文献类型：期刊文献

英文题名：Rearranging spin electrons by axial-ligand-induced hybridization state transition to boost the activity of nickel single-atom-catalysts for electrochemical CO2 reduction

作者：Peng, Mingxia[1];Huang, Kai[2];Hu, Xiuyuan[3];Zitolo, Andrea[4];Liu, Honglai[1,5];Lian, Cheng[1,5];Li, Jingkun[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[2]Taizhou Univ, Sch Pharmaceut & Chem Engn, Taizhou 318000, Zhejiang, Peoples R China;[3]East China Normal Univ, 2 High Sch, 555 Chenhui Rd, Shanghai 201203, Peoples R China;[4]Orme Merisiers, Synchrotron SOLEIL, Departementale 128, F-91190 St Aubin, France;[5]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2025

卷号：16

期号：17

起止页码：7387

外文期刊名：CHEMICAL SCIENCE

收录：;EI(收录号：20251318148424);WOS:【SCI-EXPANDED(收录号:WOS:001451904700001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (22102114).

语种：英文

外文关键词：Catalyst selectivity - Chlorine compounds - Electrolytic reduction - Nickel - Oxygen reduction reaction

摘要：Single-atom catalysts (SACs) with M-N4 active sites show great potential to catalyze the electrochemical CO2 reduction reaction (eCO2RR) toward CO. The activity and selectivity of SACs are determined by the local coordination configuration of central metal atoms in M-N4 sites, which is readily tuned by axial ligands. In this work, we construct axial ligands in situ on two Ni-N4-type model SACs, NiPc and Ni-N-C, by adding Cl- into the electrolyte taking advantage of the strong chemisorption of Cl- over Ni-N4. Cl axial ligand lowers the energy barrier of the potential-determining step for the eCO2RR due to a hybridization state transition of Ni orbitals and the resulting rearrangement of spin electrons. Consequently, both NiPc and Ni-N-C with axial Cl exhibit superior activity for the eCO2RR toward CO. Finally, we propose the magnetic moment of Ni as a universal descriptor for the eCO2RR toward CO on Ni-N4 with various axial ligands.