Department of Biology and Chemistry, Institute of Molecular Functional Materials, and State Key Laboratory in Marine Pollution, City University of Hong Kong , Tat Chee Avenue, Kowloon Tong, Hong Kong, China.
CAS Key Laboratory of Crust-Mantle and the Environment, School of Earth and Space Sciences, University of Science and Technology of China , Hefei, Anhui 230026, China.
J Am Chem Soc. 2016 Aug 3;138(30):9413-6. doi: 10.1021/jacs.6b06002. Epub 2016 Jul 26.
The design of highly efficient and selective photocatalytic systems for CO2 reduction that are based on nonexpensive materials is a great challenge for chemists. The photocatalytic reduction of CO2 by Co(qpy)(OH2)2 (1) (qpy = 2,2':6',2″:6″,2‴-quaterpyridine) and Fe(qpy)(OH2)2 (2) have been investigated. With Ru(bpy)3(2+) as the photosensitizer and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole as the sacrificial reductant in CH3CN/triethanolamine solution under visible-light excitation (blue light-emitting diode), a turnover number (TON) for CO as high as 2660 with 98% selectivity can be achieved for the cobalt catalyst. In the case of the iron catalyst, the TON was >3000 with up to 95% selectivity. More significantly, when Ru(bpy)3(2+) was replaced by the organic dye sensitizer purpurin, TONs of 790 and 1365 were achieved in N,N-dimethylformamide for the cobalt and iron catalysts, respectively.
设计高效、选择性的基于廉价材料的 CO2 还原光催化体系是化学家面临的巨大挑战。通过Co(qpy)(OH2)2（1）（qpy=2,2':6',2″:6″,2‴- 喹啉并[2,3-b]吡啶）和Fe(qpy)(OH2)2（2）的光催化还原研究，探讨了 CO2 的还原。在可见光激发（蓝光发光二极管）下，以 Ru(bpy)3(2+)为光敏剂，1,3-二甲基-2-苯基-2,3-二氢-1H-苯并[d]咪唑为牺牲还原剂，在 CH3CN/三乙醇胺溶液中，钴催化剂的 CO 转化率高达 2660，选择性为 98%。对于铁催化剂，TON 大于 3000，选择性高达 95%。更重要的是，当 Ru(bpy)3(2+)被有机染料敏化剂紫红素取代时，钴和铁催化剂在 N,N-二甲基甲酰胺中的 TON 分别达到了 790 和 1365。
