Publications, Presentations, and Theses

vii

List of Tables

xi

List of Figures

xii

Chapter

I.

Introduction

1

1.1

Overview

1

1.2

Objective

3

1.3

Scope

3

II.

Literature Review

6

2.1

Fischer-Tropsch Reaction

6

2.2

CO Insertion

8

2.2.1

CO Insertion in Hydroformylation

2.3

Active Site

10

2.4

Catalysts for High Oxygenate Synthesis

13

2.5

Effect of Promoters

14

2.6

Reactive Probing

16

2.7

Sulfur Poisoning

17

2.8

Infrared Spectroscopy in Catalytic Reactions

21

2.8.1

Infrared Spectroscopy:  Theory

21

2.8.2

Application to Catalytic Reaction

24

2.8.2.1

CO Chemisorption

25

2.8.2.2

Surface Hydrocarbons

25

2.8.2.3

Surface Oxygenates

31

III.

Experimental

35

3.1

Catalyst Preparation and Characterization

35

3.2

Reactor System

36

IV.

Infrared Study of the CO Insertion Reaction on Reduced Oxidized, and Sulfided Rh/SiO₂ Catalysts

40

4.1

Introduction

40

4.2

Experimental

42

4.2.1

Catalyst Preparation and Characterization

42

4.2.2

Experimental Procedure

42

4.3

Results

43

4.3.1

X-Ray Photoelectron Spectroscopy

43

4.3.2

CO Adsorption

43

4.3.3

Reaction and Adsorbed CO with C₂H₄ and H₂

49

4.3.4

Steady State Ethylene Hydroformylation

55

4.4

Discussion

63

4.4.1

Characterization of the Rh Surface by Infrared Spectroscopy of CO Adsorption

63

4.4.2

CO Insertion

64

4.5

Conclusions

70

V.

Higher Oxygenate Synthesis From Reaction of Ethylene with Syngas on Ni/SiO₂ and Sulfided Ni/SiO₂

72

5.1

Introduction

72

5.2

Experimental

73

5.2.1

Catalyst Preparation and Characterization

73

5.2.2

Experimental Procedure

73

5.3

Results and Discussion

74

5.3.1

CO/H₂ Reaction on Ni/SiO₂

74

5.3.2

C2H₄/CO/H₂ Reaction on Ni/SiO₂

77

5.3.3

Sulfur Effect on Ethylene Hydroformylation

81

5.4

Conclusions

85

Part 2

VI.

AN in Situ Infrared Study of CO Hydrogenation and Ethylene Hydroformation on Ru/SiO₂ and Sulfided Ru/SiO₂

86

6.1

Introduction

86

6.2

Experimental

88

6.2.1

Catalyst Preparation and Characterization

88

6.2.2

Experimental Procedure

89

6.3

Results and Discussion

90

6.3.1

CO Adsorption

90

6.3.2

CO Hydrogenation on Ru/SiO₂

92

6.3.3

CO Hydrogenation on Sulfided Ru/SiO₂

96

6.3.4

Ethylene Hydroformylation on Ru/SiO₂

98

6.3.5

Ethylene Hydroformylation on Sulfided Ru/SiO₂

102

6.3.6

Dynamic Behavior of Adsorbed Propionaldehyde

104

6.3.7

Temperature Programmed Reaction with H₂

106

6.3.8

CO Hydrogenation and Ethylene Hydroformylation on the Washed Ru/SiO₂

108

6.4

Conclusions

112

VII.

The Effect of Silver Promotion on CO Hydrogenation and Ethylene Hydroformylation Over Rh/SiO₂ Catalysts

114

7.1

Introduction

114

7.2

Experimental

115

7.2.1

Catalyst Preparation and Characterization

115

7.2.2

Experimental Procedure

116

7.3

Results

116

7.3.1

X-Ray Photoelectron Spectroscopy

116

7.3.2

CO Adsorption

118

7.3.3

No Adsorption

118

7.3.4

CO Hydrogenation

123

7.3.5

Ethylene Hydroformylation

126

7.4

Discussion

129

7.4.1

Catalyst Characterization

129

7.4.2

Ag Promotion of C₂₊ Oxygenate Formation

132

7.5

Conclusions

132

VIII.

The Effect of Chemical Additives on CO Hydrogenation and Ethylene Addition Over Rh/SiO₂ Catalyst

134

8.1

Introduction

134

8.2

Experimental

135

8.2.1

Catalyst Preparation

135

8.2.2

Experimental Procedure

135

8.3

Results and Discussion

136

IV. 

Summary

146

9.1

Overview

146

9.2

CO Adsorption

147

9.3

Nature of the Active Site for CO Insertion

149

9.4

Effect of Silver on C₂₊ Oxygenate Synthesis

150

9.5

Oxygenate Synthesis on Ni/SiO₂ and Ru/SiO₂

151

9.6

Effects of Additives

152

9.7

Concluding Remark

152

Bibliography

155

Appendices

164

A.

Infrared Spectra of Gaseous Hydrocarbons

165

B.

Infrared Spectra of Gaseous Alcohols and Aldehydes

166