Affiliation:
1. MOE International Joint Laboratory of Materials Microstructure Institute for New Energy Materials and Low Carbon Technologies School of Materials Science and Engineering School of Chemistry and Chemical Engineering Tianjin University of Technology Tianjin 300384, China E-mails: E-mails
2. Department of Chemistry, Faculty of Science Kyushu University Motooka 744 Nishi-ku Fukuoka 819-0395 Japan
Abstract
AbstractDinuclear metal synergistic catalysis (DMSC) has been proved an effective approach to enhance catalytic efficiency in photocatalytic CO2 reduction reaction, while it remains challenge to design dinuclear metal complexes that can show DMSC effect. The main reason is that the influence of the microenvironment around dinuclear metal centres on catalytic activity has not been well recognized and revealed. Herein, we report a dinuclear cobalt complex featuring a planar structure, which displays outstanding catalytic efficiency for photochemical CO2‐to‐CO conversion. The turnover number (TON) and turnover frequency (TOF) values reach as high as 14457 and 0.40 s−1 respectively, 8.6 times higher than those of the corresponding mononuclear cobalt complex. Control experiments and theoretical calculations revealed that the enhanced catalytic efficiency of the dinuclear cobalt complex is due to the indirect DMSC effect between two CoII ions, energetically feasible one step two‐electron transfer process by Co2I,I intermediate to afford Co2II,II(CO22−) intermediate and fast mass transfer closely related with the planar structure.
Funder
National Natural Science Foundation of China