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研究生： 李光中
Koung Chung-Li
論文名稱： 利用理論計算探討Tricarbonyl 8-oxyquinoline Rhenium(I) 錯合物將CO2 還原的催化循環過程
Theoretical Studies on CO2 Reduction by a Tricarbonyl 8-oxyquinoline Rhenium(I) Complex: Modeling a Catalytic Cycle
指導教授： 蔡明剛
Tsai, Ming-Kang
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2012
畢業學年度： 100
語文別： 中文
論文頁數： 96
中文關鍵詞： CO2 還原 、p型奈米半導體 、8-oxyquinoline 、Tricarbonyl Rhenium(I)
英文關鍵詞： CO2 Reduction, p-Type Nanoparticle Semiconductor Electrodes, 8-oxyquinoline, Tricarbonyl Rhenium(I)
論文種類： 學術論文
相關次數： 點閱：166  下載：4 
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    • 利用太陽能將CO2 還原於p型奈米半導體電極的目標主要是在開發下一代將CO2 還原的催化劑，將解決一些在傳統上利用光催化還原CO2 催化劑的主要限制，並且獲得可利用的再生能源。目前對於利用勻相催化劑將CO2 還原固有的問題是依賴犧牲電子的提供者，最後使催化劑產生出毒性。而在此我們研究利用捕光電極透過分子自組裝單分子膜(SAMs)的新型氧化還原催化劑，不需要犧牲試劑作為還原劑且可利用較低的電位將CO2 進行催化還原。
    經由與Rochford教授的合作，我們選定許多含有釕和錸金屬的複合物做為光敏劑，其中分別含有8-oxyquinoline (8-OQN) ligand與bpy ligand做比較，而催化劑的部份則是選擇tricarbonyl rhenium(I) 接上8-oxyquinoline (8-OQN) 的複合物，並且利用理論計算去探討光敏劑的光化學性質和催化劑將如何在電催化和光催化下進行CO2 還原的循環過程。

    The Solar CO2 Reduction on p-Type Nanoparticle Semiconductor Electrodes project is aimed at developing the next generation of CO2 reduction catalysts that will overcome the major limitations of state-of-the-art catalysts and usher in a new era of fuel generation from renewable resources. The inherent problem with current homogeneous CO2 reduction catalysts is their dependence upon sacrificial electron donors that eventually poison the catalyst. The current approach focuses at several light-sensitized redox active catalystic systems that do not require sacrificial reductants and, furthermore, catalyze CO2 reduction at very low overpotentials.
    Several Ru and Re complexes are chosen as the ligh sensitizers, being chelated with 8-oxyquinoline (8-OQN) and bpy types of ligand. The catalytic center used tricarbonyl rhenium (I) complex corrdinated with 8-OQN ligand. A comprehensive theoretical analysis is carried out to investigate the electrochemical and photophysical properties aling CO2 reduction catalytic cycle.

    圖目錄 3 表目錄 6 中文摘要 7 英文摘要 8 第一章 緒論 9 1-1 前言 9 1-2 背景和意義 10 1-3 質子耦合電子轉移(PROTON-COUPLED ELECTRON TRANSFER) 12 1-4 均相光化學還原介紹 14 1-5 二氧化碳配位至過渡金屬複合物介紹 15 1-6 過渡金屬複合物 17 1-6-1 釕金屬複合物的介紹 17 1-6-2 錸金屬複合物的介紹 20 第二章 理論計算方法與原理 26 2-1 計算化學原理 26 2-2 初始法(AB INITIO) 28 2-3 半經驗法 29 2-4 密度泛函理論（DENSITY FUNCTIONAL THEORY, DFT） 29 2-5 基底函數(BASIS SETS) 30 2-6 計算方法(SINGLE POINT ENERGY) 34 2-6-1 單點能量（Single point energy） 34 2-6-2 幾何優化(Geometry optimization) 34 2-6-3 振動頻率（Frequency） 36 2-6-4 溶劑模型（Solvation Model） 36 2-7 溶液中的自由能、電位與PKA的計算 38 2-8 激發態的計算(EXCEITED STATES ) 40 2-9 本論文採用的計算方法 41 第三章 結果與討論 43 3-1 研究目標 43 3-2 二氧化碳還原催化劑設計 45 3-3 8-OXYQUINOLINE (8-OQN)的介紹 47 3-4 光敏劑電子激發態和吸收光譜的分析 50 3-4-1 Re-a-PA-Cl、Re-a-Py-Cl和Re-a-Th-Cl 50 3-4-2 Re-a-PA-POEt3、Re-a-Py-POEt3和Re-a-Th- POEt3 56 3-4-3 Re-b-PA、Re-b-Py和Re-b-Th 61 3-4-4 Ru-c-PA、Ru-c-Py和Ru-c-Th 67 3-4-5 Ru-d-PA、Ru-d-Py和Ru-d-Th 72 3-5 REOQN(CO)3電化學還原CO2的催化循環 77 3-6 REOQN(CO)3光化學還原CO2的催化循環 80 第四章 結論 86 第五章 參考文獻 87

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