Heterogenization of a Dinuclear Cobalt Molecular Catalyst in Porous Polymers via Covalent Strategy for CO_(2)Photoreduction with Record CO Production Efficiency  

作　　者：Yun-Nan Gong Si-Ya Lv Hao-Yu Yang Wen-Jie Shi Jing-Jing Wang Long Jiang Di-Chang Zhong Tong-Bu Lu 

机构地区：[1]MOE International Joint Laboratory of Materials Microstructure,Institute for New Energy Materials and Low Carbon Technologies,School of Materials Science and Engineering,Tianjin University of Technology,Tianjin 300384 [2]Instrumental Analysis and Research Center,Sun Yat-Sen University,Guangzhou 510275

出　　处：《CCS Chemistry》2024年第12期3030-3040,共11页中国化学会会刊(英文)

基　　金：supported by National Key R&D Program of China(grant no.2022YFA1502902);the National Natural Science Foundation of China(grant nos.22371208,22271218,22071182,and 21931007);the Science&Technology Development Fund of Tianjin Education Commission for Higher Education(grant no.2018KJ129).

摘　　要：Photocatalytic CO_(2)reduction into chemical fuels is a promising route for alleviating the energy crisis and environmental issues.However,reported catalysts still exhibit low catalytic efficiencies,which hinders the development of this important reaction.Herein,we report the heterogenization of a dinuclear cobalt molecular catalyst into two porous polymers(Co_(2)-P1 and Co_(2)-P2)using a covalent strategy for photocatalytic CO_(2)reduction.As a result,Co_(2)-P1 with a phenyl group as the linker exhibited high catalytic performance for the photochemical CO_(2)-to-CO conversion with a CO production rate of 568.8 mmol g-1 h-1 and turnover frequency(TOF)of 11.6 min-1(CO selectivity,95.2%).More impressively,by extending the phenyl to biphenyl linker,the resulting Co_(2)-P2 shows obviously enhanced photocatalytic efficiency for CO_(2)reduction to CO,with a record CO production rate of 1063.0 mmol g-1 h-1 and TOF of 23.6 min-1(CO selectivity,94.9%)under a laboratory light source.Furthermore,Co_(2)-P2 also shows outstanding catalytic activity for photocatalytic CO_(2)reduction under natural sunlight,with a CO production rate of 544.1 mmol g-1 h-1 and TOF of 12.1 min-1(CO selectivity,97.2%).Systematic studies demonstrated that fast electron transfer from the photosensitizer to the catalyst greatly contributes to the superior catalytic activity of Co_(2)-P2.

关 键 词：molecular catalyst HETEROGENIZATION covalent strategy polymer photocatalysis CO_(2)reduction 

分 类 号：O64[理学—物理化学]