Catalysis in Confined Frameworks

Preface xiii 1 Engineering of Metal Active Sites in MOFs 1 Carmen Fernández-Conde, María Romero-Ángel, Ana Rubio-Gaspar, and Carlos Martí-Gastaldo 1.1 Metal Node Engineering 2 1.1.1 Frameworks with Intrinsically Active Metal Nodes 3 1.1.1.1 Metal–Organic Frameworks with Only One Metal 3 1.1.1.2 Metal–Organic Frameworks with more than One Metal in its Cluster 6 1.1.2 Introducing Defectivity as a Powerful Tool to Tune Metal-node Catalytic Properties in MOFs 8 1.1.3 Incorporating Metals to Already-Synthetized Metal–Organic Frameworks: Isolating the Catalytic Site 12 1.1.4 Metal Exchange 14 1.1.5 Attaching Metallic Units to the MOF 14 1.1.6 Grafting of Organometallic Complexes into the MOF Nodes 18 1.2 Ligand Engineering 21 1.2.1 Ligands as Active Metal Sites 22 1.2.1.1 Creating Metal Sites in the Organic Linkers. Types of Ligands 22 1.2.1.2 Cooperation Between Single-Metal Sites and Metalloligands 28 1.2.1.3 Ligand Accelerated Catalysis (LAC) 28 1.2.2 Introduction of Metals by Direct Synthesis 31 1.2.2.1 In-situ Metalation 32 1.2.2.2 Premetalated Linker 32 1.2.2.3 Postgrafting Metal Complexes 33 1.2.3 Introduction of Metals by Post-synthetic Modifications 34 1.2.3.1 Post-synthetic Exchange or Solvent-Assisted Linker Exchange (sale) 34 1.2.3.2 Post-synthetic Metalation 36 1.3 Metal-Based Guest Pore Engineering 38 1.3.1 Encapsulation Methodologies in As-Made Metal–Organic Frameworks 39 1.3.1.1 Incipient Wetness Impregnation 39 1.3.1.2 Ship-in-a-Bottle 42 1.3.1.3 Metal–Organic Chemical Vapor Deposition (MOCVD) 42 1.3.1.4 Metal-Ion Exchange 46 1.3.2 In Situ Guest Metal–Organic Framework Encapsulations 47 1.3.2.1 Solvothermal Encapsulation or One Pot 47 1.3.2.2 Co-precipitation Methodologies 49 List of Abbreviations 52 References 53 2 Engineering the Porosity and Active Sites in Metal–Organic Framework 67 Ashish K. Kar, Ganesh S. More, and Rajendra Srivastava 2.1 Introduction 67 2.2 Active Sites in MOF 69 2.2.1 Active Sites Near Pores in MOF 69 2.2.2 Active Sites Near Metallic Nodes in MOF 70 2.2.3 Active Sites Near Ligand Center in MOF 70 2.3 Synthesis and Characterization 70 2.4 Engineering of Active Sites in MOF Structure for Catalytic Transformations 72 2.4.1 Pore Tunability 73 2.4.2 Metal Nodes 77 2.4.3 Ligand Centers 83 2.5 Conclusion 90 References 91 3 Characterization of Organic Linker-Containing Porous Materials as New Emerging Heterogeneous Catalysts 97 Ali R. Oveisi, Saba Daliran, and Yong Peng 3.1 Introduction 97 3.2 Microscopy Techniques 98 3.2.1 Scanning Electron Microscopy (SEM) 98 3.2.2 Transmission Electron Microscopy (TEM) 100 3.2.3 Atomic Force Microscopy (AFM) 103 3.3 Spectroscopy Techniques 104 3.3.1 X-ray Spectroscopy 104 3.3.1.1 X-ray Diffraction (XRD) 104 3.3.1.2 X-ray Photoelectron Spectroscopy (XPS) 105 3.3.1.3 X-ray Absorption Fine Structure (XAFS) Techniques 107 3.3.2 Nuclear Magnetic Resonance (NMR) 109 3.3.3 Electron Paramagnetic Resonance (EPR) 110 3.3.4 Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV–Vis DRS) 111 3.3.5 Inductively Coupled Plasma (ICP) Analysis 112 3.4 Other Techniques 114 3.4.1 Thermogravimetric Analysis (TGA) 114 3.4.2 N2 Adsorption 115 3.4.3 Density Functional Theory (DFT) Calculations 118 3.5 Conclusions 121 Acknowledgments 121 References 121 4 Mixed Linker MOFs in Catalysis 127 Mohammad Y. Masoomi and Lida Hashemi 4.1 Introduction 127 4.1.1 Introduction to Mixed Linker MOFs 127 4.2 Strategies for Synthesizing Mixed-Linker MOFs 128 4.2.1 IML Frameworks 128 4.2.2 HML Frameworks 129 4.2.3 TML Frameworks 130 4.3 Types of Mixed-Linker MOFs 131 4.3.1 Pillared-Layer Mixed-Linker MOFs 131 4.3.2 Cage-Directed Mixed-Linker MOFs 132 4.3.3 Cluster-Based Mixed-Linker MOFs 132 4.3.4 Structure Templated Mixed-Linker MOFs 132 4.4 Introduction to Catalysis with MOFs 133 4.5 Mixed-Linker MOFs as Heterogeneous Catalysts 133 4.5.1 Mixed-Linker MOFs with Similar Size/Directionality Linkers 134 4.5.2 Mixed-Linker MOFs with Structurally Independent Linkers 140 4.6 Conclusion 148 References 148 5 Acid-Catalyzed Diastereoselective Reactions Inside MOF Pores 151 Herme G. Baldoví, Sergio Navalón, and Francesc X. Llabrés I Xamena 5.1 Introduction 151 5.2 Diastereoselective Reactions Catalyzed by MOFs 154 5.2.1 Meerwein–Ponndorf–Verley Reduction of Carbonyl Compounds 154 5.2.2 Aldol Addition Reactions 158 5.2.3 Diels–Alder Reaction 162 5.2.4 Isomerization Reactions 164 5.2.5 Cyclopropanation 168 5.3 Conclusions and Outlook 176 Acknowledgments 176 References 176 6 Chiral MOFs for Asymmetric Catalysis 181 Kayhaneh Berijani and Ali Morsali 6.1 Chiral Metal–Organic Frameworks (CMOFs) 181 6.2 Synthesis Methods of CMOFs with Achiral and Chiral Building Blocks 184 6.2.1 Spontaneous Resolution 185 6.2.2 Direct Synthesis 187 6.2.3 Indirect Synthesis 190 6.3 Chiral MOF Catalysts 192 6.3.1 Brief History of CMOF-Based Catalysts 192 6.3.2 Designing CMOF Catalysts 193 6.4 Examples of Enantioselective Catalysis Using CMOF-Based Catalysts 194 6.4.1 Type I: Chiral MOFs in Simple Asymmetric Reactions 194 6.4.2 Type II: Chiral MOFs in Complex Asymmetric Reactions 206 6.5 Conclusion 210 References 210 7 MOF-Supported Metal Nanoparticles for Catalytic Applications 219 Danyu Guo, liyu Chen, and Yingwei li 7.1 Introduction 219 7.2 Synergistic Catalysis by MNP@MOF Composites 220 7.2.1 The Inorganic Nodes of MOFs Cooperating with Metal NPs 220 7.2.2 The Organic Linkers of MOFs Cooperating with Metal NPs 220 7.2.3 The Nanostructures of MOFs Cooperating with Metal NPs 221 7.3 Electrocatalysis Applications 221 7.3.1 Hydrogen Evolution Reaction 221 7.3.2 Oxygen Evolution Reaction 223 7.3.3 Oxygen Reduction Reaction 224 7.3.4 CO2 Reduction Reaction 224 7.3.4.1 CO 225 7.3.4.2 HCOOH 225 7.3.4.3 C2H4 225 7.3.5 Nitrogen Reduction Reaction 227 7.3.6 Oxidation of Small Molecules 228 7.4 Photocatalytic Applications 229 7.4.1 Photocatalytic Hydrogen Production 229 7.4.2 Photocatalytic CO2 Reduction 232 7.4.2.1 CO2 Photoreduction to CO 232 7.4.2.2 CO2 Photoreduction to CH3OH 233 7.4.2.3 CO2 Photoreduction to HCOO−/HCOOH 234 7.4.3 Photocatalytic Organic Reactions 235 7.4.3.1 Photocatalytic Hydrogenation Reactions 235 7.4.3.2 Photocatalytic Oxidation Reactions 235 7.4.3.3 Photocatalytic Coupling Reaction 236 7.4.4 Photocatalytic Degradation of Organic Pollutants 237 7.4.4.1 Degradation of Pollutants in Wastewater 237 7.4.4.2 Degradation of Gas-Phase Organic Compounds 239 7.5 Thermocatalytic Applications 239 7.5.1 Oxidation Reactions 239 7.5.1.1 Gas-Phase Oxidation Reactions 239 7.5.1.2 Liquid-Phase Oxidation Reactions 240 7.5.2 Hydrogenation Reactions 241 7.5.2.1 Hydrogenation of C=C and C≡C Groups 241 7.5.2.2 The Reduction of −NO2 Group 242 7.5.2.3 The Reduction of C=O Groups 244 7.5.3 Coupling Reactions 244 7.5.3.1 Suzuki–Miyaura Coupling Reactions 244 7.5.3.2 Heck Coupling Reactions 246 7.5.3.3 Glaser Coupling Reactions 246 7.5.3.4 Knoevenagel Condensation Reaction 246 7.5.3.5 Three-Component Coupling Reaction 247 7.5.4 CO2 Cycloaddition Reactions 247 7.5.5 Tandem Reactions 248 7.6 Conclusions and Outlooks 250 References 251 8 Confinement Effects in Catalysis with Molecular Complexes Immobilized into Porous Materials 273 Maryse Gouygou, Philippe Serp, and Jérôme Durand 8.1 Introduction 273 8.2 Immobilization of Molecular Complexes into Porous Materials 279 8.2.1 Confinement of Molecular Complexes in Mesoporous Silica 279 8.2.2 Confinement of Molecular Complexes in Zeolites 281 8.2.3 Confinement of Molecular Complexes in Covalent Organic Frameworks (COF) 282 8.2.4 Confinement of Molecular Complexes in Metal–Organic Frameworks (MOFs) 283 8.2.5 Confinement of Molecular Complexes in Carbon Materials 285 8.3 Characterization of Molecular Complexes Immobilized into Porous Materials 285 8.4 Catalysis with Molecular Complexes Immobilized into Porous Materials and Evidences of Confinement Effects 287 8.4.1 Hydrogenation Reactions 288 8.4.2 Hydroformylation Reactions 289 8.4.3 Oxidation Reactions 290 8.4.4 Ethylene Oligomerization and Polymerization Reactions 291 8.4.5 Metathesis Reactions 291 8.4.6 Miscellaneous Reactions on Various Supports 293 8.4.6.1 Zeolites 293 8.4.6.2 Mesoporous Silica 293 8.4.6.3 MOFs 294 8.4.7 Asymmetric Catalysis Reactions 295 8.5 Conclusion 298 References 299 9 Size-Selective Catalysis by Metal–Organic Frameworks 315 Amarajothi Dhakshinamoorthy and Hermenegildo García 9.1 Introduction 315 9.2 Friedel–Crafts Alkylation 319 9.3 Cycloaddition Reactions 320 9.4 Oxidation of Olefins 323 9.5 Hydrogenation Reactions 325 9.6 Aldehyde Cyanosilylation 326 9.7 Knoevenagel Condensation 328 9.8 Conclusions 329 References 330 10 Selective Oxidations in Confined Environment 333 Oxana A. Kholdeeva 10.1 Introduction 333 10.2 Transition-Metal-Substituted Molecular Sieves 334 10.2.1 Ti-Substituted Zeolites and H2O2 334 10.2.2 Co-Substituted Aluminophosphates and O2 337 10.3 Mesoporous Metal–Silicates 338 10.3.1 Mesoporous Ti-Silicates in Oxidation of Hydrocarbons 339 10.3.2 Mesoporous Ti-Silicates in Oxidation of Bulky Phenols 340 10.3.3 Alkene Epoxidation over Mesoporous Nb-Silicates 342 10.4 Metal–Organic Frameworks 343 10.4.1 Selective Oxidations over Cr- and Fe-Based MOFs 343 10.4.2 Selective Oxidations with H2O2 over Zr- and Ti-Based MOFs 347 10.5 Polyoxometalates in Confined Environment 349 10.5.1 Silica-Encapsulated POM 350 10.5.2 MOF-Incorporated POM 350 10.5.3 POMs Supported on Carbon Nanotubes 352 10.6 Conclusion and Outlook 353 Acknowledgments 354 References 354 11 Tailoring the Porosity and Active Sites in Silicoaluminophosphate Zeolites and Their Catalytic Applications 363 Jacky H. Advani, Abhinav Kumar, and Rajendra Srivastava 11.1 Introduction 363 11.2 Synthesis of SAPO-n Zeolites 365 11.3 Characterization of SAPO Zeolites 370 11.4 SAPO-Based Catalysts in Organic Transformations 370 11.4.1 Acid Catalysis 370 11.4.2 Reductive Transformations 374 11.4.2.1 Selective Catalytic Reduction (SCR) 374 11.4.2.2 Hydroisomerization 379 11.4.2.3 Hydroprocessing 383 11.4.2.4 CO2 Hydrogenation 385 11.5 Conclusion 387 References 388 12 Heterogeneous Photocatalytic Degradation of Pharmaceutical Pollutants over Titania Nanoporous Architectures 397 Surya Kumar Vatti and Parasuraman Selvam 12.1 Introduction 397 12.2 Advanced Oxidation Process 399 12.2.1 Ozonation 401 12.2.2 UV Irradiation (Photolysis) 401 12.2.3 Fenton and Photo-Fenton Process 402 12.2.4 Need for Green Sustainable Heterogeneous AOP 402 12.2.5 Heterogeneous Photocatalysis 402 12.3 Semiconductor Photocatalysis Mechanism 403 12.4 Factors Affecting Photocatalytic Efficiency 404 12.5 Crystal Phases of TiO2 404 12.6 Semiconductor/Electrolyte Interface and Surface Reaction 406 12.7 Visible-Light Harvesting 409 12.8 Photogenerated Charge Separation Strategies 412 12.8.1 TiO2/Carbon Heterojunction 412 12.8.2 TiO2/SC Coupled Heterojunction 412 12.8.3 TiO2/ TiO2 Phase Junction 414 12.8.4 Metal/ TiO2 Schottky Junction 415 12.9 Ordered Mesoporous Materials 415 12.10 Ordered Mesoporous Titania 417 12.10.1 Synthesis and Characterization 418 12.10.2 Photocatalytic Degradation Studies 420 12.10.3 Complete Mineralization Studies 424 12.10.4 Spent Catalyst 425 12.11 Conclusion 427 Acknowledgment 428 References 429 13 Catalytic Dehydration of Glycerol Over Silica and Alumina-Supported Heteropoly Acid Catalysts 433 Sekar Mahendran, Shinya Hayami, and Parasuraman Selvam 13.1 Introduction 433 13.2 Value Addition of Bioglycerol 434 13.3 Interaction Between HPA and Support 437 13.4 Bulk Heteropoly Acid 438 13.5 Silica-Supported HPA 439 13.5.1 Effect of Textural Properties of Support on Product Selectivity 439 13.5.2 Effect of Catalyst Loading 440 13.5.3 Effect of Acid Sites 440 13.5.4 Effect of Type of Heteropoly Acids 443 13.6 Tuning the Acidity 444 13.7 Conclusions 446 Acknowledgments 447 References 447 14 Catalysis with Carbon Nanotubes 451 Mohammad Y. Masoomi and Lida Hashemi 14.1 Introduction 451 14.1.1 Why CNT may be Suitable to be Used as Catalyst Supports? 451 14.1.1.1 From the Point of Structural Features 452 14.1.1.2 From the Point of Electronic Properties 455 14.1.1.3 From the Point of Adsorption Properties 455 14.1.1.4 From the Point of Mechanical and Thermal Properties 456 14.2 Catalytic Performances of CNT-Supported Systems 456 14.2.1 Different Approaches for the Anchoring of Metal-Containing Species on CNT 457 14.2.2 Different Approaches for the Confining NPs Inside CNTs and Their Characterization 457 14.2.2.1 Wet Chemistry Method 458 14.2.2.2 Production of CNTs Inside Anodic Alumina 459 14.2.2.3 Arc-Discharge Synthesis 459 14.2.3 Hydrogenation Reactions 459 14.2.4 Dehydrogenation Reactions 460 14.2.5 Liquid-Phase Hydroformylation Reactions 461 14.2.6 Liquid-Phase Oxidation Reactions 462 14.2.7 Gas-Phase Reactions 464 14.2.7.1 Syngas Conversion 464 14.2.7.2 Ammonia Synthesis and Ammonia Decomposition 464 14.2.7.3 Epoxidation of Propylene in DWCNTs 465 14.2.8 Fuel Cell Electro Catalyst 465 14.2.9 Catalytic Decomposition of Hydrocarbons 466 14.2.10 CNT as Heterogeneous Catalysts 466 14.2.11 Sulfur Catalysis 467 14.3 Metal-Free Catalysts of CNTs 467 14.4 Conclusion 468 References 469 Index 473