Characterization of Catalytic Materials

by Israel E. Wachs

Overview

Characterization of Catalytic Materials is a modern, comprehensive reference volume covering the analysis of catalytic materials used in commercial applications. This book provides information for understanding the performance of each class of catalytic material and discusses the applications of these materials in different kinds of technologies such as in pollution control, and chemical and petroleum processing. Each chapter is written by individuals who are internationally recognized as experts in their respective areas and is organized for easy reference by catalytic classes, and the types of surface, interface, and bulk characterization that might be sought. Written from the materials perspective, Characterization of Catalytic Materials focuses on the properties to be measured rather than on the techniques to be used.

Product Details

ISBN-13:	9781606501849
Publisher:	Momentum Press
Publication date:	12/01/2009
Pages:	202
Product dimensions:	6.10(w) x 9.30(h) x 0.70(d)

Table of Contents

Preface to the Reissue of the Materials Characterization Series x

Preface to Series xi

Preface to the Reissue of Characterization of Catalytic Materials xii

Preface xiii

Contributors xv

Bulk Metals and Alloys

1.1 Introduction 1

The Role of Metals and Alloys in Catalysis 1

1.2 Preparation of Bulk Alloy or Bimetallic Catalysts 2

1.3 Bulk Metal Characterization Methods 4

Bulk Chemical Analysis 4

Determination of Crystal Structure 5

Morphology and Microstructure 6

Quantification of Surface Area 8

Surface Composition 9

Gas-Surface Interactions 11

Surface Structure of Single Crystals and Metal Films 12

1.4 Surface Composition-Structure and Catalysis Relationship 14

Supported Metals

2.1 Introduction 17

Characteristics of Supported Metals 18

Conditions of Characterization of Supported Metals 18

2.2 Typical Approaches to Metals Characterization 19

Chemisorption 19

Methods of Measuring Chemisorption 20

2.3 Reaction Studies of Supported Metals 25

2.4 X-ray Diffraction and Scattering Methods 27

Particle Sizes from Line-Broadening 27

Small-Angle X-ray Scattering 28

2.5 Electron Microscopy 29

2.6 X-ray Absorption Spectroscopy 30

Preparation for Measurements 32

Interpretation of Information 32

Strengths and Weaknesses of XAS 36

2.7 Mossbauer Spectroscopy 37

2.8 Photoelectron/Photoemission Spectroscopy 38

2.9 Magnetic Methods 42

2.10 Summary 43

Bulk Metal Oxides

3.1 Introduction 47

Oxides as Catalysts 47

Mechanistic Features of Oxide Catalyzed Reactions 48

3.2 Synthesis Methods 49

3.3 Properties of Oxides and Their Relation to Catalytic Behavior 51

Determination of Bulk Structure 51

Bulk Composition 57

Metal Oxidation State and Local Structural Environment 57

Characterization by Electron Microscopy 60

Surface Characterization Using Molecular Probes 61

Surface Characterization Using Spectroscopic Analyses 63

Reducibility and Oxide Ion Mobility 64

Magnetic and Electronic Properties 65

3.4 Summary 66

Supported Metal Oxides

4.1 Introduction 69

4.2 Synthesis Methods 70

4.3 Characterization 71

Structure of the Supported Metal Oxide Phase 71

Surface Coverage of the Supported Metal Oxide Phase 73

Oxidation States and Local Structural Environments of Supported Metal Oxide Phases 75

Morphology of the Supported Metal Oxide Phase 77

Surface Chemistry of Supported Metal Oxides 77

Characterization Summary 79

4.4 Impregnating Solution Chemistry 79

4.5 Supported Metal Oxide Catalysts Under Ambient Conditions 80

4.6 Supported Metal Oxide Catalysts Under In Situ Conditions 81

4.7 Catalysis and Structure-Reactivity Relationship 82

4.8 Summary 85

Bulk Metal Sulfides

5.1 Introduction 89

5.2 Preparation of Bulk TMS Catalysts 90

Binary Sulfides 90

Mixed Metal Sulfides 91

5.3 Bulk Characterization 92

Structures of TMS and Stable Catalytic Phases 92

Morphology, Particle Size, and Surface Area 94

Metal Oxidation State and Structural Environment 95

5.4 Surface Composition 96

Chemisorption and Molecular Probes 96

Surface Characterization Using Spectroscopic Techniques 97

5.5 Structure-Function Relationships 100

Importance of the Electronic Structure 100

Effect of the Crystallographic Structure 102

Effect of the Sulfur Vacancies 104

5.6 Summary 105

Supported Metal Sulfides

6.1 Introduction 109

6.2 Structure of the Oxidic Catalyst 110

6.3 Structure of the Sulfidic Catalyst 114

Structure of Molybdenum 114

Structure of Cobalt and Nickel 116

6.4 Specific Surface Area 119

6.5 Structure-Reactivity Relationships 120

Role of Molybdenum 121

Role of the Promoter 122

Role of Phosphate 123

6.6 Summary 124

Zeolites and Molecular Sieves

7.1 Introduction 129

7.2 Structure of Zeolites and Molecular Sieves 129

7.3 X-ray, Neutron, and Electron Diffraction 132

Identification of Zeolites 134

Compositional and Phase Changes 135

Structure Determination by Diffraction Techniques 137

7.4 High-Resolution Electron Microscopy 138

7.5 Solid State NMR Spectroscopy 139

Framework Composition 139

Tetrahedral Atom Ordering 141

New Developments 141

7.6 Adsorption 142

Void Volume 142

Pore Size 143

7.7 Structure and Catalytic Behavior 144

7.8 Summary 145

Alumina Pillared Clays: Methods of Preparation and Characterization

8.1 Introduction 149

8.2 Synthesis Methods 151

8.3 Properties of Pillared Clays 152

X-ray Diffraction Pattern 152

Elemental Analysis 153

Electron Microscopy 154

Pore Structure by Adsorption-Desorption Techniques 155

Surface Acidity 158

²⁹Si and ²⁷Al MAS-NMR 158

Pillared Clays As Catalysts 159

8.4 Summary 161

Appendixes Techniques Summaries

1 Auger Electron Spectroscopy (AES) 167

2 Dynamic Secondary Ion Mass Spectrometry (D-SIMS) 168

3 Electron Energy-Loss Spectroscopy in the Transmission Electron Microscope (EELS) 169

4 Electron Paramagnetic Resonance/Electron Spin Resonance 170

5 Electron Probe X-Ray Microanalysis (EPMA) 171

6 Energy-Dispersive X-Ray Spectroscopy (EDS) 172

7 Extended X-Ray Absorption Fine Structure (EXAFS) 173

8 Fourier Transform Infrared Spectroscopy (FTIR) 174

9 High-Resolution Electron Energy Loss Spectroscopy (HREELS) 175

10 Inductively Coupled Plasma Mass Spectrometry (ICPMS) 176

11 Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) 177

12 Ion Scattering Spectroscopy (ISS) 178

13 Low-Energy Electron Diffraction (LEED) 179

14 Mossbauer Spectroscopy 180

15 Neutron Activation Analysis (NAA) 181

16 Neutron Diffraction 182

17 Physical and Chemical Adsorption for the Measurement of Solid State Areas 183

18 Raman Spectroscopy 184

19 Scanning Electron Microscopy (SEM) 185

20 Scanning Transmission Electron Microscopy (STEM) 186

21 Scanning Tunneling Microscopy and Scanning Force Microscopy (STM and SFM) 187

22 Solid State Nuclear Magnetic Resonance (NMR) 188

23 Static Secondary Ion Mass Spectrometry (Static SIMS) 189

24 Temperature Programmed Techniques 190

25 Transmission Electron Microscopy (TEM) 191

26 Ultraviolet Photoelectron Spectroscopy (UPS) 192

27 X-Ray Diffraction (XRD) 193

28 X-Ray Fluorescence (XRF) 194

29 X-Ray Photoelectron and Auger Electron Diffraction (XPD and AED) 195

30 X-Ray Photoelectron Spectroscopy (XPS) 196

Index 197