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1.Carbide and Nitride Overlayers on Early Transition Metal Surfaces:
Preparation, Characterization, and Reactivities
Jingguang G. Chen
Corporate Research Laboratories, Exxon Research and Engineering Company, Annandale, New Jersey 08801
Contents
I. Introduction 1477
II. Bulk Properties of Carbides and Nitrides 1478
1. Structural Properties 1478
2. Electronic Properties 1479
3. Catalytic Properties 1480
III. Preparation of Carbide and Nitride Overlayers 1480
1. Carbide-Modified Surfaces 1480
2. Nitride-Modified Surfaces 1483
IV. Characterization of Carbide and Nitride
Overlayers
1485
1. Ionic and Covalent Nature of
Metal-Nonmetal Bonding
1485
2. Band Structures of Carbide/Nitride Overlayers 1485
3. Chemisorption of CO on Carbide Surfaces 1486
V. Surface Reactivities of Carbide and Nitride
Overlayers
1488
1. Reactions with Saturated and Unsaturated
Hydrocarbons
1488
2. Reactions with Oxygenate Molecules 1494
3. Reactions with Sulfur- and
Nitrogen-Containing Organic Molecules
1495
4. General Similarities and Differences 1496
VI. Future Research Opportunities 1496
VII. Acknowledgments 1497
VIII. References 1497

2.Surface Chemistry of Transition Metal Carbides
Henry H. Hwu and Jingguang G. Chen*,
Department of Materials Science and Engineering, Department of Chemical Engineering, Center for Catalytic Science and Technology (CCST),
University of Delaware, Newark, Delaware 19716
Contents
1. Introduction 185
2. Characterization of Carbide Surfaces 186
2. 1. Common Carbide Surface Structures 186
2. 2. Preparation of Carbide Surfaces 186
2. 3. Common Characterization Techniques for
Carbide Surfaces
188
2. 3.1. Groups 4 and 5 Carbides 188
2. 3.2. Group 6 Carbides 189
3. Reactions with Diatomic Molecules 191
3. 1. Hydrogen 191
3. 2. Oxygen 191
3. 3. Carbon Monoxide 192
3. 4. Nitric Oxide 194
4. Reactions with Hydrocarbon Molecules 194
4. 1. Linear Hydrocarbons 195
4. 1.1. C1 and C2 Molecules 195
4. 1.2. C3 and C4 Molecules 196
4. 2. Cyclic Hydrocarbons 197
4. 3. Aromatics 199
5. Reactions with Oxygen-Containing Molecules 200
5. 1. Water 200
5. 2. Alcohols 201
5. 3. Carbon Dioxide 204
6. Reactions with Sulfur-Containing Molecules 204
6. 1. Thiophene 204
6. 2. Alkanethiol 205
6. 3. SO2 205
7. Reactions with Nitrogen-Containing Molecules 206
7. 1. Ammonia 206
7. 2. Nitrile 206
8. Correlating Surface Reactivity with Electronic
Properties
206
8. 1. Similarities and Differences between TMC
and Pt-Group Metal Surfaces
206
8. 2. Theoretical Modeling of Surface Properties 207
9. Future Research Opportunities 208
10. Acknowledgment 209
11. Appendix: List of Abbreviations of
Characterization Techniques
209
12. References 209

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