 1.2.1.2 Low–Valence Cations and Highly Complexing Ligands 9 1.2.1.3 High–Valence Cations and Highly Complexing Ligands 11 1.2.2 Protecting the Coordination Bond 12 1.2.2.1 Introducing Bulky and/or Hydrophobic Groups 12 1.2.2.2 Coating MOFs with Hydrophobic Matrices 13 1.3 Thermal Stability 14 1.4 Mechanical Stability 17 1.5 Concluding Remarks 19 Acknowledgments 20 References 20 2 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 Rochat 2.1 Introduction 29 2.2 Post–synthetic Modification Reactions 30 2.2.1 Covalent Post–synthetic Modification 31 2.2.2 Inorganic Post–synthetic Modification 32 2.2.3 Extent of the Reaction 33 2.3 PSM for Enhanced Gas Adsorption and Separation 34 2.3.1 PSM for Carbon Dioxide Capture and Separation 34 2.3.2 PSM for Hydrogen Storage 35 2.4 PSM for Catalysis 37 2.4.1 Catalysis with MOFs Possessing Metal Active Sites 37 2.4.2 Catalysis with MOFs containing Reactive Organic Functional Groups 39 2.4.3 Catalysis with MOFs as Host Matrices 41 2.5 PSM for Sequestration and Solution Phase Separations 42 2.5.1 Metal Ion Sequestration 42 2.5.2 Anion Sequestration 43 2.5.3 Removal of Organic Molecules from Solution 43 2.6 PSM for Biomedical Applications 44 2.6.1 Therapeutic MOFs and Biosensors 44 2.6.2 PSM by Change of Physical Properties 46 2.7 Post–synthetic Cross–Linking of Ligands in MOF Materials 46 2.7.1 Pre–synthetically Cross–Linked Ligands 47 2.7.2 Post–synthetic Cross–Linking of MOF Linkers 47 2.7.3 Post–synthetically Modifying the Nature of Cross–Linked MOFs 49 2.8 Conclusions 51 References 51 3 Synthesis of MOFs at the Industrial Scale 57Ana D. G. Firmino, Ricardo F. Mendes, João P.C. Tomé, and Filipe A. Almeida Paz 3.1 Introduction 57 3.2 MOF Patents from Academia versus the Industrial Approach 58 3.3 Industrial Approach to MOF Scale–up 64 3.4 Examples of Scaled–up MOFs 66 3.5 Industrial Synthetic Routes toward MOFs 69 3.5.1 Electrochemical Synthesis 69 3.5.2 Continuous Flow 70 3.5.3 Mechanochemistry and Extrusion 72 3.6 Concluding Remarks 74 Acknowledgments 75 List of Abbreviations 75 References 76 4 From Layered MOFs to Structuring at the Meso–/Macroscopic Scale 81David Rodríguez–San–Miguel, Pilar Amo–Ochoa, and Félix Zamora 4.1 Introduction 81 4.2 Designing Bidimensional Networks 82 4.3 Methodological Notes Regarding Characterization of 2D Materials 84 4.3.1 Morphological and Structural Characterization 84 4.3.2 Spectroscopic and Diffractometric Characterization 88 4.4 Preparation and Characterization 92 4.4.1 Bottom–Up Approaches 92 4.4.1.1 On–Surface Synthesis 92 4.4.1.2 Synthesis at Water/Air or Solvent–to–Solvent Interface 92 4.4.1.3 Synthesis at the Liquid–Liquid Interface 100 4.4.2 Miscellaneous 104 4.4.2.1 Direct Colloidal Formation 104 4.4.2.2 Surfactant Mediated 104 4.4.3 Top–Down Approaches 105 4.4.3.1 Liquid Phase Exfoliation (LPE) 106 4.4.3.2 Micromechanical Exfoliation 110 4.5 Properties and Potential Applications 111 4.5.1 Gas Separation 111 4.5.2 Electronic Devices 112 4.5.3 Catalysis 113 4.6 Conclusions and Perspectives 115 Acknowledgments 116 References 116 5 Application of Metal–Organic Frameworks (MOFs) for CO2 Separation 123Mohanned Mohamedali, Hussameldin Ibrahim, and Amr Henni 5.1 Introduction 123 5.2 Factors Influencing the Applicability of MOFs for CO2 Capture 124 5.2.1 Open Metal Sites 125 5.2.2 Amine Grafting on MOFs 132 5.2.3 Effects of Organic Ligand 138 5.3 Current Trends in CO2 Separation Using MOFs 139 5.3.1 Ionic Liquids/MOF Composites 139 5.3.2 MOF Composites for CO2 Separation 143 5.3.3 Water Stability of MOFs 144 5.3.3.1 Effect of Water on MOFs with Open Metal Sites 146 5.3.3.2 Effects of the Organic Ligand on Water Stability of MOFs 147 5.4 Conclusion and Perspective 150 References 151 6 Current Status of Porous Metal–Organic Frameworks for Methane Storage 163Yabing He, Wei Zhou, and Banglin Chen 6.1 Introduction 163 6.2 Requirements for MOFs as ANG Adsorbents 165 6.3 Brief History of MOF Materials for Methane Storage 167 6.4 The Factors Influencing Methane Adsorption 168 6.4.1 Surface Area 169 6.4.2 Pore Size 170 6.4.3 Adsorption Heat 170 6.4.4 Open Metal Sites 170 6.4.5 Ligand Functionalization 171 6.5 Several Classes of MOFs for Methane Storage 171 6.5.1 Dicopper Paddlewheel–Based MOFs 171 6.5.2 Zn4O–Cluster Based MOFs 180 6.5.3 Zr–Based MOFs 182 6.5.4 Al–Based MOFs 186 6.5.5 MAF Series 189 6.5.6 Flexible MOFs for Methane Storage 190 6.6 Conclusion and Outlook 192 References 195 7 MOFs for the Capture and Degradation of Chemical Warfare Agents 199Elisa Barea, Carmen R. Maldonado and Jorge A. R. Navarro 7.1 Introduction to Chemical Warfare Agents (CWAs) 199 7.2 Adsorption of CWAs 201 7.3 Catalytic Degradation of CWAs 206 7.3.1 Hydrolysis of Nerve Agents and Their Simulants 206 7.3.2 Oxidation of Sulfur Mustard and Its Analogues 211 7.3.3 Multiactive Catalysts for CWA Degradation 212 7.4 MOF Advanced Materials for Protection against CWAs 214 7.5 Summary and Future Prospects 218 References 219 8 Membranes Based on MOFs 223Pasquale F. Zito, Adele Brunetti, Alessio Caravella, Enrico Drioli and Giuseppe Barbieri 8.1 Introduction 223 8.2 Characteristics of MOFs 224 8.3 MOF–Based Membranes for Gas Separation 225 8.3.1 MOF in Mixed Matrix Membranes 226 8.3.1.1 MOF–based MMMs: Experimental Results 228 8.3.2 MOF Thin–Film Membranes 232 8.3.2.1 Stability of Thin–Film MOF Membranes 242 8.3.3 Modeling the Permeation through MOF–based MMMs 244 Acknowledgments 246 References 246 9 Composites of Metal–Organic Frameworks (MOFs): Synthesis and Applications in Separation and Catalysis 251Devjyoti Nath, Mohanned Mohamedali, Amr Henni and Hussameldin Ibrahim 9.1 Introduction 251 9.2 Synthesis of MOF Composites 252 9.2.1 MOF–Carbon Composites 252 9.2.1.1 MOF–CNT Composites 252 9.2.1.2 MOF–AC Composites 255 9.2.1.3 MOF–GO Composites 255 9.2.2 MOF Thin Films 256 9.2.3 MOF–Metal Nanoparticle Composites 262 9.2.3.1 Solution Infiltration Method 263 9.2.3.2 Gas Infiltration Method 266 9.2.3.3 Solid Grinding Method 266 9.2.3.4 Template–Assisted Synthesis Method 266 9.2.4 MOF–Metal Oxide Composites 266 9.2.5 MOF–Silica Composites 272 9.3 Applications of MOF Composites in Catalysis and Separation 274 9.3.1 MOF Composites for Catalytic Application 274 9.3.2 MOF Composites for Gas Adsorption and Storage Applications 276 9.3.3 MOF Composites for Liquid Separation Applications 285 9.4 Conclusions 286 References 286 10 Tuning of Metal–Organic Frameworks by Pre– and Post–synthetic Functionalization for Catalysis and Separations 297Christopher F. Cogswell, Zelong Xie, and Sunho Choi 10.1 Introduction 297 10.1.1 Terminology for Functionalization on MOFs 297 10.1.2 General Design Parameters for Separations and Catalysis 299 10.2 Pre–synthetic Functionalization 303 10.2.1 Explanation of this Technique 303 10.2.2 Separations Applications 304 10.2.3 Catalytic Applications 307 10.3 Type 1 or Physical Impregnation 309 10.3.1 Explanation of this Technique 309 10.3.2 Separations Applications 310 10.3.3 Catalytic Applications 312 10.4 Type 2 or Covalent Attachment 313 10.4.1 Explanation of this Technique 313 10.4.2 Separations Applications 314 10.4.3 Catalytic Applications 316 10.5 Type 3 or In Situ Reaction 318 10.5.1 Explanation of this Technique 318 10.5.2 Separations Applications 319 10.5.3 Catalytic Applications 321 10.6 Type 4 or Ligand Replacement 321 10.7 Type 5 or Metal Addition 322 10.7.1 Explanation of this Technique 322 10.7.2 Separations Applications 325 10.7.3 Catalytic Applications 325 10.8 Conclusions 326 References 327 11 Role of Defects in Catalysis 341Zhenlan Fang and Qiang Ju 11.1 Introduction 341 11.2 Definition of MOF Defect 342 11.3 Classification of MOF Defects 343 11.3.1 Defects Classified by Defect Dimensions 343 11.3.2 Defects Classified by Distribution, Size, and State 343 11.3.3 Defects Classified by Location 343 11.4 Formation of MOF Defects 343 11.4.1 Inherent Defects of MOFs 343 11.4.1.1 Inherent Surface Defect 344 11.4.1.2 Inherent Internal Defect 344 11.4.1.3 Post–crystallization Cleavage 345 11.4.2 Intentionally Implanted Defects via Defect Engineering 346 11.4.2.1 Defects Introduced during De Novo Synthesis 347 11.4.2.2 Defects Formed by Post–synthetic Treatment 351 11.5 Characterization of Defects 352 11.5.1 Experimental Methods for Analyzing Defects 352 11.5.1.1 Assessing Presence of Defects 352 11.5.1.2 Imaging Defects 355 11.5.1.3 Probing Chemical and Physical Environment of Defects 357 11.5.1.4 Distinguish between Isolated Local and Correlated Defects 358 11.5.2 Theoretical Methods 359 11.6 The Role of Defect in Catalysis 363 11.6.1 External Surface Linker Vacancy 363 11.6.2 Inherent Linker Vacancy of Framework Interior 366 11.6.3 Intentionally Implanted Defects 367 11.6.3.1 Implanted Linker Vacancy by TML Strategy 367 11.6.3.2 Implanted Linker Vacancy by LML Strategy 368 11.6.3.3 Implanted Linker Vacancy by Post–synthetic Treatment 369 11.6.3.4 Implanted Linker Vacancy by Fast Precipitation 370 11.6.3.5 Implanted Linker Vacancy by MOF Partial Decomposition 370 11.7 Conclusions and Perspectives 372 Acknowledgment 372 References 372 12 MOFs as Heterogeneous Catalysts in Liquid Phase Reactions 379Maksym Opanasenko, Petr Nachtigall, and Jiří Čejka 12.1 Introduction 379 12.2 Synthesis of Different Classes of Organic Compounds over MOFs 380 12.2.1 Alcohols 380 12.2.2 Carbonyl and Hydroxy Carbonyl Compounds 383 12.2.3 Carboxylic Acid Derivatives 385 12.2.4 Acetals and Ethers 389 12.2.5 Terpenoids 390 12.3 Specific Aspects of Catalysis by MOFs 392 12.3.1 Concept of Concerted Effect of MOF’s Active Sites: Friedländer Reaction 392 12.3.2 Dynamically Formed Defects as Active Sites: Knoevenagel Condensation 394 12.4 Concluding Remarks and Future Prospects 395 References 396 13 Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis 399Karen Leus, Himanshu Sekhar Jena, and Pascal Van Der Voort 13.1 Introduction 399 13.1.1 Impregnation Methods 400 13.1.1.1 Liquid Phase Impregnation 400 13.1.1.2 Solid Phase Impregnation 401 13.1.1.3 Gas Phase Impregnation 401 13.1.2 Assembly Methods 402 13.2 Nanoparticles in MOFs for Gas and Liquid Phase Oxidation Catalysis 405 13.3 Nanoparticles in MOFs in Hydrogenation Reactions 411 13.4 Nanoparticles in MOFs in Dehydrogenation Reactions 424 13.5 Nanoparticles in MOFs in C─C Cross–Coupling Reactions 430 13.6 The Use of Nanoparticles in MOFs in Tandem Reactions 433 13.7 Conclusions and Outlook 437 References 438 14 MOFs as Supports of Enzymes in Biocatalysis 447Sérgio M. F. Vilela and Patricia Horcajada 14.1 Introduction 447 14.2 MOFs as Biomimetic Catalysts 449 14.3 Enzyme Immobilization Strategies 454 14.3.1 Surface Immobilization 455 14.3.2 Diffusion into the MOF Porosity 456 14.3.3 In Situ Encapsulation/Entrapment 457 14.4 Biocatalytic Reactions Using Enzyme–MOFs 459 14.4.1 Esterification and Transesterification 463 14.4.2 Hydrolysis 464 14.4.3 Oxidation 466 14.4.4 Synthesis of Warfarin 468 14.4.5 Other Applications Based on the Catalytic Properties of Enzyme–MOFs 468 14.5 Conclusions and Perspectives 469 Acknowledgments 470 References 471 15 MOFs as Photocatalysts 477Sergio Navalón and Hermenegildo García 15.1 Introduction 477 15.2 Properties of MOFs 482 15.3 Photophysical Pathways 483 15.4 Photocatalytic H2 Evolution 490 15.5 Photocatalytic CO2 Reduction 493 15.6 Photooxidation Reactions 494 15.7 Photocatalysis for Pollutant Degradation 496 15.8 Summary and Future Prospects 497 Acknowledgements 498 References 498 Index 503