2019-08-012024-05-18https://scholars.lib.ntu.edu.tw/handle/123456789/713935摘要：有機共軛分子具有特殊的光電性質，因此廣泛地被應用於染料、發光二極體、場效電晶體、太陽能電池等不同領域。我們最近的研究發現，具有特殊共軛球體形狀的碳六十，可有效催化二氧化碳的光驅動還原反應，若將其鍵結以發色基團，更可大幅提高催化效率，而且可透過變換發色基團的化學結構來調控產物種類與產率。本計畫擬針對富勒烯與有機/無機敏化物形成的分子/混成共催化系統做深入的研究探討，其將透過設計及合成一系列不同化學組成、分子結構之有機化合物，系統性地分析催化劑結構對於反應機制、產物種類與催化效能的影響，期能開發出高效能之新型二氧化碳光還原催化劑。第一年的工作將著重於有機共軛發色基團的分子結構設計，包含引入不同的富電子單元、缺電子單元、共軛性/烷基間隔單元等，藉以調整分子能階、吸收光譜、消光係數及分子內電子轉移效率；第二年的研究將包含合成一系列可以吸附或鍵結於無機半導體奈米粒子的富勒烯衍生物，進而組成有機/無機混成催化系統，另外，導入極性助溶基團，將富勒烯/有機發色基團及富勒烯/無機半導體量子點兩系統應用於均相溶液反應；第三年將延伸第一年度的研究成果，再透過分子結構設計，把多個有機發色基團鍵結至同一個富勒烯上，以提供更多的光激電子進行光化學反應，期能觸發需更多電子轉移之還原產物的生成。<br> Abstract: Due to their unique optoelectronic properties, organic conjugated molecules have been extensively used in various fields such as pigment, light-emitting diode, field-effect transistor and solar cell. Our recent research results demonstrated that C60 derivatives can be applied as promising catalyst of light-driven reduction of carbon dioxide. Moreover, its functionalization with organic chromophore significantly increased the catalytic efficiency, and both the composition and molecular structure of chromophore critically affected the type of products and their generation rates. This project aims to gain insight into the novel cocatalyst system consisting of fullerene and organic/inorganic sensitizer through synthesizing a series of organic compounds with various chemical compositions and molecular structure to systematically investigate how the structure of catalyst influences the reaction mechanism and production yield. In the first year, the molecular structure of chromophore will be designed and tailored by incorporating proper electron-rich and electron-deficient blocks, conjugated spacer and alkyl chain to fine-tune its optoelectronic properties, including energy levels, light-absorption spectrum, extinction coefficient and the efficiency of intramolecular electron transfer. In the second year, the functionalization of fullerene with different anchoring groups, such as -OH, -COOH, -SH, -PO3H2, will be conducted to build up fullerene/inorganic quantum dot catalysts. In addition, both molecular and hybrid systems will be applied to the homogeneous light-driven reaction by the incorporation of solubilizing group onto fullerene adducts. In the third year, several chromophore segments will be bounded onto one fullerene cage forming a structure of fullerene-(chromophore)n to broaden absorption spectrum and enhance molar absorption coefficient, producing more economically valuable products and increasing the catalytic efficiency.有機共軛材料富勒烯光驅動化學反應催化劑二氧化碳Organic conjugated materialsfullereneslight-driven chemical reactioncatalystcarbon dioxide