Bi Jiaojiao, Hou Pengfei, Liu Fang-Wei, Kang Peng
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, 29 Zhongguancun East Rd, Beijing, 100190, P.R. China.
University of Chinese Academy of Sciences, 19A Yuquan Rd, Beijing, 100049, P.R. China.
ChemSusChem. 2019 May 21;12(10):2195-2201. doi: 10.1002/cssc.201802929. Epub 2019 May 3.
The iron complex of tetradentate tris[2-(diphenylphosphino) ethyl]phosphine (PP ), Fe(PP )(MeCN) , was able to electrocatalytically reduce CO to formate with a Faradaic efficiency (FE) of approximately 97.3 % in acetonitrile. Upon addition of diethylamine as a cocatalyst, electrocatalytic reduction to methanol was achieved with an FE of 68.5 %, and other products were formamide and formate. A mechanistic study suggested that the FeH(PP ) hydride complex was the active species in the electrocatalysis. Added amine as cocatalyst could react with CO to form carbamate, which could then be reduced to formamide and further to methanol. By contrast, free CO could only be reduced to formate as the end-product.
四齿三[2-(二苯基膦基)乙基]膦(PP)的铁配合物Fe(PP)(MeCN)，在乙腈中能够将CO电催化还原为甲酸盐，法拉第效率(FE)约为97.3%。加入二乙胺作为助催化剂后，实现了将CO电催化还原为甲醇，FE为68.5%，其他产物为甲酰胺和甲酸盐。机理研究表明，氢化物配合物FeH(PP)是电催化中的活性物种。加入的胺作为助催化剂可与CO反应生成氨基甲酸盐，然后氨基甲酸盐可被还原为甲酰胺并进一步还原为甲醇。相比之下，游离CO只能被还原为甲酸盐作为最终产物。
