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