【作者】 陈金平； 都新丰； 李嫕；

【Author】 Jinping Chen;Xinfeng Du;Yi Li;Key Laboratory of Photochemical Conversion and Optoelectronic Materials,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences;

【机构】 中国科学院理化技术研究所,光化学转换与功能材料重点实验室；

【摘要】 本文设计并合成了四种联吡啶配体上共价修饰不同取代基的三羰基铼配合物fac-Re（L）（CO）₃Cl:即取代基分别为甲基（Re-Me）、羧基（Re-Ac）、季铵盐（Re-Qa）以及咪唑盐（Re-Im）的铼配合物,化合物的结构均经过核磁氢谱、质谱以及红外光谱的的确认,测定了四种配合物第一和第二还原电位。分别以该系列铼配合物为催化剂和光敏剂、三乙醇胺为电子牺牲体构建了均相可见光催化还原CO₂体系,配体上取代基对催化剂的催化效果有显著的影响,催化活性Re-Qa>Re-Ac≈Re-Me>Re-Im。研究表明,铼配合物的催化效果和其在催化过程中的失活速率密切相关,其变化趋势与催化剂失活速率一致,催化剂的失活发生在催化剂得到一个电子后的单电子还原态中间体（One-electron reduced species,OER）。瞬态吸收光谱检测到了催化过程中的OER的生成,证实光催化还原CO₂过程通过生成OER中间体进行的。更多还原

【Abstract】 a series of rhenium tricarbonyl catalysts（Re-Me, Re-Ac, Re-Qa and Re-Im） with different substitutes to 2,2-bipyridine ligand were synthesized and characterized（Figure 1）. These catalysts were successfully applied to a light induced CO₂ reduction system with TEOA as sacrificial reagent, exhibiting different turnover numbers for different catalysts. The highest turnover numbers was achieved for the catalyst of Re-Qa, while Re-Im exhibits almost no activity in the photocatalytic conversion of CO₂ to CO. UV-vis spectra show that the rate of deactivation is linked to the decomposition of the catalysts in the photocatalytic system. The transient absorption spectra conformed the formation of one-electron-reduced（OER） species in the catalytic system.更多还原