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博碩士論文 etd-0627113-025754 詳細資訊
Title page for etd-0627113-025754
論文名稱
Title
苯胺在銅與二氧化鈦單晶表面的吸附及反應研究
Adsorption and Reactions of Aniline on Copper and Titania Single Crystal Surfaces
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
68
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2013-07-24
繳交日期
Date of Submission
2013-07-27
關鍵字
Keywords
苯胺、苯基異氰酸酯、TiO2(101)、Cu(111)、超高真空系統、偶氮苯
azobenzene, phenyl isocyanate, aniline, TiO2(101), ultra-high vacuum system, Cu(111)
統計
Statistics
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中文摘要
偶氮染料的應用極其廣泛,而尋找更有效率並且更環保的催化劑來合成偶氮染料分子是相當重要的議題。苯胺(aniline)是製造染料、藥物、樹脂的原料,文獻中指出苯胺在銅催化下可合成偶氮苯(azobenzene),另外在二氧化鈦單晶表面的研究發現苯胺亦能產生偶氮苯,且反應的中間體是吸附態的phenyl imide (C6H5N(ad))。本研究選擇苯胺及苯基異氰酸酯(phenyl isocyanate)做為前驅物,探討發生在銅與二氧化鈦單晶表面上之熱化學反應機構,檢驗反應中間體,及是否能合成偶氮苯。實驗於超高真空系統中進行,使用了程溫脫附質譜(TPD)、反射吸收式紅外光譜(RAIR)與歐傑電子能譜(AES)等表面分析技術。
苯胺在銅表面之研究顯示,194K時TPD測量到有多層分子脫附,228K為單層分子脫附,300~400K間有aniline裂解後釋發的H2,但還未能確認存在於230K至400K之中間體的身份。苯基異氰酸酯在銅表面之熱化學反應頗為複雜,100K吸附於銅表面的C6H5NCO,升溫至195K時TPD測量到分子脫附,紅外光譜顯示150K開始有C6H5NCO之dimer、trimer,與縮合產物C6H5NCNC6H5形成。dimer與trimer分別在230K與250K時脫附, 230K出現benzoyl nitrene C6H5C(=O)N中間體訊號穩定存在至350K。C6H5C(=O)N在銅表面催化下又形成C6H5CN,在360K左右由表面脫附。350K後C6H5NCNC6H5在高溫裂解成兩部分,C6H5N(ad)部分與腔體內殘留之H2O形成C6H5NH2脫附,C6H5NC部分與表面氧原子又形成C6H5NCO而在360K左右脫附,鍵結很強的C6H5NC,最後裂解成積碳與積氮。
金屬氧化物TiO2(101)單晶之研究為實驗室發展的新方向,尋找此樣品的正確使用條件經歷多次嘗試錯誤過程,因時間關係未能對TiO2之特性及行為全盤了解,只能在未臻理想的條件下進行實驗,所得到aniline與phenyl isocyanate之表面反應結果有限。
Abstract
The applications of azo dye are extremely versatile; therefore, searching for more efficient and environmentally friendly catalysts to synthesize azo dye molecule has become a very important issue. Aniline can be used to synthesize azobenzene in the presence of a copper catalyst. Titanium dioxide can also catalyze the conversion from aniline to azobenzene, and the reaction intermediate is believed to be surface-bound phenyl imide species. In this study, we selected aniline and phenyl isocyanate as precursors to investigate their thermal chemistry on copper and titanium dioxide single crystal surfaces. Experiments were carried out under ultrahigh vacuum conditions and various surface analytic techniques, including temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIR) and Auger electron spectroscopy (AES), were employed to characterize the reaction products and intermediates.
The study of aniline on Cu(111) shows that multilayer and monolayer desorption occurred at 194K and 228K, respectively. H2 was released at 300 ~ 400K as a result of aniline dehydrogenation. The definitive identity of the surface intermediates remains unclear. The thermal chemistry of phenyl isocyanate on Cu(111) is complex. RAIR spectra showed that C6H5NCO underwent dimerization, trimerization , and condensation to form diphenyl carbodiimide (C6H5NCNC6H5) and CO2 at 150K. Dimer and trimer desorbed at 230K and 250K, respectively. Benzoyl nitrene (C6H5C(= O) N) was proposed as an intermediate produced at 230K, and remained stable until 350K. Benzoyl nitrene then decomposed into C6H5CN and desorbed at about 360K. Carbodiimide split into two parts , C6H5N(ad) and C6H5NC fragments, at 350K, reacting with H2O and O respectively to form aniline and phenyl isocyanate evolved at 390K and 360K. Some strongly bonded C6H5NC species eventually decomposed into nitrogen and carbon deposits on the surface at high temperature.
The study on TiO2 (101) single crystal is only preliminary. The cleaning of the TiO2 surface could not be achieved, so experiements were conducted under non-ideal conditions. The results of surface reactions for aniline and phenyl isocyanate are inconclusive.
目次 Table of Contents
第壹章、介紹 1
第貳章、實驗設備 9
2.1 儀器裝置 9
2.2 Density Functional Theory (DFT) Calculations 11
2.3 實驗藥品 12
第參章、實驗結果與詮釋 13
3.1苯胺在單晶表面上之熱化學研究 13
3.1.1 苯胺在Cu(111)表面上之TPD實驗沒有發現偶氮苯脫附 13
3.1.2 DFT計算結果顯示230K IR對應之表面物種為phenyl amide或azobenzene 18
3.1.3 DFT計算結果顯示300K IR光譜不是所推測的吸附態苯基 22
3.1.4 苯胺在TiO2(101)表面上吸附與反應 24
3.2苯基異氰酸酯在單晶表面上之熱化學研究 29
3.2.1 苯基異氰酸酯在Cu(111)表面上產生了benzonitrile及aniline,但未發現azobenzene 29
3.2.2 DFT計算結果顯示150K至230K之表面生成苯基異氰酸酯的二聚體與三聚體 33
3.2.3 150K表面發現carbodiimide形成,230K觀察到benzoyl nitrene 38
3.2.4 依據實驗結果與文獻資料研判IR光譜中最終表面物種分子可能為C6H5-NC 43
3.2.5 推論苯基異氰酸酯在Cu(111)表面之反應路徑 46
3.2.6 苯基異氰酸酯在TiO2(101)表面上之熱化學反應 47
第肆章、討論 49
4.1 苯基異氰酸酯的聚合與縮合反應 49
4.2 苯基異氰酸酯熱化學反應之其它可能的最終表面物種 51
第伍章、結論 53
第陸章、參考文獻 54
參考文獻 References
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