近年來為了減少石油資源的使用，替代能源的開發成為很重要的目標。而有些替代能源正在發展及被使用中，如太陽能、風力發電、氫能、地熱、與生質能等。由於氫能沒有汙染，可再生利用，並可由廣泛的來源取得，故燃料電池則成為一個重要且具有高效率低污染等特性的替代能源。除了水的電解,氫氣也可從生質能源與石油化學材料中取得。一般來說，氫產物可基於酒精分解、蒸氣重組、部分氧化、以及氧化蒸氣重組等反應中取得。然而，在產氫的實驗過程中容易因為氧化不完全而有毒化反應產生。因此，以微觀模擬分析及研究氧化蒸氣重組反應的機制改善製氫過程為本研究的重點。
在本研究中，我們利用密度泛函理論與動態蒙地卡羅去模擬蒸氣氧化重組反應實驗中以銠金屬作為催化劑的化學機制。首先，利用密度泛函理論去建立與最佳化計算各個在氧化蒸氣重組反應中的反應物結構與最佳吸附位置，並利用微動彈性帶方法找出各反應的過度態。再者，我們利用動態蒙地卡羅方法去模擬各反應物在平衡狀態下的吸附、脫附和擴散等化學行為。根據實驗的結果，我們調整系統中氧與酒精 (氧氣/酒精=0.687/1, 0.802/1, 0.916/1, 1.030/1, 1.145/1, 1.260/1, 1.374/1, 1.489/1, 1.603/1)，以及水與酒精(水/酒精＝1/1, 3/1, 5/1, 10/1) 的比例來探討以氧化乙醇來提供重組反應之能量的乙醇氧化蒸氣重組反應對氧氣的靈敏度與系統的影響。藉由動態蒙地卡羅法模擬結果可知氧氣以及水含量增加會改變蒸氣氧化重組反應的反應路徑，並可降低一氧化碳的生成以及提高二氧化碳的產量，這研究可進一步幫助我們去預測實驗上最佳的控制條件，提高乙醇氧化蒸氣重組的轉換效率。

In recent years, in order to reduce the use of petroleum resources, the development of alternative energy sources has become an important goal. Alternative energy sources such as solar energy, wind power, hydrogen energy, geothermal, and biomass energy have been developed. Fuel cells are an important element of alternative energy due to their high efficiency and low pollution, with hydrogen the best material due to the convenience in obtaining it from biomass energy and petrochemical materials. In general, hydrogen is produced from ethanol decomposition, steam reforming, and partial oxidation, as well as oxidative steam reforming (OSR) and other reactions. The most important issues for production are how to prevent poisoning from these reactions. Due to its specific advantages, the OSR reaction is studied here to improve efficiency by investigating its mechanism at the nanometer scale.
In this work, the reaction mechanism of the OSR of ethanol on the Rh(111) surface was systematically examined by density functional theory (DFT) and the kinetic Monte Carlo (kMC) method calculation was carried out to simulate the experimental condition on an Rh-based catalyst. First, DFT was employed to optimize the local minimums and transition states for a series of elementary steps. Next, the statistical mechanics of OSR were simulated by kMC, and adsorption, desorption, and combination of the chemical reactions were illustrated under steady state conditions. According to the experimental results, various fractions of oxygen/ethanol (0.687/1, 0.802/1, 0.916/1, 1.030/1, 1.145/1, 1.260/1, 1.374/1, 1.489/1, and 1.603/1) and water/ethanol (1/1, 3/1, 5/1, 10/1,) were adjusted to investigate the effects of oxygen and water in the OSR of ethanol reaction. The computed kMC results show that the pathways will be affected by increasing oxygen and water content and adjustments can decrease CO and enhance CO2 production. This computational study can further help to predict the optimal operational conditions of OSR in order to produce the best performance.

Contents
摘要 iii
Abstract iv
Contents vi
List of Figures viii
List of Symbols xi
Chapter 1 Introduction 1
1-1 Introduction of hydrogen production from ethanol 4
1-2 Review of oxidation steam reaction of ethanol on various catalysts 7
1-3 Review of kMC simulation studies of various reactions 11
1-4 Motivation 16
1-5 Outline of this dissertation 17
Chapter 2 Density Functional Theory (DFT) 18
2-1 DFT introduction 18
2-1-1 Schrödinger equation in a multi-electron system 19
2-1-2 Born-Oppenheimer approximation 20
2-2 Hohenberg and Kohn theorems 21
2-2-1 Introduction 21
2-2-2 Kohn and Sham theory 23
2-3 Nudged elastic band (NEB) method 26
2-4 VASP introduction 27
Chapter 3 The kinetic Monte Carlo (kMC) Method 28
3-1 Introduction 28
3-2 The kMC program 30
3-3 The adsorption sites arrangement 31
3-3-1 Adsorption 32
3-3-2 Desorption 33
3-3-3 Combination 33
3-3-4 Dissociative adsorption 34
3-3-5 Desorption from the dissociative adsorption/combination 35
3-3-6 Diffusion 37
3-4 Designing the pathway channel of the chosen reaction. 38
3-5 The pathway barriers from DFT calculations 39
3-6 The rate constant calculations 40
3-6-1 The simple rate constant 40
3-6-2 The Arrhenius equation 43
3-7 Lateral interaction 47
3-7-1 Periodic boundary condition (PBC) 47
3-7-2 Neighbor list for non-bonded interaction 49
3-8 Flow chart of kinetic Monte Carlo simulation 51
Chapter 4 Results and Discussion 53
4-1 Theoretical methods and simulation models 53
4-2 The species of OSR reaction in every pathway 55
4-3 The stable configurations of relative adsorbates 57
4-4 The reaction channel of OSR (The prediction path of oxide steam reaction) 71
4-5 The effects of catalyst and condition in the OSR reaction 72
4-6 The effect of oxygen in the OSR reaction 75
4-7 The effect of water in the OSR reaction 84
Chapter 5 Conclusions and Future Works 95
5-1 Conclusions 95
5-1-1 The DFT calculations of OSR reaction 95
5-1-2 KMC simulation of effects of oxygen in the OSR reaction 96
5-1-3 KMC simulation of effects of water in the OSR reaction 98
5-2 Future Works 100
References 102

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