文献类型：期刊文献

英文题名：Weak *CO-Binding Dopants in Cu-Based Single-Atom Alloys Serving as Diffusion-Assisting Mediators to Facilitate C-C Coupling

作者：Niu, Yanpu[1,2];Tao, Haolan[1,2,3];Li, Jingkun[3];Lian, Cheng[1,2,3];Liu, Honglai[1,2,3]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2025

卷号：129

期号：43

起止页码：19371

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20254419421099);WOS:【SCI-EXPANDED(收录号:WOS:001596003300001)】；

基金：This work is sponsored by the National Key R&D Program of China (No. 2022YFB4602101), the Fundamental Research Funds for the Central Universities (No. 2022ZFJH004 and No. 2024SMECP05), the National Natural Science Foundation of China (No. 22278127, No. 22102114, and No. 22378112), the Shanghai Pilot Program for Basic Research (22T01400100-18), the China Postdoctoral Science Foundation (2024M750909), and the Postdoctoral Fellowship Program of CPSF (GZC20230801).

语种：英文

外文关键词：Adsorption - Atoms - Cobalt - Cobalt alloys - Copper - Copper alloys - Couplings - Density functional theory - Design for testability - Diffusion barriers - Zinc compounds

摘要：Copper-based single-atom alloy (SAA) catalysts exhibit tunable C-C coupling behavior during CO2 reduction, governed by dopant-dependent metal-carbon (M-C) interactions. Combining density functional theory (DFT) calculation and ab initio molecular dynamics (AIMD) simulation, this study systematically investigates dopant effects across three C-C coupling pathways: *CO+*CO, *CO+*COH, and *CO+*CHO. Compared to *COH and *CHO, *CO is identified as the primary migratory intermediate governing coupling kinetics due to its weak adsorption and low coordination number. Strong M-C interactions (e.g., Ni-doped Cu) anchor *CO at dopant sites, suppressing migration and increasing C-C coupling barriers. Conversely, weak M-C interactions (e.g., Zn-doped Cu) destabilize *CO adsorption, enabling its migration between Cu sites and reducing C-C coupling energy barriers compared to pristine Cu. We propose an assisted-diffusion mechanism in which dopants with weak M-C interactions promote *CO migration for C-C coupling by acting as diffusion mediators rather than active adsorption sites, thereby enhancing the Faraday efficiency of the overall multicarbon product. These findings provide atomic-scale insights for designing high-activity Cu-based SAAs via the targeted modulation of dopant-C interactions.