Understanding the synthesis and applications of porous solid catalysts
Heterogeneous catalysis is a catalytic process in which catalysts and reactants exist in different phases. Heterogeneous catalysis with solid catalysts proceeds through the absorption of substrates and reagents which are liquid or gas, and this is largely dependent on the accessible surface area of the solid which can generate active reaction sites. The synthesis of porous solids is an increasingly productive approach to generating solid catalysts with larger accessible surface area, allowing more efficient catalysis.
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications provides a comprehensive overview of synthesis and use of porous solids as heterogeneous catalysts. It provides detailed analysis of pore engineering, a thorough characterization of the advantages and disadvantages of porous solids as heterogeneous catalysts, and an extensive discussion of applications. The result is a foundational introduction to a cutting-edge field.
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications readers will also find: - An editorial team comprised of international experts with extensive experience - Detailed discussion of catalyst classes including zeolites, mesoporous aluminosilicates, and more - A special focus on size selective catalysis
Catalysis in Confined Frameworks: Synthesis, Characterization, and Applications is an essential reference for catalytic chemists, organic chemists, materials scientists, physical chemists, and any researchers or industry professionals working with heterogeneous catalysis.
Table of Contents
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
