Selective and Energy Efficient Electrocatalytic CO 2 ‐to‐Ethanol Conversion through Anion Modulation

• Published in: Angewandte Chemie International Edition Vol. 64; no. 35; p. e202506867
• Main Authors: Da, Yumin, Chen, Jie, Fan, Lei, Jiang, Rui, Xiao, Yukun, Wang, Meng, Chen, Ganwen, Tian, Zhangliu, Zhang, Hanqian, Jin, Hongqiang, Chen, Xiang, Ji, Chenrui, Xi, Shibo, Lum, Yanwei, Wang, Lei, Zhu, Tong, Zhang, Jia, Chen, Wei
• Format: Journal Article
• Language: English
• Published: Germany 25.08.2025
• Subjects: Ethanol; CO2 electroreduction; Anion modulation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202506867

Ethanol, with its high market value and stable global demand, stands out as an attractive product of electrocatalytic CO 2 reduction. However, achieving high ethanol selectivity and energy efficiency at industrial current densities remains challenging. In this study, we employed a blended anion modulation strategy to enhance the selectivity and energy efficiency of CO 2 ‐to‐ethanol conversion. The Cu 2 (OH) 3 F pre‐catalyst achieved Faradaic efficiencies of 50% and 93% for ethanol and C 2+ , respectively, at 700 mA cm −2 in a blended electrolyte consisting of 2 M KOH and 1 M KCl. Comprehensive electrochemical tests, combined with in situ characterizations and theoretical analysis, revealed that chloride and hydroxide increased *CO coverage for efficient C─C coupling. Moreover, hydroxide stabilizes the *CHCOH intermediate through hydrogen bonding with the adsorbed hydroxide on the catalyst surface, while Cl synergistically enhances its reactivity by promoting water dissociation toward the ethanol pathway.