文献类型：期刊文献

英文题名：Co-based molecular catalysts for efficient CO2 reduction via regulating spin states

作者：Kong, Xiangdong[1];Ke, Jingwen[1];Wang, Zhiqiang[2,3];Liu, Yan[1];Wang, Yibo[1];Zhou, Weiran[1];Yang, Zhengwu[1];Yan, Wensheng[1];Geng, Zhigang[1];Zeng, Jie[1]

机构：[1]Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale,Dept Chem Phys, CAS Key Lab Strongly Coupled Quantum Matter Phys, Natl Synchrotron Radiat Lab,Anhui Higher Educ Ins, Hefei 230026, Anhui, Peoples R China;[2]East China Univ Sci & Technol, Key Lab Adv Mat, Ctr Computat Chem, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2021

卷号：290

外文期刊名：APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY

收录：;EI(收录号：20211010021926);WOS:【SCI-EXPANDED(收录号:WOS:000630129900001)】；

基金：This work was supported by National Science Fund for Distinguished Young Scholars (21925204), NSFC (U1932146 and U19A2015), National Key Research and Development Program of China (2019YFA0405600), Key Research Program of Frontier Sciences of the CAS (QYZDB-SSW-SLH017), Fundamental Research Funds for the Central Universities, and USTC Research Funds of the Double First-Class Initiative (YD2340002002).

语种：英文

外文关键词：Co-based molecular catalysts; Spin state; CO2 electroreduction; CO2 activation

摘要：A typical mode of CO2 activation is that d electrons at the d orbital of transition metals transfer to the unoccupied pi* orbital of CO2. Thus the exploration of the relationship between d-electron behaviors and CO2 activation is of great importance. Herein, we demonstrate that high-spin state of 3d electrons in Co2+ facilitated the activation of CO2 over Co-salophen-X (X represents to Cl, Br, or I). Among these catalysts, Co-salophen-Br exhibited the highest Faradaic efficiency for CO. Notably, the Faradaic efficiency for CO over Co-salophen-Br reached 98.5 % at -0.70 V versus reversible hydrogen electrode, which was 1.5 and 1.2 times as high as those over Co-salophen-Cl (64.8 %) and Co-salophen-I (81.8 %), respectively. Density functional theory calculations revealed that high-spin state of Co sites decreased the reaction energy barrier for the formation of CO. Based on the analysis of electronic state, the ratio of high-spin state was 65.6 % for Co-salophen-Br, which was the highest among the three Co-based molecules. The Co sites with high-spin state promoted the electron transfer from high-energy 3d orbital (3d(z2) and 3d(x2-y2)) of Co to the unoccupied pi* orbital of CO2, improving catalytic performance.