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研究生: 顏宏宇
Yen, Hung-Yu
論文名稱: 以密度泛函理論計算改良鹼性析氫反應之描述符
Improvement of the Descriptor for Hydrogen Evolution Reaction in Alkaline Media by Computational Study
指導教授: 王禎翰
Wang, Jeng-Han
口試委員: 李積琛
Lee, Chi-Shen
羅夢凡
Luo, Meng-Fan
王禎翰
Wang, Jeng-Han
口試日期: 2022/06/10
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2022
畢業學年度: 110
語文別: 中文
論文頁數: 95
中文關鍵詞: 鹼性析氫反應密度泛函理論吉布斯自由能功函數雷達圖
英文關鍵詞: Alkaline hydrogen evolution reaction, density functional theory, Gibbs free energy, work function, radar chart
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202200650
論文種類: 學術論文
相關次數: 點閱:101下載:13
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  • 在過去的研究中,酸性的析氫反應只需計算氫的吸附自由能(∆GH*),即可決定催化劑的好壞。在本篇研究中,我們利用3個鹼性析氫反應中最重要的參數:氫的吸附自由能(∆GH*)、氫氧根的吸附自由能(∆GoH*)、水解離活化能(Ea(water)),繪製出雷達圖,建構出一個簡單、有用的方法,來判斷較為複雜的鹼性析氫反應活性。一開始,本篇研究先計算單金屬銀(Ag)、金(Au)、鈷(Co)、銅(Cu)、鎳(Ni)、鈀(Pd)、鉑(Pt) (皆為FCC (111)面),並數繪製成雷達圖,與文獻值的交換電流密度對數(log i0)繪製成散佈圖後,發現兩者呈現高度正相關,代表雷達圖面積可以很好的對應鹼性析氫反應的活性。接著,本篇研究測試了以鉑(Pt)和鈀(Pd)為基底的雙金屬催化劑:Pt3M、PtM、Pd3M、PdM (M = Ag、Au、Co、Ni、Pd、Pt、Rh、Ru),並且將雷達圖面積與功函數比較後,發現兩者呈線高度正相關,代表功函數也可以代表活性,並且以鉑(Pt)為基底的雙金屬催化劑的活性高於以鈀(Pd)為基底的雙金屬催化劑,其中又以Pt3Au為最高。最後,本篇研究也計算了非金屬催化劑Fe3O4(220)及FeP(111),繪製出雷達圖後,其活性趨勢為FeP(111) > Fe3O4(220),與實驗中磷化物的活性高於氧化物的趨勢相符。

    Catalytic activity of hydrogen evolution reaction (HER) in acidic media can be well predicted through hydrogen-adsorption free energy (∆GH*) previously. In the present study, we further develop a simple and useful method to diagnose the more complicated HER in alkaline media by utilizing three vital parameters of ∆GH*, hydroxide-adsorption free energy (∆GoH*), and activation energy of water dissociation (Ea(water)) in a radar chart. First, we examined single metals of Ag, Au, Co, Cu, Ni, Pd, Pt with the same crystal structure (FCC) and surface facet (111). The area of radar chart well correlated with the (logarithm of) exchange current density (log i0) from experiments, indicating the accuracy of our new method. Further, we examined Pt and Pd-based bimetallic catalysts of Pt3M, PtM, Pd3M and PdM (M = Ag, Au, Co, Ni, Pt, Pd, Rh, Ru). Excellent correlation is also found between the area and work function, representing as activity. Pt-based bimetals shows better activity than Pd-based one and Pt3Au shows the best HER activity. Finally, Fe3O4(220) and FeP(111) have been examined to extend our method in non-metallic catalysts. The predicted activity follow the trends of FeP(111) > Fe3O4(220), which consistent with the experiments that phosphides are more active than oxides.

    致謝 i 摘要 ii Abstract iii 目錄 iv 圖目錄 vi 表目錄 ix 第1章 緒論 1 1-1 前言 1 1-2 鹼性析氫反應的介紹 2 1-3 鹼性析氫反應計算值與實驗值的對應 7 1-4 研究方向 9 第2章 理論計算原理 11 2-1 密度泛函理論 (Density Functional Theory) 11 2-1-1 Thomas-Fermi模型 11 2-1-2 Thomas-Fermi-Dirac模型 12 2-1-3 Hohenberg-Kohn定理 12 2-1-4 Kohn-Sham方程式 13 2-1-5 交換關聯函數 15 2-2 固態材料之理論計算 16 2-2-1 基底函數組 (Basis set) 16 2-2-2 贋勢 (Pseudopotential) 17 2-2-3 布洛赫定理 (Bloch’s Theorem) 19 2-2-4 倒晶格 (Reciprocal Lattice) 19 2-2-5 自洽過程 (Self-consistent calculation) 21 2-3 計算系統與軟體參數設定 22 2-3-1 計算平台-國家高速網路與計算中心 (NCHC) 22 2-3-2 計算軟體-VASP 23 2-3-3 計算參數設定 23 第3章 單金屬鹼性析氫反應之計算方法 25 3-1 單金屬表面模型的建立 25 3-2 鹼性析氫反應在單金屬上之吸附模型建立 27 3-2-1 H吸附模型 28 3-2-2 OH吸附模型 29 3-2-3 H-OH共吸附模型 31 3-2-4 H2O吸附模型 33 3-2-5 水解反應模型 34 3-3 鹼性析氫反應在單金屬表面之定量方式 35 3-3-1 火山圖 (Volcano Plot) 35 3-3-2 雷達圖 36 3-3-3 雷達圖面積與交換電流密度關係圖 39 3-4 功函數與交換電流密度 40 3-4-1 功函數計算方法 40 3-4-2 功函數與交換電流關係圖 41 3-4-3 雷達圖面積與功函數關係圖 42 第4章 以鉑、鈀為基底之雙金屬鹼性析氫反應探討 44 4-1 雙金屬模型建立 44 4-1-1 Mb:M = 3:1 44 4-1-2 Mb:M = 1:1 47 4-2 鹼性析氫反應在以鉑、鈀為基底之雙金屬吸附點位 50 4-2-1 H吸附模型 50 4-2-2 OH吸附模型 52 4-2-3 H-OH共吸附模型 53 4-2-4 H2O吸附模型 55 4-2-5 水解反應模型 56 4-3 鹼性析氫反應在以鉑、鈀為基底之雙金屬表面定量方式 57 4-3-1 雷達圖 57 4-3-2 面積與功函數關係圖 59 第5章 非金屬催化劑於鹼性析氫反應之探討 61 5-1 非金屬催化劑模型 61 5-1-1 非金屬催化劑模型的建立 61 5-2 鹼性析氫反應在Fe3O4、FeP上之吸附模型建立 62 5-3 Fe3O4(220)、FeP(111)於雷達圖上的繪製與面積的比較 64 5-3-1 雷達圖 64 5-3-2 面積比較 65 第6章 結論 66 參考文獻 67 附錄 71

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