I.

Introduction

7

II.

Ammonia Synthesis

8

II.1

Kinetics over Fe single-crystal catalysts

9

II.2

Kinetics over Re single-crystal catalysts

13

III.

CO Methanation

14

III.1

CO Methanation on clean metal single crystals

15

III.1.1

Monometallic Surfaces

15

A.

Ni(100) and Ni(111)

15

B.

Ru(110) and Ru(001)

18

C.

W(110)

19

D.

Rh(111)

20

E.

Fe(111)

21

F.

Mo(100)

21

G.

Co(001)

23

H.

Summary

23

III.1.2

Bimetallic surfaces

24

A.

Ni/W(110) and Ni/W(100)

25

B.

Cu/Ru(001) and Ag/Rh(111)

27

C.

Co/W(110) and Co/W(100)

28

III.2

CO methanation on chemically modified surfaces

28

III.2.1

Electronegative impurities

30

A.

Atomic chlorine, sulfur and Phosphorus on Ni(100)

30

B.

Sulfur on Ru(001), Rh(111) NS w(110)

32

III.2.2

Electropostive impurities

33

A.

Potassium on Ni(100)

34

III.2.3

Related theory

36

III.3

Metal-support interactions and CO Methanation

36

IV.

CO Oxidation

40

VI.

CO Oxidation by O₂

40

IV .1.1

Rh(100) ND Rh(111) surfaces

41

IV.1.2

Ru(001) surface

42

IV.1.3

Pt(100) surface

43

IV.1.4

Pd(110) surface

45

IV.1.5

Ir(110) and Ir(111) surfaces

46

IV.1.6

Summary

46

IV.2

CO Oxidation by NO

47

IV.2.1

Rh(100) and Rh(111) surfaces

47

V.

Ethylene Epoxide Synthesis

47

V.1

Kinetics over Ag(110) and Ag(111) catalysts

50

V.2

Chlorine promotion of Ag(110) and Ag(111) surfaces

52

V.3

Cesium promotion of Ag(111)

53

VI.

Thiophene Hydrodesulfurization

54

VI.1

Kinetics on Mo surfaces

55

VI.2

Kinetics on Re surfaces

57

VII.

Alkane Hydrogenolysis

58

VII.1

Ethane hydrogenolysis

 59

VII.1.1

Monometallic surfaces

59

A.

Ni(100) and Ni(111)

59

B.

Ru(001) and Ru(1,1,10)

61

C.

Ir(111) and Ir(110)-1x2)

62

D.

Pt(111)

64

E.

Re(001)

65

F.

W(100)

65

G.

Summary

66

VII.1.2

Bimetallic surfaces

67

A.

Ni/W(110) and Ni/W(100)

67

B.

Ni/Pt(111)

68

C.

Re/Pt(111) and Pt/Re(001)

69

D.

Cu/Ru(001)

70

VII.2

Propane hydrogenolysis

70

VII.2.1

Ir(111) and Ir(110)-1x2) surfaces

70

VII.3

Butane hydrogenolysis

71

VII.3.1

Ir(111) and Ir(110) – (1x2) catalysts

71

VII.3.2

Rh(111) and Rh(100) catalysts

72

VIII.3.3

Pt(100), Pt(111), Pt(332), Pt(557) Pt(10,8,7) and Pt(13,1,1) catalysts

73

VII.4

Neopentane hydrogenolysis

74

VII.4.1

Ir(111) and Ir(110)-(1x2) catalysts

74

VII.4.2

Pt(111), Pt(100), Pt(10, 8, 7) and Pt(13,1, 1) catalysts

75

VII.5

N-hexane hydrogenolysis

75

VII.5.1

Pt(100), Pt(111), Pt(332), Pt(10,8,7) Pt(13, 1, 1), Au-Pt(100) NS Au-Pt(111) Catalyst

75

VII.6

N-heptane hydrogenolysis

76

VII.6.1

Pt(111), Pt(557), Pt(10, 8, 7) and Pt(25, 10, 7) catalysts

76

VII.7

Cyclopropane hydrogenolysis

77

VII.7.1

Ni(100) and Ni(111) surfaces

77

VII.7.2

Mo(100) surface

78

VII.7.3

Pt(s)-[6(111)x(100)]surface

80

VII.7.4

Ir(111) AND Ir(110)-(1x2) surfaces

80

VII.8

Methylxyxlopropane and hydrogenolysis

82

VII.8.1

Ir(111) NS Ir(110)-1x2) surfaces

82

VII.9

Methycyclopentane hydrogenolysis

83

VII.9.1

Pt(100), Pt(111), Pt(332) and Pt(557) catalysts

83

VII.10

Cyclohexane hydrogenolysis

84

VII.10.1

Pt(111), Pt(557), Pt(25, 10, 7) and Pt(10, 8, 7) catalysts

84

VII.10.2

Ru(001) ND Cu/Ru(001) catalysts

84

VIII.

Isomerization and Cyclization of Alkanes

85

VIII.1

Butane isomerization

86

VIII.1.1

Pt(111), Pt(100), Pt(332), Pt(557) Pt(13, 1, 1) and Pt(10, 8, 7) catalysts

86

VIII.2

Neopentane isomerization

87

VIII.2.1

Pt(100), Pt(111), Pt(13, 1, 1) and Pt(10, 8, 7) catalysts

87

VIII.3

Methylpentane isomerization and cyclization

88

VIII.3.1

Pt(111), Pt(119) and Pt(557) Catalysts

88

VIII.4

N-hexane isomerization and cyclization

89

VIII.4.1

Pt(100), Pt(111), Pt(332), Pt(13, 1, 1), Pt(10, 8, 7), Au-Pt(100) and Au-Pt(111) Catalysts

89

VIII.5

N-heptane cyclization

91

VIII.5.1

Pt(111), Pt(557), Pt(10, 8, 7) and Pt(25, 10, 7) catalysts

91

VIII.6

Summary

92

IX.

Hydrogenation of Olefins

93

IX.1

Ethylene hydrogenation

94

IX.1.1

Pt(111) surface

94

IX.1.2

Ni(100), Ni(110) and Ni(111) surfaces

96

IX.2

Propylene hydrogenation

97

IX.2.1

Ir(111) and Ir(110)-(1x2) surfaces

98

IX.3

1,3 butadiene hydrogenation

98

IX.3.1

Pt(100), Pt(110), Pt(111) and Ni_0.5Pt_0.5(111) surfaces

98

IX.4

Cyclohexene hydrogenation

102

IX.4.1

Pt(223) surface

104

X.

Dehydrogenation of Cyclohexane

103

X.1

Kinetics on Pt surfaces

104

X.2

Kinetics on Ru surfaces

106

X.3

Kinetics on W surfaces

108

XI.

Cyclotrimerization of Acetylene

109

XI.1

Kinetics on Pd surfaces

109

XII.

Water-Gas Shift Reaction

110

XII.1

Kinetics over Cu(110) and Cu(111) catalysts

111

XII.2

Sulfur poisoning of Cu(111) catalysts

113

XII.3

Cesium Promotion of Cu(110) and Cu(111) catalysts

114

XIII.

Methanol Synthesis

115

XIII.1

Kinetics on Pd(110)

116

XIII.2

Studies on Cu(111), Cu(100) ZnOx/Cu(111) and Cu/Zn_O(0001) surfaces

117

Conclusions

119

Acknowledgements

121

References

122

Figure Captions

136

Tables

145

Figures

148