Liu Fang-Wei, Bi Jiaojiao, Sun Yuanyuan, Luo Shuping, 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, PR China.
University of Chinese Academy of Sciences, 19A Yuquan Rd, Beijing, 100049, PR China.
ChemSusChem. 2018 May 25;11(10):1656-1663. doi: 10.1002/cssc.201800136. Epub 2018 May 2.
An imino bipyridine cobalt(II) complex was developed for the electrocatalytic reduction of CO to formate in acetonitrile with a faradaic efficiency of approximately 80 %. For comparison, a symmetric bis-imino pyridine complex showed lower catalytic activity because of less conjugation in the system. Cyclic voltammetry, electron paramagnetic resonance and IR spectroscopy studies provided mechanistic details and the structures of the key intermediates. DFT calculations confirmed the role of large π-conjugated groups for stabilizing key intermediates through electronic conjugation.
开发了一种亚氨基联吡啶钴（II）配合物，用于在乙腈中将CO电催化还原为甲酸盐，法拉第效率约为80%。相比之下，一种对称的双亚氨基吡啶配合物由于体系中共轭较少，催化活性较低。循环伏安法、电子顺磁共振和红外光谱研究提供了机理细节和关键中间体的结构。密度泛函理论计算证实了大π共轭基团通过电子共轭稳定关键中间体的作用。
