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研究生： 楊子賢
Yang, Zi-Xian
論文名稱： 2-氯丙酸在銅(100)和氧/銅(100)表面上的熱反應研究
Thermal Chemistry of 2-Chloropropanoic Acid 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： 2015
畢業學年度： 103
語文別： 中文
論文頁數： 98
中文關鍵詞： 超高真空系統 、程式控溫反應/脫附(TPR/D) 、X光光電子能譜 、Cu(100) 、2-氯丙酸
外文關鍵詞： 2-chloropropionic acid, temperature-programmed reaction/desorption (TPR/D), X-ray photoelectron spectroscopy (XPS), Cu(100)
相關次數： 點閱：144  下載：1 
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    • 本篇論文是研究在超高真空系統中，2-氯丙酸(CH3CHClCOOH)於Cu(100)單晶表面的熱分解反應，探討中間態及反應氣相產物。而利用的表面分析技術包括：程序控溫反應/脫附(temperature- programmed reaction/desorption)、反射式紅外光吸收光譜分析(reflection-absorption infrared spectroscopy)、歐傑電子能譜分析(Auger electron spectroscopy)和X-光光電子能譜(X-ray photoelectron spectroscopy, XPS)。
    CH3CHClCOOH/Cu(100)其熱反應的主要脫附產物有H2、H2O、H2C=CH2、CO、CO2、HCl、CH3CH=C=O。由RAIRS與XPS實驗，發現在無氧面120 K時僅有小部分的CH3CHClCOOH斷O-H和C-Cl鍵。到250 K時O-H鍵已完全斷裂，此時表面中間物為CH3CHClCOO(a)與CH3CH2COO(a)。持續升溫到400 K時表面只留下CH3CH2COO(a)，接著400 K後CH3CH2COO(a)開始分解形成H2、H2C=CH2、CO、CO2脫附，而710 K後有高溫產物HCl、CH3CH=C=O的產生。
    CH3CHClCOOH在O/Cu(100)其熱反應的主要脫附產物與無氧時相同。根據RAIRS與XPS實驗發現在有氧表面會幫助斷O-H鍵，且抑制C-Cl鍵的斷裂。在120 K時大約一半的CH3CHClCOOH斷O-H鍵形成CH3CHClCOO(a)羧酸根結構。隨著溫度上升到250 K時，O-H鍵已完全斷裂而C-Cl鍵幾乎保持完整。到了380 K時C-Cl鍵才完全斷裂並形成CH3CH2COO(a)與新吸附結構η2-CH3CHCOO(a)，接著400 K後開始有產物H2、H2C=CH2、CO、CO2脫附，而720 K後有高溫產物HCl、CH3CH=C=O的產生。

    Thermal decomposition of CH3CHClCOOH on Cu(100) causes the desorption of H2, H2O, H2C=CH2, CO, CO2, HCl and CH3CH=C=O. At 120 K, RAIRS and XPS show that a small portion of adsorbed CH3CHClCOOH molecules undergoes O–H and C–Cl bond scission, but most of them remain intact. After the O–H bond scission at 250 K, two intermediates of CH3CH2COO(a) and CH3CHClCOO(a) are generated on the surface. CH3CHClCOO(a) decreases continuously due to C–Cl bond scission in the temperature range of 250 K~400 K, being transformed into CH3CH2COO(a). Upon heating to a temperature higher than 400 K, CH3CH2COO(a) starts to decompose to form H2, H2C=CH2, CO, CO2, which are desorbed between 400 K and 500 K. The high temperature products HCl and CH3CH=C=O are generated above 710 K.

    The presence of preadsorbed oxygen promotes O–H bond cleavage of CH3CHClCOOH at 120 K, but suppressing the C–Cl bond dissociation. Only a trace amount of the molecule breaks their C–Cl bonds even at 250 K. RAIRS and XPS show that about half of the CH3CHClCOOH undergoes O–H scission at 120 K, forming CH3CHClCOO(a). Upon heating to 380 K, two intermediates of CH3CH2COO(a) and η2-CH3CHCOO(a) are generated, at the sacrifice of CH3CHClCOO(a). On an oxygen-precovered Cu(100), the thermal decomposition products are similar to those from clean surface.

    第一章 緒論 ............................................ 1 1.1 表面的定義 ........................................ 1 1.2 表面的性質 ........................................ 1 1.3 表面的吸附 ........................................ 1 1.4 真空的定義及應用 .............................. 3 1.5 研究動機 ........................................... 3 第二章 表面研究之分析技術 ....................... 9 2.1 程式控溫反應/脫附(Temperature-Programmed Reaction /Desorption, TPR/D) ........................... 9 2.2 反射式吸收紅外光譜(Reflection-Absorption Infrared Spectroscopy, RAIRS) .......................... 13 2.3 歐傑電子能譜(Auger Electron Spectroscopy, AES) ........................ 16 2.4 X-光光電子能譜(X-ray photoelectron spectroscopy, XPS) .............. 17 第三章 實驗系統與方法 ............................ 20 3.1 超高真空系統(UHV System)................. 20 3.2 單晶之前處理方法 .............................. 24 3.3 氧化表面製備方法 .............................. 24 3.4 藥品之前處理方法 .............................. 25 第四章 結果與討論 .................................... 26 4.1 CH3CHClCOOH 在Cu(100)和O/Cu(100)表面上的程溫脫附反應研究 ...... 26 4.1.1 CH3CHClCOOH 在Cu(100)表面上的TPR/D 研究 ........................ 26 4.1.2 CH3CHClCOOH 在O/Cu(100)表面上的TPR/D 研究 ......................... 48 4.2 CH3CHClCOOH 在Cu(100)和O/Cu(100)表面上的反射式吸收紅外光譜(RAIRS)研究 ........................ 66 4.2.1 CH3CHClCOOH 在Cu(100)表面上的RAIRS 研究 ...................... 66 4.2.2 CH3CHClCOOH 在O/Cu(100)表面上的RAIRS 研究 ........................ 74 4.3 CH3CHClCOOH 在Cu(100)和O/Cu(100)表面上的X 光光電子能譜(XPS)研究 ................... 81 4.3.1 CH3CHClCOOH 在Cu(100)表面上的XPS 研究 .................................... 81 4.3.2 CH3CHClCOOH 在O/Cu(100)表面上的XPS 研究 ............................... 86 第五章 結論.................................... 92 參考文獻....................................... 93

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