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研究生: 陳憲璁
Chen, Sian-Cong
論文名稱: 3-氯丙醇在銅(100)和氧/銅(100)表面上的熱化學研究
Thermal Chemistry of 3-Chloro-1-propanol on Cu(100) and O/Cu(100) Surfaces
指導教授: 林榮良
Lin, Jong-Liang
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 65
中文關鍵詞: 超高真空系統3-氯丙醇銅(100)氧/銅(100)程序控溫反應/脫附
外文關鍵詞: ultra-high vacuum system, 3-chloro-1-propanol, Cu(100), O/Cu(100), temperature-programmed reaction/desorption
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  • 本論文是以程溫反應/脫附(TPR/D)探討超高真空系統中3-氯丙醇在Cu(100)和O/Cu(100)的反應。3-氯丙醇在Cu(100)表面上會分解形成丙烷、丙烯、乙烷、一氧化碳、水和氫脫附,其中丙烷、丙烯、乙烯在120 K就已經形成。我們推測3-氯丙醇在120 K就部份斷C-Cl、C-OH、O-H鍵形成-CH2CH2CH2-、-OCH2CH2CH2-中間物。-CH2CH2CH2- 獲得表面上的H(a)形成丙烷或脫去β-H形成-CH2CH=CH2後再獲得表面上的H(a)形成丙烯。-OCH2CH2CH2-在表面形成η3(C,C,O)中間物,經由電子轉移造成C-C斷裂,產生乙烯及一氧化碳。
    3-氯丙醇在O/Cu(100)表面上會分解形成丙醛、水、氫、二氧化碳,由於氧未覆蓋整個表面,故也會產生無氧表面時的產物,如丙烷、丙烯、乙烯、一氧化碳。我們推測3-氯丙醇在低溫可形成-OCH2CH2CH2-和-OCH2CH2CH2Cl中間物,以致在~400 K產生丙醛脫附。

    In this research, temperature-programmed reaction/desorption (TPR/D) has been employed to investigate the thermal reactions of ClCH2CH2CH2OH on Cu(100) and on O/Cu(100) in an ultra-high vacuum chamber. Propane, propene, ethene, CO, H2O and H2 are the reaction products found from ClCH2CH2CH2OH decomposition on Cu(100). At 120 K, propane, propene and ethene have already been formed. We suggest that ClCH2CH2CH2OH is dissociatively adsorbed in the forms of -CH2CH2CH2- and -OCH2CH2CH2- due to C-Cl, C-OH and O-H bond scission. -CH2CH2CH2- recombines with surface H (H(a)) to form propane or undergoes β-H elimination to form -CH2CH=CH2, which reacts with H(a) to form propene. -OCH2CH2CH2-, in η3(C,C,O) bonding structure, produces ethene and CO(a) via C-C breakage.
    Propionaldehyde, H2O, H2 and CO2 are the reaction products from ClCH2CH2CH2OH decomposition on the oxygen-precovered surface. Since the Cu(100) surface is not fully covered with oxygen atoms in our case, propane, propene, ethene and CO are still produced. We suggest that on O/Cu(100) ClCH2CH2CH2OH is adsorbed in the forms of -OCH2CH2CH2- and -OCH2CH2CH2Cl at low temperatures. These intermediates are responsible for the product of propionaldehyde at ~400 K.

    摘要 I Abstract II 第一章 緒論 1.1 表面化學簡介 1 1.2 表面定義與Cu(100)表面 2 1.3 真空的定義與應用 3 1.4 表面吸附 4 1.5 研究動機 5 第二章 表面研究分析技術 2.1 歐傑電子能譜 9 2.2 程式控溫反應/脫附 11 第三章 實驗系統與方法 3.1 超高真空系統 13 3.2 單晶表面清潔 15 3.3 含氧表面製備 16 3.4 藥品與前處理 17 第四章 結果與討論 4.1 ClCH2CH2CH2OH在Cu(100)表面上的熱反應研究 4.1 程溫反應/脫附 18 4.2 ClCH2CH2CH2OH在O/Cu(100)表面上的熱反應研究 4.2 程溫反應/脫附 41 第五章 結論 60 參考文獻 61

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