文献类型：期刊文献

英文题名：Chlorine-dopant dynamically stabilizes Cu0/Cu+ active sites for selective CO2 electroreduction to multicarbon products

作者：Li, Congcong[1];Guo, Zhongyuan[2];Cui, Jialin[1];Zhang, Tingting[1];Liu, Zhongliang[1];Mao, Xiaoqing[1];Shen, Yongjun[1];Yang, Saiwu[1];Jiang, Yingfang[1];Tang, Pinghui[1];Li, Hao[2];Li, Huihui[1];Li, Chunzhong[1,3]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China;[2]Tohoku Univ, Adv Inst Mat Res WPI AIMR, Sendai 9808577, Japan;[3]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China

年份：2025

卷号：71

期号：10

外文期刊名：AICHE JOURNAL

收录：;EI(收录号：20252718713349);WOS:【SCI-EXPANDED(收录号:WOS:001519165000001)】；

基金：This work was supported by the National Natural Science Foundation of China (U22B20143, U24A20546, 22478121), Shanghai Municipal Science and Technology Major Project, the Science and Technology Commission of Shanghai Municipality (22dz1205900), Postdoctoral Fellowship Program of CPSF (GZC20241472), and JSPS KAKENHI (JP25K01737). The authors thank the Shanghai synchrotron Radiation Facility (14W1, SSRF) for the use of their services, the Center for Computational Materials Science, Institute for Materials Research, Tohoku University for the use of MASAMUNE-IMR (202412-SCKXX-0211) and the Institute for Solid State Physics (ISSP) at the University of Tokyo for the use of their supercomputers.

语种：英文

外文关键词：chlorine-dopant; Cu-0/Cu+ active sites; electrochemical CO2 reduction; multicarbon products

摘要：The electrochemical CO2 reduction reaction (CO2RR) to multicarbon (C2+) products faces significant challenges rooted in the high energy barriers of C-C coupling, which can be addressed through dopant-mediated stabilization of Cu+ species on Cu catalysts. Here, we present an in-situ chlorine (Cl) doping strategy achieving dynamic stabilization of Cu-0/Cu+ active sites, consequently resulting in an improved selectivity for C2+ product with a partial current density of 280 mA cm(-2). In-situ x-ray diffraction (XRD) and ex-situ x-ray photoelectron spectroscopy (XPS) analyses confirmed sustained Cu+ species and Cl dopant retention throughout CO2RR operation and membrane electrode assembly (MEA) durability assessment (over 55 h). Theoretical study demonstrated that Cl-dopant could extract electrons from Cu during CO2RR to dynamically produce Cu-0/Cu+ active sites to lower the free energy toward CO2RR and improve the adsorption of *CO and *CHO intermediates, which is key for the C-C coupling. Our findings demonstrate that Cl-dopant serves as an efficient electron extractor for generating Cu+ species, thereby emphasizing the efficacy of the in-situ doping strategy in creating a high density of stable interfacial Cu-0/Cu+ active sites.