Gong Yun-Nan, Zhao Si-Qi, Wang Hong-Juan, Ge Zhao-Ming, Liao Chen, Tao Ke-Ying, Zhong Di-Chang, Sakai Ken, Lu Tong-Bu
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.
Department of Chemistry, Faculty of Science, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan.
Angew Chem Int Ed Engl. 2024 Nov 4;63(45):e202411639. doi: 10.1002/anie.202411639. Epub 2024 Aug 23.
Dinuclear metal synergistic catalysis (DMSC) has been proved an effective approach to enhance catalytic efficiency in photocatalytic CO 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 CO-to-CO conversion. The turnover number (TON) and turnover frequency (TOF) values reach as high as 14457 and 0.40 s 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 Co ions, energetically feasible one step two-electron transfer process by Co intermediate to afford Co (CO ) intermediate and fast mass transfer closely related with the planar structure.
双核金属协同催化（DMSC）已被证明是提高光催化CO还原反应催化效率的有效方法，然而设计能够展现DMSC效应的双核金属配合物仍然具有挑战性。主要原因在于双核金属中心周围微环境对催化活性的影响尚未得到充分认识和揭示。在此，我们报道了一种具有平面结构的双核钴配合物，其在光化学CO到CO的转化中表现出卓越的催化效率。周转数（TON）和周转频率（TOF）值分别高达14457和0.40 s，比相应的单核钴配合物高出8.6倍。对照实验和理论计算表明，双核钴配合物催化效率的提高归因于两个Co离子之间的间接DMSC效应、通过Co中间体进行的能量上可行的一步双电子转移过程以生成Co(CO)中间体以及与平面结构密切相关的快速传质。
