Chen Lingjing, Qin Yanfei, Chen Gui, Li Mingya, Cai Lirong, Qiu Yongfu, Fan Hongbo, Robert Marc, Lau Tai-Chu
School of Environment and Civil Engineering, Dongguan University of Technology, Guangdong, 523808, China.
Dalton Trans. 2019 Jul 2;48(26):9596-9602. doi: 10.1039/c9dt00425d.
A new pentadentate quinoline-pyridine ligand and its iron (1), cobalt (2) and nickel (3) complexes have been synthesized and characterized. The iron complex exhibits excellent photocatalytic activity towards CO2-to-CO conversion with a TON(CO) of 544 and a selectivity of 99.3% using the commercially available organic dye purpurin as the photosensitiser and BIH as the electron donor. In contrast, the cobalt and nickel complexes result in very low activity for CO production with a TON of only 8 and 15, respectively. On the other hand, all the three complexes show good electrocatalytic activity for CO2 reduction when using 2,2,2-trifluoroethanol as the proton source with the active intermediate of M0 species. The lack of activity in photocatalytic CO2 reduction by 2 and 3 can be attributed to the redox potential of MI/M0 which is significantly more negative than that of PP-/PP2- while in the case of 1 the FeI/Fe0 redox potential becomes more positive than that of the PP-/PP2- couple.
合成并表征了一种新型五齿喹啉 - 吡啶配体及其铁（1）、钴（2）和镍（3）配合物。以市售有机染料紫红素作为光敏剂、BIH作为电子供体时，铁配合物对二氧化碳转化为一氧化碳表现出优异的光催化活性，一氧化碳的转化数（TON(CO)）为544，选择性为99.3%。相比之下，钴和镍配合物产生一氧化碳的活性非常低，TON分别仅为8和15。另一方面,当使用2,2,2 - 三氟乙醇作为质子源且活性中间体为M0物种时，这三种配合物对二氧化碳还原均表现出良好的电催化活性。2和3在光催化二氧化碳还原中缺乏活性可归因于MI/M0的氧化还原电位明显比PP-/PP2-的更负，而对于1，FeI/Fe0的氧化还原电位比PP-/PP2-电对更正。
