Table of Contents
Preface xiii
1 The Stability of Metal–Organic Frameworks 1
Georges 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 29
Andrew 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 57
Ana 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 81
David 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 123
Mohanned 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 163
Yabing 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 199
Elisa 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 223
Pasquale 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 251
Devjyoti 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 297
Christopher 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 341
Zhenlan 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 379
Maksym 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 399
Karen 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 447
Sérgio 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 477
Sergio 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
