臺灣博碩士論文加值系統

本篇論文利用密度泛函理論(DFT)的計算來探討在鎳(111)表面上的水氣轉移反應和乙醇的裂解。水氣轉移反應在鎳(111)表面上有兩種機制，一種是redox mechanism，另一種是carboxyl mechanism。此兩種反應路徑的速率決定步驟皆為水分解這個步驟，其反應能障為0.94 eV。由計算結果可知乙醇有兩種穩定的吸附結構。結構A是以乙醇的氧端和亞甲基端吸附於表面上，此乙醇裂解主要路徑是CH3CH2OH → CH3CHOH → CH3CHO → CH3CO → CH3+CO，其速率決定步驟為乙醇中Cα–H鍵裂解，反應能障為1.13 eV。結構B則是以乙醇的氧端和甲基端吸附於表面上，其乙醇裂解主要路徑是CH3CH2OH → CH2CH2OH → CH2CH2O → CHCH2O → CCH2O → CCH2+O，速率決定步驟為2–羥乙基 (CH2CH2OH)中O–H鍵裂解，反應能障為1.49 eV。

Water-gas shift (WGS) reaction and ethanol decomposition on Ni (111) surface were studied using periodic DFT calculations. Two mechanisms of WGS reaction on Ni (111) surface, redox and carboxyl mechanisms, were considered in this study. The rate-determining step for both two mechanisms of WGS reaction is water activation which reaction barrier of this step is 0.94 eV. The calculations indicate that there are two favorable adsorption sites for ethanol on the Ni (111) surface. Both structures feature EtOH adsorbed on top of a Ni atom through its O atom, with the CH2 and CH3 groups sitting above the neighboring Ni atom for model A and model B, respectively. The most favorable pathway of ethanol decomposition in model A is CH3CH2OH → CH3CHOH → CH3CHO → CH3CO → CH3+CO and the rate-determining step of this pathway is the cleavage of Cα–H bond in ethanol with barrier of 1.18 eV. For ethanol decomposition in model B, the most favorable pathway is CH3CH2OH → CH2CH2OH → CH2CH2O → CHCH2O → CCH2O → CCH2+O and the rate-determining step of this pathway is the cleavage of O–H bond in 2–hydroxyethyl with barrier of 1.49 eV.

Abstract I
摘要 II
Contents III
Index of Figure V
Index of Table VIII
Chapter 1. Introduction 1
1.1 Fuel Cells 1
1.2 Water-Gas Shift Reaction 4
1.3 Hydrogen Production via Ethanol 7
1.4 Catalytic Performances 9
1.5 This Research 11
Chapter 2 Theoretical Background 12
2.1 Hartree Approximation 12
2.2 DFT Method 13
2.2.1 Description of Theory 13
2.2.2 Derivation and Formalism 16
2.3 Basis Set 20
2.4 Bloch’s Theorem and Plane Wave Basis Set 21
2.4.1 Bloch’s Theorem 21
2.4.2 Plane Wave Basis Set 24
2.4.3 K-Point Sampling 27
2.5 PAW Pseudopotential 28
2.5.1 Pseudopotential 28
2.5.2 Projected Augmented Wave (PAW) 34
2.6 GGA Approximation 36
2.7 NEB method 37
Chapter 3: Computational Details 40
3.1 Method 40
3.2 Surface Model 42
3.2.1 Bulk 42
3.2.2 Ni (111) surface 43
Chapter 4. Results and Discussion 45
4.1 Water-Gas Shift Reaction 45
4.1.1 Structure and Energetics of Absorbed Intermediates 45
4.1.2 Reaction Mechanisms 50
4.2 Ethanol Decomposition on Ni(111) Surface 62
4.2.1 Adsorption Properties of Reaction Intermediates 62
4.2.2 Reaction Mechanisms of Ethanol Decomposition on Ni(111) Surface 70
Chapter 5. Conclusion 95
Reference 96

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