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

李光中(Koung Chung-Li)

指導教授 ： 蔡明剛

國立臺灣師範大學/理學院/化學系/碩士(2012年)

摘要

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。

關鍵字

CO2 還原 ； p型奈米半導體 ； 8-oxyquinoline ； Tricarbonyl Rhenium(I)

並列摘要

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.

並列關鍵字

CO2 Reduction ； p-Type Nanoparticle Semiconductor Electrodes ； 8-oxyquinoline ； Tricarbonyl Rhenium(I)

參考文獻

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