石墨烯是由碳原子以六角晶格排列形成的二維材料，石墨烯完整的π共軛系統使其具有極高的化學穩定性，因此，官能化石墨烯在近幾年成為熱門研究之一。文獻指出利用有機過氧化物經由照光後分解成自由基片段可修飾石墨烯，選擇di-tert butyl peroxide (DTBP) 及tert-butyl peroxybenzoate (TBPB) 作為自由基前驅物，以365 nm LED作為光源，分別探討發生在石墨烯表面之熱化學及光化學反應機構。實驗於超高真空系統下進行，程溫脫附質譜 (Temperature-programmed desorption) 及反射吸收式紅外光譜 (Reflection-absorption infrared spectroscopy) 為所使用之表面分析技術。
DTBP在石墨烯表面的研究結果由TPD得知僅在194 K時偵測到分子脫附峰，即使經過照光仍未見任何光產物，判定DTBP與石墨烯既無熱化學反應也無光化學反應發生。TBPB的光化學研究上，在照光一小時後於TPD測量發現相同溫度下已不見分子脫附，利用RAIRS則發現在照光後1765 cm-1(C=O伸縮)及855 cm-1(O-O伸縮)訊號消失且伴隨924 cm-1及1210 cm-1新訊號產生，證實TBPB與石墨烯確實照光發生光解形成自由基中間體，所有紅外光譜上的訊號在300 K即全數消失，說明pheneyl radical及methyl radical並未與石墨烯形成共價化學鍵，而是自由基彼此作用進行歧化反應生成tert-butanol、benzene、isobutylene epoxide，以上產物皆於200 K以下生成且自石墨烯表面脫離。由於TBPB本身是不吸收365 nm的光，應是石墨烯吸收光能後產生熱電子並傳遞至吸附其上的TBPB之LUMO軌域，TBPB分子HOMO軌域之電子亦同步轉移回石墨烯填滿其電洞，這代表是藉電子交換而發生的能量轉移現象而非電子轉移，結果使激發態之TBPB得以發生裂解。

Graphene is a two-dimensional material composed of carbon atoms that are arranged in a single-layer hexagonal crystal lattice form. Due to its complete conjugated  system, graphene is chemically stable and thus has high potential in a variety of applications. Therefore, research on graphene has become popular and challenging in recent years. Previous studies have indicated that organic peroxides could undergo photolysis upon irradiation. In this research, we select di-tert butyl peroxide (DTBP) and tert-butyl peroxybenzoate (TBPB) as the radical initiator, respectively, and 365 nm LED as the light source to investigate the thermochemistry and photochemistry between graphene and adsorbed peroxides. Experiments were carried out in our ultrahigh vacuum system and in situ surface analytic techniques, including temperature programmed desorption (TPD) and reflection adsorption infrared spectroscopy (RAIRS), were employed.
The interaction of DTBP with the surface of graphene showed that only the monolayer desorption was observed at 194 K. Neither thermochemistry nor photochemistry reactions happened.The results of reacting TBPB with the surface of graphene showed that TBPB was found to be depleted by 1 hour UV irradiation in the PITPD measurement. RAIR spectra showed that both carbonyl stretching vibration at 1765 cm-1 and peroxyl stretching vibration at 835 cm-1 almost disappeared after 1 hour irradiation, but two new peaks (1210 and 930 cm -1) simultaneously emerged. Hence, we confirmed TBPB underwent photolysis along with the formation of radical intermediates. Since all IR features faded out above 300 K, covalent bond formation between the expected photochemically generated phenyl or methyl radicals and the graphene carbons didn’t occurred. Instead, these radicals underwent disproportionation and thus formed benzene, tert-butanol and isobutylene epoxide as the final products. All products generated desorbed from the graphene surface before 200 K. TBPB itself does not absorb 365 nm wavelength of light but graphene does. Photoexcited graphene serves as a photosensitizer responsible for delivering hot electrons to the LUMO of TBPB. Meanwhile, an electron within the TBPB HOMO transferred to graphene, the energy transfer resulted from the electron-exchange triggered formation of ground state graphene and excited state TBPB. The excited state TBPB was decomposed via homolytic cleavage of O-O bond to render radicals.

第壹章、 介紹 1
1-1研究背景 1
1-2研究動機 7
第貳章、實驗設備與方法 8
2-1超高真空系統與實驗裝置 8
2-1-1 程溫脫附實驗 (Temperature Programmed Desorption，TPD) 10
2-1-2反射式吸收紅外光譜 (Reflection-Absorption Infrared Spectroscopy，RAIRS) 11
2-2 拉曼光譜 (Raman Spectroscopy) 14
2-3 密度泛涵理論計算 15
2-4 LED-UV點光源 16
2-5 石墨烯、Cu(111)單晶及實驗藥品 17
2-5-1 石墨烯的製備 17
2-5-2 Cu(111)單晶及藥品 19
第參章、實驗結果與詮釋 20
3-1-1 DTBP在石墨烯表面的熱化學研究 20
3-1-2 DTBP在石墨烯表面的光化學研究 25
3-2-1 TBPB在石墨烯表面的熱化學研究 29
3-2-2 TBPB在石墨烯表面的光化學研究 35
3-3-1 TBPB在Cu(111)表面的熱化學研究 50
3-3-2 DTBP在Cu(111)表面的熱化學研究 53
第肆章、討論與結論 57
4-1 DFT計算與實驗結果之比較 57
4-2 未來工作 63
4-3 結論 64
第伍章、參考文獻 65

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