金的催化多以其奈米粒子沉積在金屬氧化物載體為研究對象上，本論文不同於前例，以Au(111)單晶為基材，在超高真空系統中，利用程溫脫附實驗(TPD)搭配四級質譜儀、反射式吸收紅外光譜(RAIRS)及密度泛函理論計算(DFT)去探討nitrobenzene、aniline、phenyl isocyanate及benzyl azide表面化學和光化學反應。
nitrobenzene、aniline、phenyl isocyanate在單晶表面的熱脫附及光化學實驗顯示，只能夠觀察到單純分子的脫附，未觀察到任何的熱及光化學產物生成。Benzyl azide之熱脫附實驗顯示，同樣只觀察到分子脫附，但在光化學實驗中，觀察到在280、310 K出現新的脫附峰，根據質譜碎片分析比對，可能的產物分別為phenylmethanimine及benzonitrile，並利用反射式吸收紅外光譜以及DFT理論計算進一步推測產物身份。
若事先以離子槍轟擊(sputter)單晶表面且不高溫退火(annealing)，使單晶表面產生缺陷(defect)，再進行benzyl azide吸附，在400 K發現到新的脫附峰，同樣以質譜資料庫與實驗結果進行比對，可能的產物為bisbenzyl，若增加離子槍轟擊的時間，則可以促使bisbenzyl產率增加。

For gold catalysis research the most commonly used catalyst contain metal nanoparticle deposited on metal oxide support. Unlike the previous examples, I used Au (111) single crystal substrate to study interactions between gold and nitrobenzene, aniline, phenyl isocyanate and benzyl azide under ultra high vacuum conditions. Temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations were combined to elucidate the surface thermal and photo chemistry.
Nitrobenzene, aniline, phenyl isocyanate photo and thermal experiment display only the molecular desorption on Au (111). In the study of benzyl azide, only thermal molecular desorption was observed. However, under 365 nm UV light irradiation, new desorption peaks were found at 280 K and 310 K, respectively. By analysis of the fragmentation pattern, the possible products was phenylmethanimine and benzonitrile. RAIRS and DFT calculations somewhat support the speculation on the product.
When the surface was subject the ion gun bombardment without high temperature annealing, thermal desorption experiments of benzyl azide showed a peak at 400 K was observed to a peak. The probable product was bisbenzyl. Increasing the ion gun bombardment time, bisbenzyl yields can be enhanced.

目錄
第壹章、介紹 1
1-1 研究背景 1
1-2 研究動機 6
第貳章、實驗設備及方法 7
2.1 儀器裝置 7
2.1.1 程溫脫附實驗(TPD) 8
2.1.2 反射式吸收紅外光譜(RAIRS) 10
2.1.3 歐傑電子能譜(AES) 13
2.2 密度泛函理論計算(density functional theory calculations，DFT) 13
2.3實驗藥品 14
第參章、實驗結果與詮釋 15
3.1 Phenyl isocyanate在Au(111)表面上之熱化學及光化學研究 15
3.1.1 Phenyl isocyanate在Au(111)表面上之TPD實驗 15
3.1.2 Phenyl isocyanate在Au(111)表面上之PITPD實驗 17
3.1.3 DFT計算與RAIR光譜 19
3.2 Nitrobenzene在Au(111)表面上之熱化學及光化學研究 20
3.2.1 Nitrobenzene在Au(111)表面上之TPD實驗 20
3.2.2 Nitrobenzene在Au(111)表面上之PITPD實驗 22
3.2.3 DFT計算與RAIR光譜 24
3.3 Aniline在Au(111)表面上之熱化學及光化學研究 25
3.3.1 Aniline在Au(111)表面上之TPD實驗 25
3.3.2 Aniline在Au(111)表面上之PITPD實驗 27
3.3.3 DFT計算與RAIR光譜 29
3.4 Benzyl azide 在Au(111)表面上之熱化學及光化學研究 30
3.4.1 Benzyl azide (BA)在Au(111)表面上之熱化學 30
3.4.2 Benzyl azide在Au(111)表面上之光化學研究 32
3.4.3 BA在有著defect之Au(111)表面上熱化學及光化學研究 43
第肆章、討論與結論 46
4.1 Nitrene形成的方法 46
4.2 nitrene所能進行的反應及應用 48
4.3 結論 51
第伍章、參考文獻 52

第伍章、參考文獻

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