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研究生: 賴盈任
Ying-Ren Lai
論文名稱: 理論計算探討乙醇於Rh/γ-Al2O3(110)表面上之吸附結構與脫氫的反應機構
Computational Studies of the Adsorption Configurations and Dehydrogenation Mechanisms of Ethanol on the Rh/γ-Al2O3(110) Surface
指導教授: 何嘉仁
Ho, Jia-Jen
林倫年
Hayashi Michitoshi
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2007
畢業學年度: 95
語文別: 中文
論文頁數: 60
中文關鍵詞: 蒸氣重組氫氣氧化鋁乙醇吸附
英文關鍵詞: steam reforming, hydrogen, Al2O3, ethanol, adsorption
論文種類: 學術論文
相關次數: 點閱:192下載:23
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  • 利用periodic DFT的計算方法, 我們探討乙醇於Rh/γ-Al2O3(110)表面之吸附結構與分解路徑。相較於乙醇吸附於Rh上的結果,乙醇吸附於表面的鋁離子上具有較好的吸附能,然而此酸性性質的γ-Al2O3載體會幫助乙醇脫水形成乙烯,因此我們考慮了其他的吸附結構來探討乙醇的分解路徑。由乙醇以α碳端吸附於Rh原子上的結構作為起始架構,相繼的反應路徑為脫附兩個α氫原子;能障分別為2.59與7.35 kcal/mol。下一步驟的脫氫反應是脫附O-H之氫形成中間產物CH3C(a)O + 3H(a),所需克服的能障為10.13 kcal/mol,由此中間產物斷去C-C鍵,所需克服的能障為12.06 kcal/mol,形成C(a)H3 + C(a)O + 3H(a)等中間產物吸附於表面,於此所計算的乙醇分解路徑,在實驗上有類似的觀察結果。

    We applied periodic density-functional theory (DFT) to investigate the adsorption configurations and decomposition paths of ethanol on a Rh/γ-Al2O3(110) surface. Adsorption of ethanol onto a Al atom in the surface performs a larger adsorption energy than it adsorbed onto a Rh atom. But it is well known that the acidic support, γ-Al2O3 promotes dehydration of ethanol to ethylene. Therefore, we consider another ethanol adsorption configuration for the calculation of ethanol dehydrogenation pathways. In this configuration, ethanol adsorbed onto a Rh via α-cabon, two α-hydrogen atoms from ethanol are first eliminated; the barriers for abstraction of this two α-hydrogen atoms are calculate to be 2.59 and 7.35 kcal/mol, respectively. The dehydrogenation continues with the loss of one hydrogen from the O-H, forming an intermediate species CH3C(a)O + 3H(a), for which the successive barrier is 10.13 kcal/mol. Cleavage of the C-C bond occurs at this stage with a dissociation barrier Ea = 12.06 kcal/mol, to form C(a)H3 + C(a)O + 3H(a). The aforementioned reaction mechanism was also proposed and discussed by experiment.

    目 錄 中文摘要 iii 英文摘要 iv 第一章 緒論.....1 第二章 計算方法 2-1 Computational methods.....7 2-2 γ-Al2O3 bulk and γ-Al2O3(110) model.....8 2-3 Gas-phase geometries and comparison of energies and geometries of water adsorption on γ-Al2O3(110) with experiment and Digne’s results.....11 第三章 結果與討論 3-1 Adsorption of Rhodium on γ-Al2O3(110) surface.....16 3-2 Adsorption of ethanol on clear γ-Al2O3(110) surface and Rh/γ-Al2O3(110) surface.....21 3-3 Pathways for ethanol decomposition on Rh/γ-Al2O3(110).....35 第四章 結論.....51 參考文獻.....53 附錄.....56

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