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研究生：	王雅甄 Wang, Ya-Chen
論文名稱：	利用密度泛函理論計算機理性探討二氧化碳還原反應在金銅合金與金銀合金之催化效果 Mechanism Study of CO2 Reduction Reaction on CuAu and CuAg Alloys by Density Functional Theory Calculation
指導教授：	王禎翰 Wang, Jeng-Han
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2020
畢業學年度：	108
語文別：	英文
論文頁數：	58
中文關鍵詞：	二氧化碳還原反應、反應機理、密度泛涵理論計算、銅金合金、銅銀合金
英文關鍵詞：	Carbon dioxide reduction reaction, Reaction mechanism, Density functional theory (DFT) calculation, CuAu alloy, CuAg alloy
DOI URL：	http://doi.org/10.6345/NTNU202001075
論文種類：	學術論文
相關次數：	點閱：160 下載：3
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隨著人類文明快速發展，溫室問題已成為全球關注的重要問題。將二氧化碳轉化為可再生能源，可以緩和溫室效應加劇的速度。在本研究中，我們通過密度泛函理論（DFT）的計算，機理性探討轉化過程的基本反應：二氧化碳還原為一氧化碳。分析機制後發現，中間體COOH*和CO*的吸附以及其對應的吉布斯自由能是控制還原反應的關鍵：COOH*的吸附力更高，吉布斯自由能越低，有利於啟動CO2還原反應； CO*的吸附力越弱，吉布斯自由能越高，代表CO越容易被脫除，以完成整體的還原反應。銅具有前者的優勢，而金和銀具有後者的優勢。因此，期望金銅和金銀合金可以結合兩種金屬的特性，形成有利於COOH *吸附且擁有最佳還原活性的催化劑。合金上的吸附受電子結構和整體效應的影響，我們找出在銅核金殼/金核銅殼/銅核銀殼中的最佳合金比例為：CuAu6，AuCu16和CuAg7其中又以AuCu16最好。

With the rapid development of human civilization, greenhouse problem become an important issue of global concern. Converting carbon dioxide into renewable energy resources is an effective way to resolve the detrimental problem. In the present study, we mechanistically examine the reduction reaction of carbon dioxide to carbon monoxide, the fundamental reaction for the converting process, by density functional theory (DFT) calculation. The resolved mechanism indicates that adsorption and the related Gibbs free energy of the two key intermediates COOH* and CO* control the reduction reaction: stronger adsorption of COOH* with lower Gibbs free energy to initiate the CO2 reduction and weaker adsorption of CO* with higher Gibbs free energy to remove the product of CO can essentially promote the reduction reaction. Copper has the advantage for the former adsorption, while gold and silver have those for the later one. Thus, the alloys of CuAu and CuAg are expected to benefit both adsorptions and achieve the best activity for the reduction reaction. The adsorptions on the alloys are affected by the electronic structural and ensemble effects. Accordingly, the best alloy ratios have been rationally determined: CuAu6, AuCu16 and CuAg7 are the optimal Cu-core/Au-shell, Au-core/Cu-shell and Cu-core/Ag-shell catalysts, respectively; among them AuCu16 is the best one.

謝誌  i

摘要  ii
Abstract  iii

Table of Contents  iv
List of Figures  vi
List of Tables  ix

Chapter 1 Introduction  1
1-1 Background  1
1-2 CO2 Reduction Reaction  2
1-3 Motivation  5

Chapter 2 Principle of Theoretical Calculation  6
2-1 Density Functional Theory  6
2-1-1 Hohenberg-Kohn theorem  6
2-1-2 Kohn-Sham equations  7
2-1-3 Exchange-correlation functional  8
2-2 Foundation Theory of Solid State Materials  9
2-2-1 Basis set  9
2-2-2 Pseudopotential  9
2-2-3 Bloch’s theorem  10
2-2-4 Self-consistent calculation  10
2-3 System Setting  11
2-3-1 VASP calculation setting  11
2-3-2 Computing system  13
2-4 Surface Structure  13
2-4-1 Pure Metal  13
2-4-2 CuAu  14
2-4-3 AuCu  16
2-4-4 CuAg  16

Chapter 3 Result and Discussion  17
3-1 Pure Metal  17
3-1-1 Adsorption  17
3-1-2 Charge density  19
3-1-3 Density of State state(DOS)  21
3-1-4 Free energy diagram  23
3-2 CuAu Alloy  24
3-2-1 Adsorption  24
3-2-2 Density of state(DOS)  30
3-2-3 Free energy diagram  35
3-3 AuCu Alloy  36
3-3-1 Adsorption  36
3-3-2 Density of state(DOS)  39
3-3-3 Free energy diagram  41
3-4 CuAg Alloy  43
3-4-1 Adsorption  43
3-4-2 Density of state(DOS)  45
3-4-3 Free energy diagram  47
3-5 Electron Localization Function(ELF)  48
3-5-1 Pure metal  48
3-5-2 Alloy  50
3-6 Bader Charge  51
3-6-1 Pure metal  51
3-6-2 Alloy  52

Chapert 4 Conclusions  53

References  55
                                

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