Facet- switching of rate- determining step on copper in CO2-to- ethylene electroreduction

• 成果类型: Article
• 署名作者: Zhang, Yu-Cai; Zhang, Xiao-Long; Wu, Zhi-Zheng; Niu, Zhuang-Zhuang; Chi, Li-Ping; Gao, Fei-Yue; Yang, Peng-Peng; Wang, Ye-Hua; Yu, Peng-Cheng; Duanmu, Jing-Wen; Sun, Shu-Ping; Gao, Min-Rui
• 署名单位: Chinese Academy of Sciences; University of Science & Technology of China, CAS
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-11616
• DOI: 10.1073/pnas.2400546121
• 发表日期: 2024-06-18
• 关键词: co reduction; conversion; ph

摘要

Reduction of carbon dioxide (CO2) by renewable electricity to produce multicarbon chemicals, such as ethylene (C2H4), continues to be a challenge because of insufficient Faradaic efficiency, low production rates, and complex mechanistic pathways. Here, we report that the rate-determining steps (RDS) on common copper (Cu) surfaces diverge in CO2 electroreduction, leading to distinct catalytic performances. Through a combination of experimental and computational studies, we reveal that C & horbar;C bond-making is the RDS on Cu(100), whereas the protonation of *CO with adsorbed water becomes rate-limiting on Cu(111) with a higher energy barrier. On an oxide-derived Cu(100)-dominant Cu catalyst, we reach a high C2H4 Faradaic efficiency of 72%, partial current density of 359 mA cm(-2), and long-term stability exceeding 100 h at 500 mA cm(-2), greatly outperforming its Cu(111)-rich counterpart. We further demonstrate constant C2H4 selectivity of >60% over 70 h in a membrane electrode assembly electrolyzer with a full-cell energy efficiency of 23.4%.