Abstract

vi

Acknowledgements

ix

1.

Introduction

1

1.1

Introduction

1

1.2

The Hydrogenation of Carbon Monoxide

3

1.3

The Cyclotrimerization of Acetylene

4

1.4

References

5

2.

Experimental Methods

6

2.1

Instrumentation

6

2.2

Surface Analysis Methods:  Introduction

19

2.3

Auger Electron Spectroscopy (AES)

19

2.4

X-ray Photoelectron Spectroscopy (FPS or ESCA)

29

2.5

Temperature-programmed Description (TD or TDS)

34

2.6

Work Function Measurements

37

2.7

Low Energy Electron Diffraction (LEED)

39

2.8

Materials

42

2.9

Catalyst Samples

44

2.10

Dosing Materials and Procedures

47

2.11

Low Pressure Studies

48

2.12

High Pressure Studies

52

2.13

References

54

Introduction to Chapter Three, Four and Five:  Hydrogenation of Carbon Monoxide

56

3.

Deuterium Isotope Effects on Hydrogenation of Carbon Monoxide over Rhodium

62

3.1

Introduction

62

3.2

Results and Discussion

63

3.3

References

72

4.

Hydrogenation of Carbon Monoxide Over Oxides of Rhodium and 3d Transition Metal Perovskites

73

4.1

Introduction

73

4.2

Results and Discussion

75

4.3

References

86

5.

Hydrogenation of Carbon Monoxide on Mo(100) Single Crystals and Polycrystaline Foils

87

5.1

Introduction

87

5.2

Results

89

5.3

Discussion

100

5.4

References

109

6.

Model Catalytic Hydrogenitrogenation and hydrogenoxygenation reactions over clean and sulfided molybdenum Single Crystals and Foils

111

6.1

Introduction

111

6.2

Clean Mo Surfaces

112

6.3

Sulfdied Mo Surfaces

116

6.4

Discussion

118

6.5

References

119

7.

The Conversion of Acetylene to form Benzene over Palladium Single Crystal Surfaces

120

7.1

Introduction

120

7.2

Results:  Introduction

122

7.3

Ultra-high Vacuum Studies: Fd(111)

123

7.4

Effect of as atoms on Cyclotrimerization at Low Pressures: (Pd(111)

127

7.5

Ultra-high Vacuum Studies: Pd(110)

131

7.6

Effect of Adatoms on Cyclotrimerization at Low Pressures: Pd(110)

133

7.7

Ultra-high Vacuum Studies: Pd(100)

136

7.8

Effect of Adatoms on Cyclotrimerization at Low Pressures: Pd(100)

138

7.9

Coverage Dependence of Additives

144

7.10

Conversion of Acetylene to Benzene at High Pressures

146

7.11

Effect of Adatoms on Cyclotrimerization at High Pressures: Introduction

151

7.12

Effect of Adatoms on Cyclotrimerization at High Pressures: Pd(111) and Pd(100)

152

7.13

Effect of Adatoms on Cyclotrimerization at High Pressures: Pd(110)

155

7.14

Discussion of UHV and High Pressure Studies on Clean Pd Single Crystal Surfaces:  Introduction

156

7.15

Discussion of UHV and High Pressure Studies on Clean Pd Single Crystal Surfaces

162

7.16

Discussion of UHV and High Pressure Studies on Promoted Pd Single Crystal Catalysts:  Introduction

163

7.17

Discussion of UHV and High Pressure Studies on Promoted Pd Single Crystal Catalysts:  Adatom Properties

169

7.18

Discussion of High Pressure Studies on Promoted Pd Single Crystal Catalysts:  Introduction

170

7.19

Discussion of High Pressure Studies on Promoted Pd Single Crystal Catalysts:  Pd(111) and Pd(100)

171

7.20

Discussion of High Pressure Studies on Promoted Pd Single Crystal Catalysts:  Pd(110)

172

7.21

Discussion of UHV Studies on Promoted Pd Single Crystal Catalysts: Pd(100), Pd(111) ad Pd(110)

177

7.22

Comparison of Results of UHV and High Pressure Studies on Promoted Pd Single Crystal Surfaces

177

7.23

References

178

8.

Conclusions

181

8.1

Overview

181

8.2

Hydrogenation of Carbon Monoxide

182

8.3

Cyclotrimerization of Acetylene

184

Appendix:

Cylindrical Mirror Analyzer Schematics and Photographs

185

A.1

Materials and Suppliers

185

A.2

Overview of Schematics

186

A.3

Abbreviations Used in Schematics

187

A.4

Figs. A.1-A.12

188

A.5

Figs. A.13-A.18

201

A.6

Figs. A.19-A.22

208

A.7

Figs. A.23-A.37

213

A.8

Photographs A.38-A.52

229