以密度泛函理論研究甲醇及水在鈀/氧化鋅(100)表面上的裂解反應

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研究生：	洪育倫 Yu-Lun Hung
論文名稱：	以密度泛函理論研究甲醇及水在鈀/氧化鋅(100)表面上的裂解反應 DFT Study of Methanol Decomposition and Water Dissociation on Pd/ZnO(100) Surface
指導教授：	江志強 Jyh-Chiang Jiang
口試委員:	黃炳照 Bing-Joe Hwang 趙聖德 Sheng-Der Chao
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	英文
論文頁數：	108
中文關鍵詞：	密度泛函理論、氧化鋅(100) 、鈀金屬、甲醇裂解反應、水分解反應
外文關鍵詞：	DFT; ZnO(10 0)
相關次數：	點閱：187 下載：4
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本文利用密度泛函理論(DFT)方法研究在鈀/氧化鋅(100)表面上的甲醇裂解及水分解反應。我們探討鈀金屬散佈於氧化鋅表面的兩種模式，2Pd/ZnO、6Pd/ZnO。前者用來研究鈀-鋅介面的反應性，後者則描述鈀金屬表面上的反應情形。此外，最佳化的吸附結構、能量、以及振動頻率皆計算於文章中。甲醇裂解反應的最初路徑包含了O-H鍵裂解產生CH3O，或是經由C-H鍵裂解生成CH2OH中間產物，接著生成CH2O、CHO、CO。相對的，經由C-O鍵裂解是較不可行的路徑。另外，我們也研究在鈀/氧化鋅上的水分解反應生成OH 和H。綜合以上兩種反應，其結果指出在鈀-鋅介面的反應性較在鈀金屬表面上佳。也就是說，當鈀原子散佈於氧化鋅表面時，低覆蓋率者有較好的反應活性。

First-principles density-functional theory (DFT) calculations have been performed to investigate sequential methanol decomposition, and water dissociation on the Pd/ZnO(100) surfaces. To explore the catalytic sites of the zinc oxide supported palladium surface, two surface models, 2Pd/ZnO and 6Pd/ZnO, were considered. The former was used to investigate the activity at the Pd-ZnO interface, and the latter for the reaction on the supported-Pd surface. The optimized structures, energetics and vibrational frequencies of the intial adsorbed states, intermediates and transition states were determined on these two surface models. In this work, we have investigated three possible methanol decomposition pathways including dehydrogenation via the O-H bond breaking to form methoxide (CH3O) fragment or C-H bond scission to generate hydroxymethyl (CH2OH) fragment at the beginning step, followed by steps involving formation of CH2O, CHO, CO, are found to be the most favorable reaction pathways. In contrast, pathways involving C-O bond cleavage are much less energetically favorable. In addition, the H2O dissociation on Pd/ZnO(10 0) surfaces was also investigated, and the results indicate that the activity for above reactions at the Pd-ZnO interface is higher than on the supported-Pd surface. From our calculations, we suggest that the low coverage of Pd atoms on ZnO surface should have better catalytic activity.

ABSTRACT .................................................................................................................. I
CONTENTS............................................................................................................... III
INDEX OF FIGURE ................................................................................................... V
INDEX OF TABLE ................................................................................................ VIII
Chapter 1: Introduction .............................................................................................. 1
1.1 Fuel cell ........................................................................................................... 1
1.1.1 Background ........................................................................................... 1
1.1.2 Fuel Cell Principle and Fuel Cell Types ............................................... 2
1.1.3 The Hydrogen Generation via Methanol .............................................. 3
1.1.4 CO Oxidation ........................................................................................ 7
1.1.5 Water Dissociation ................................................................................ 7
1.2 Catalytic Performances ................................................................................. 9
1.2.1 Catalyst Development ........................................................................... 9
1.2.2 Bravais-Miller index - Case of Hexagonal Structures ........................ 11
1.2.3 Palladium–Based Catalysts ................................................................. 12
1.3 This Research ............................................................................................... 16
Chapter 2: Methodology ............................................................................................ 17
2.1 Theoretical background............................................................................... 17
2.1.1 Quantum Chemistry ............................................................................ 17
2.1.2 Density Functional Theory ................................................................. 17
2.1.3 Periodic Systems ................................................................................. 20
2.1.4 Brillouin Zone Sampling..................................................................... 23
2.1.5 Plane Wave Basis Set .......................................................................... 27
2.1.6 Pseudopotential ................................................................................... 30
2.1.7 Ultrasoft-pseudopotential .................................................................... 34
2.1.8 Projected Augmented Wave (PAW) .................................................... 35
2.1.9 Generalized Gradient Approximation (GGA) ..................................... 38
2.1.10 Nudged Elastic Band Method (NEB) ............................................... 39
2.1.11 Linear Synchronous Transit (LST) ................................................... 41
2.2 Computational details .................................................................................. 43
2.2.1 Computational Methods ...................................................................... 43
2.2.2 Surface Model ..................................................................................... 45
a. Bulk .................................................................................................. 45
b. The Clean ZnO Surfaces .................................................................. 46
c. The Pd/ZnO(10 0) Surface .............................................................. 47
Ι. 2Pd/ZnO(10 0) Surface ........................................................... 47
ΙΙ. 6Pd/ZnO(10 0) surface ........................................................... 49
Chapter 3: Results and discussion ............................................................................ 50
3.1 Adsorbed Intermediates of Methanol Decomposition. ............................. 50
3.1.1 2Pd/ZnO(10 0) Surface ...................................................................... 50
3.1.2 6Pd/ZnO(10 0) Surface ...................................................................... 58
3.2 Reaction Pathways for Methanol Decomposition ..................................... 63
3.2.1 Hydrogen Atom Diffusion on Pd/ZnO Surface .................................. 63
3.2.2 Methanol Decomposition on 2Pd/ZnO(10 0) Surface ....................... 64
a. IS-A .................................................................................................. 64
b. IS-B .................................................................................................. 76
c. IS-B with Low H Coverage on Pd ................................................... 83
3.2.3 Methanol Decomposition on 6Pd/ZnO(10 0) Surface ....................... 88
3.2.4 CO Oxidation ...................................................................................... 93
3.3 Adsorption Configurations of Water .......................................................... 95
3.3.1 Water Monomer .................................................................................. 95
a. 2Pd/ZnO(10 0) Surface ................................................................... 95
b. 6Pd/ZnO(10 0) Surface ................................................................... 96
3.3.2 Water Dmer ......................................................................................... 97
3.4 Water Dissociation ....................................................................................... 99
3.4.1 Water Monomer .................................................................................. 99
a. 2Pd/ZnO(10 0) Surface ................................................................. 100
b. 6Pd/ZnO(10 0) Surface ................................................................. 101
3.4.2 Water dimer ....................................................................................... 103
Chapter 4: Conclsuion ............................................................................................. 107
References ................................................................................................................. 109

                                

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