The first comprehensive textbook on the timely and rapidly developing topic of inorganic porous materials
This is the first textbook to completely cover a broad range of inorganic porous materials. It introduces the reader to the development of functional porous inorganic materials, from the synthetic zeolites in the 50’s, to today’s hybrid materials such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and related networks. It also provides the necessary background to understand how porous materials are organized, characterized, and applied in adsorption, catalysis, and many other domains. Additionally, the book explains characterization and application from the materials scientist viewpoint, giving the reader a practical approach on the characterization and application of the respective materials.
Introduction to Inorganic Porous Materials begins by describing the basic concepts of porosity and the different types of pores, surfaces, and amorphous versus crystalline materials, before introducing readers to nature’s porous materials. It then goes on to cover everything from adsorption and catalysis to amorphous materials such as silica to inorganic carbons and Periodic Mesoporous Organosilicas (PMOs). It discusses the synthesis and applications of MOFs and the broad family of COFs. It concludes with a look at future prospects and emerging trends in the field.
- The only complete book of its kind to cover the wide variety of inorganic and hybrid porous materials
- A comprehensive reference and outstanding tool for any course on inorganic porous materials, heterogeneous catalysis, and adsorption
- Gives students and investigators the opportunity to learn about porous materials, how to characterize them, and understand how they can be applied in different fields
Introduction to Inorganic Porous Materials is an excellent book for students and professionals of inorganic chemistry and materials science with an interest in porous materials, functional inorganic materials, heterogeneous catalysis and adsorption, and solid state characterization techniques.
Table of Contents
Preface xi
About the Authors xiii
1 Nature’s Porous Materials: From Beautiful to Practical 1
1.1 Living Porosity 1
1.1.1 Butterflies 1
1.1.2 Algae 4
1.1.3 Bamboo 8
1.2 Clay Minerals 8
1.2.1 Natural Clays 8
1.2.2 Pillared Interlayered Clays - PILCs 12
References 13
2 Theory of Adsorption and Catalysis: Surface Area and Porosity 15
2.1 Determination of Surface Area and Porosity by Gas Sorption 15
2.1.1 Introduction 15
2.1.2 Chemisorption and Physisorption 15
2.1.3 Reversible Monolayer Adsorption - The Langmuir Isotherm 16
2.2 The BET (Brunauer, Emmet, Teller) Model 21
2.2.1 The BET Equation 21
2.2.2 Multipoint BET Analysis 23
2.3 Capillary Condensation and Pore Size, the Type IV Isotherm 25
2.3.1 The Kelvin and the Halsey Equation 25
2.3.2 Barrett, Joyner, Halenda (BJH) Pore Size Distributions 27
2.3.3 Types of Adsorption Isotherms 32
2.3.4 Adsorption Hysteresis 34
2.3.5 Evaluation of Micropores 36
2.4 Liquid Phase Adsorption - Langmuir and Freundlich Isotherms 37
2.4.1 Adsorption Kinetics 38
2.4.2 Adsorption Isotherms 40
2.5 Heterogeneous Catalysis 42
2.5.1 Introduction 42
2.5.2 Types of Catalysis 44
2.5.3 Toward Green and Sustainable Industrial Chemistry 46
2.5.4 Kinetics in a Heterogeneous Catalytic Reaction 50
2.5.5 Diffusion Phenomena 57
2.A Appendix 66
Exercises 68
Answers to the Problems 71
References 73
3 Zeolites and Zeotypes 75
3.1 Crystallographic Directions and Planes 75
3.1.1 Crystallographic Directions 75
3.1.2 Crystallographic Planes 77
3.2 X-Ray Diffraction 80
3.3 Zeolite Structures 82
3.4 Applications of Zeolites 85
3.4.1 Ion-Exchange, Water Softening 85
3.4.2 Catalysis 88
3.4.3 Gas Sorption and Purification 109
3.5 Solid-State NMR 111
3.5.1 Introduction to the Technique NMR 111
3.5.2 Nuclear Magnetic Resonance: The Basics 112
3.5.3 Solid-State NMR: The Challenges 115
3.5.4 The Application of Solid-State NMR 118
References 118
4 Silica, A Simple Oxide - A Case Study for FT-IR Spectroscopy 121
4.1 Different Methods to Synthesize Silica 121
4.1.1 Silica Gels and Sols 121
4.1.2 Pyrogenic Silicas 126
4.1.3 Precipitated Silicas 127
4.2 The Surface of Silica 127
4.3 Fourier Transform Infrared Spectroscopy 129
4.3.1 Principles of Infrared Spectroscopy 130
4.3.2 Principles of FT-IR 133
4.3.3 DRIFTS - Diffuse Reflectance Infrared Fourier Transform Spectroscopy 138
4.3.4 Attenuated Total Reflection 140
References 142
5 Ordered Mesoporous Silica 145
5.1 MCM-41 and MCM-48 - Revolution by the Mobil Oil Company 145
5.1.1 The Original Papers and Patents 145
5.1.2 Calculating the Wall Thickness 150
5.1.3 Interaction Between Surfactant and Inorganic Precursor 151
5.1.4 The Surfactant Packing Parameter 154
5.1.5 Hexagonal Mesoporous Silica 156
5.1.6 Stable Ordered Mesoporous Silica - SBA 157
5.1.7 Plugged Hexagonal Templated Silica 161
5.1.8 The New MCM-48: KIT-6 163
5.1.9 Further Developments of Mesoporous Silica 165
5.1.10 Pore Size Engineering 167
5.1.11 Making Thin Films - The EISA Principle 167
5.2 Applications of Mesoporous Silica 168
5.2.1 In Heterogeneous Catalysis - Functionalization of Mesoporous Silica 168
5.2.2 In Adsorption 183
5.2.3 As a Drug Carrier 188
5.2.4 Low-k Dielectrics 189
References 191
6 Carbons 195
6.1 Activated Carbon 195
6.2 General Introduction to Mesoporous Carbons 197
6.2.1 Synthesis of Hard-Templated Mesoporous Carbons 198
6.2.2 Synthesis of Soft-Templated Mesoporous Carbons 204
6.2.3 Influence of Synthesis Conditions on the Soft-Templated Method 207
6.2.4 Transformation of Polymer into Carbon, the Carbonization Temperature 215
6.2.5 (Hydro)Thermal and Mechanical Stability 216
6.3 Surface Modification of Mesoporous Polymers and Carbons 217
6.3.1 Pre-Modification of Polymers/Carbons 218
6.3.2 Post-Modification of Polymers/Carbons 218
6.4 Nanocarbons 218
6.4.1 Fullerenes 219
6.4.2 Carbon Nanotubes 224
6.5 Application of Porous Carbon-Based Materials 227
6.5.1 The Adsorption of Pollutants 227
6.5.2 As Catalytic Support or Direct Heterogeneous Catalyst 231
6.5.3 Electrochemical Applications: Energy Storage 237
Exercises 243
Answers to the Problems 243
References 245
7 The Era of the Hybrids - Part 1: Periodic Mesoporous Organosilicas or PMOS 249
7.1 Introduction 249
7.2 Synthesis of PMOs 253
7.2.1 General Aspects of PMO Synthesis 253
7.2.2 PMOs with Aliphatic Bridges 257
7.2.3 PMOs with Olefinic and Aromatic Bridges 258
7.2.4 PMOs with Multi-Organic Bridges 264
7.3 General Properties of PMOs 265
7.3.1 Pore Size Engineering 265
7.3.2 (Hydro)thermal and Chemical Stability 267
7.3.3 Metamorphosis in PMOs 269
7.4 Post-Modification of PMOs 270
7.4.1 Post-Functionalization of the Unsaturated Bridges 271
7.4.2 Post-Modification of the Aromatic Ring 275
7.5 Applications of PMOs 276
7.5.1 As Heterogeneous Catalysts 276
7.5.2 As Adsorbents of Metals, Organic Compounds, and Gases 290
7.5.3 As Solid Chromatographic Packing Materials 294
7.5.4 As Low-k Films 297
7.5.5 As Biomedical Supports 298
Exercises 300
Answers to the Problems 302
References 303
8 Era of the Hybrids - Part 2: Metal-Organic Frameworks 309
8.1 Introduction 309
8.2 Isoreticular Synthesis 312
8.3 Well-Known MOFs 313
8.3.1 Cu-BTC 314
8.3.2 MIL-53 314
8.3.3 MIL-101 315
8.3.4 UiO-66 315
8.3.5 NU-1000 317
8.3.6 ZIF-8 318
8.4 Stability of MOFs 318
8.5 Preparation of MOFs 320
8.5.1 Hydro- and Solvothermal Synthesis 320
8.5.2 Microwave-Assisted Synthesis 320
8.5.3 Electrochemical Synthesis Route 321
8.5.4 High-Throughput Analysis 321
8.6 Functionalities in MOFs 321
8.6.1 Active Sites in MOFs 321
8.6.2 Multifunctional MOFs 322
8.7 Applications of MOFs 332
8.7.1 MOFs in Gas Storage and Gas Separation 332
8.7.2 MOFs in Catalysis 351
8.7.3 Luminescent MOFs 355
8.8 Industrial Applications of MOFs 364
8.9 Transmission Electron Microscopy 366
8.9.1 Electron Diffraction and Bright Field Imaging 367
8.9.2 High-Resolution Transmission Electron Microscopy 368
8.9.3 Scanning Transmission Electron Microscopy 369
8.9.4 Energy Dispersive X-Ray Spectroscopy 371
8.9.5 Electron Energy Loss Spectroscopy 371
8.9.6 Electron Tomography 371
Exercises 372
Answers to the Problems 374
References 377
9 Beyond the Hybrids - Covalent Organic Frameworks 381
9.1 Classification and Nature of COFs 381
9.2 Design of COFs 383
9.3 Boron-Based COFs 386
9.3.1 Introduction 386
9.3.2 Other Synthetic Routes to Obtain Boron-Based COFs 389
9.3.3 Methods to Increase the Stability of Boron-Based COFs 391
9.3.4 Applications of Boron-Containing COFs 392
9.4 Covalent Triazine Frameworks 395
9.4.1 Ionothermal Synthesis of Covalent Triazine Frameworks 395
9.4.2 Acid Assisted Synthesis Route 398
9.4.3 Mechanochemical Synthesis 398
9.4.4 Applications of CTFs 399
9.5 Imine COFs 404
9.5.1 Solvothermal Synthesis: COF-300 404
9.5.2 Room Temperature Synthesis of Imine COFs 406
9.5.3 Liquid Assisted Grinding 407
9.5.4 Applications of Imine COFs 408
Exercises 414
Answers to the Problems 415
References 417
Index 419
