文献类型：期刊文献

英文题名：Phosphorus-Mediated Oxygen Vacancy Engineering in Cu2O for Highly Selective CO2 Electroreduction to Multicarbon Products

作者：Mao, Xiaoqing[1];Guo, Zhongyuan[2];Yang, Saiwu[1];Shen, Yongjun[1];Wei, Li[3];Li, Congcong[1];Jiang, Hongliang[1];Li, Hao[1];Li, Huihui[1];Li, Chunzhong[1]

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]Univ Sydney, Sch Chem & Biomol Engn, Sydney, NSW 2006, Australia

年份：2025

卷号：19

期号：23

起止页码：21669

外文期刊名：ACS NANO

收录：;EI(收录号：20252418576211);WOS:【SCI-EXPANDED(收录号:WOS:001503719900001)】；

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), JSPS KAKENHI (JP25K01737), and the Postdoctoral Fellowship Program of CPSF under the Grant Number (GZC20241472), and the AIMR Fusion Research. The authors thank 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：oxygen vacancy; P-doping mediation; CO2 reduction reaction; *CO intermediate; multicarbonproducts

摘要：Copper (Cu)-based electrocatalysts are acknowledged as pivotal catalysts for the electroreduction of CO2 into multicarbon (C2+) products; however, achieving high C2+ selectivity at industrial-level current densities remains a significant challenge. Herein, we propose a "phosphorus (P)-doping mediation" strategy to introduce an oxygen vacancy into the Cu2O lattice, resulting in a C2+ Faradaic efficiency of 87.0% at a partial current density of 347.8 mAcm(-2). Mechanistic studies unveil that P dopants dynamically regulate the formation of high-density oxygen vacancies in Cu2O lattices through the formation and subsequent detachment of the P-O bond, predominantly in the form of phosphite within an aqueous electrolyte environment. In situ Raman spectroscopy coupled with density functional theory calculations further reveals that the OV-rich structure optimizes the surface coverage of active *CO intermediates. This microenvironment not only accelerates the energetically favorable C-C coupling pathway but also suppresses competitive protonation reactions, thereby breaking the intrinsic activity-selectivity trade-off. Our work provides atomic-level insights into defect dynamics manipulation for designing high-rate CO2 conversion systems.