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Author: 林于媫
Thesis Title: 以理論計算的方式研究(1)NO在NixPt(4-x), xNi@Pt, (4-x)Pt@Ni (x = 0~4)的吸附與分解反應 (2)CH3CO、CH3CN與CH3CH2在M(111)、core/shell Cu/M(111)與Pt/M(111) (M = Ni or Rh)表面之吸附與C-C斷鍵反應
Advisor: 何嘉仁
Degree: 碩士
Master
Department: 化學系
Department of Chemistry
Thesis Publication Year: 2011
Academic Year: 99
Language: 中文
Number of pages: 122
Keywords (in Chinese): 理論計算NO雙金屬core/shellNi-PtC-C斷鍵
Thesis Type: Academic thesis/ dissertation
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  • 第一部分:NO在NixPt(4-x), xNi@Pt, (4-x)Pt@Ni (x = 0~4 )的吸附與分解反應

    我們使用密度泛函理論來研究NO在三個雙金屬系統(1) NixPt(4-x)、(2) xNi@Pt、(3) (4-x)Pt@Ni (x = 0~4 )的吸附與分解反應,計算結果顯示,NO的吸附能大小在表層金屬原子組成相同時,都會依照xNi@Pt > NixPt(4-x) > (4-x)Pt@Ni的順序;而LDOS的分析結果顯示這也是d band center靠近Fermi level程度的大小順序,以及NO斷鍵的活化能大小順序則是跟吸附能呈相反順序,吸附能越大則活化能會越小,NO在4Ni@Pt這個表面可以得到最大的吸附能-2.97 eV,和最小的斷鍵能障1.20 eV;比起純Ni表面的吸附能-2.48 eV及活化能1.49 eV, 4Ni@Pt催化效果明顯增加;相反地,NO在4Pt@Ni這個表面有最小的吸附能-0.92 eV及最大的斷鍵能障3.34 eV,比起純Pt的吸附能-1.88 eV及斷鍵能障2.50 eV,催化NO斷鍵的效果下降;這些現象我們從LDOS的分析都得到合理的解釋。

    第二部分:CH3CO、CH3CN與CH3CH2在M(111)、core/shell Cu/M(111)與Pt/M(111) (M = Ni or Rh)表面之吸附與C-C斷鍵反應研究
    我們使用密度泛函理論來探討CH3CO、CH3CN與CH3CH2在M(111)、core/shell Cu/M(111)與Pt/M(111) (M = Ni or Rh)表面之C-C斷鍵反應,分成Ni-shell或Rh-shell兩個系統來討論,除了探討C-C斷鍵反應之外,對於三個分子的吸附能及吸附結構也有詳細的描述,結果顯示在兩個系統中三個分子的吸附能都是Pt/M > Cu/M > M (M = Ni or Rh ),此現象跟內層core金屬影響表層shell金屬的電子結構有很大關係;而CH3CO、CH3CN、CH3CH2在這三個分子本身的吸附能大小則是CH3CO > CH3CH2 > CH3CN,除了在Pt/Ni上CH3CN比CH3CH2還要穩定一些;三個分子比較之下,CH3CO是最容易斷鍵的分子,而CH3CH2是最困難的,我們發現這跟他們吸附到表面後C-C鍵的拉長多寡很有關係;而CH3CO的斷鍵活化能在兩個系統的順序都是Pt/M > M > Cu/M (M = Ni or Rh);CH3CN則是Ni > Cu/Ni > Pt/Ni 及 Rh > Pt/Rh > Cu/Rh;而CH3CH2是Ni > Cu/Ni > Pt/Ni 及 Pt/Rh > Cu/Rh > Rh;這些結果我們都提出了LDOS的分析來佐證,得到了合理的解釋。

    總目錄 總目錄 i 中文摘要 iii 英文摘要 v 第一章 緒論 1 第二章 理論與計算方法 3 §2-1 固態材料的電子結構理論 3 §2-1-1 密度泛函理論 3 § 2-1-2局部密度近似法 (Local Density Approximation, LDA) 6 § 2-1-3 廣義梯度近似法 (Generalized Gradient Approximation, GGA) 7 § 2-1-4空間週期性 (periodic boundary condition) 8 § 2-1-5布洛赫定理(Bloch Theorem) 9 § 2-1-6虛位勢 (pseudopotential) 11 § 2-1-7 VASP計算軟體 15 §2-2 擾動彈簧模型(Nudged Elastic Band; NEB) 16 §2-3 態密度(Density of state, DOS) 18 第三章 NO在NixPt(4-x), xNi@Pt, (4-x)Pt@Ni (x = 0~4 )的吸附與分解反應 19 §3-1 前言 19 §3-2 計算方法與模型建立 22 §3-3 結果與討論 34 §3-3-1 NO在表面的吸附結構及吸附能研究 34 §3-3-2 xNi@Pt,NixPt(4-x),(4-x)Pt@Ni (x=0~4)雙金屬表面的電子結構研究 38 §3-3-3 NO在xNi@Pt,NixPt(4-x),(4-x)Pt@Ni (x=0~4)雙金屬表面的斷鍵反應能障研究 42 §3-4 本章結論 48 第四章 CH3CO、CH3CN與CH3CH2在M(111)、core/shell Cu/M(111)與Pt/M(111) (M = Ni or Rh)表面之C-C斷鍵反應研究 51 §4-1 前言 51 §4-2 計算方法與模型 53 §4-3 CH3CO、CH3CN與CH3CH2在純Ni、core/shell Cu/Ni與Pt/Ni表面的吸附與C-C斷鍵反應的活化能分析 58 §4-3-1 CH3CO、CH3CN與CH3CH2在Ni、Cu/Ni與Pt/Ni表面的吸附能與吸附結構分析 58 §4-3-2 CH3CO、CH3CN與CH3CH2在Ni、Cu/Ni與Pt/Ni金屬表面上的C-C斷鍵反應研究 68 §4-3-3綜合比較及表面電子結構研究 77 §4-4 CH3CO、CH3CN與CH3CH2在Rh、Cu/Rh、Pt/Rh的吸附與C-C斷鍵的活化能分析 86 §4-4-1 CH3CO、CH3CN與CH3CH2在Rh、Cu/Rh、Pt/Rh的吸附能與吸附結構分析 86 §4-4-2 Ni與Rh系統表面電子結構研究與吸附能比較 96 §4-4-3 CH3CO、CH3CN與CH3CH2在Rh、Cu/Rh、Pt/Rh的C-C斷鍵反應活化能分析 101 §4-5本章結論 110 第五章 總結 113 參考文獻 115

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