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 Mes