Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO2 Electroreduction

• Published in: Journal of the American Chemical Society Vol. 144; no. 1; pp. 259 - 269
• Main Authors: Wu, Zhi-Zheng, Zhang, Xiao-Long, Niu, Zhuang-Zhuang, Gao, Fei-Yue, Yang, Peng-Peng, Chi, Li-Ping, Shi, Lei, Wei, Wen-Sen, Liu, Ren, Chen, Zhi, Hu, Shaojin, Zheng, Xiao, Gao, Min-Rui
• Format: Journal Article
• Language: English
• Published: American Chemical Society 12.01.2022
• Subjects: activation energy; adsorption; carbon dioxide; catalysts; dimerization; electrosynthesis; feedstocks
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.1c09508

The electrosynthesis of valuable multicarbon chemicals using carbon dioxide (CO2) as a feedstock has substantially progressed recently but still faces considerable challenges. A major difficulty lines in the sluggish kinetics of forming carbon–carbon (C–C) bonds, especially in neutral media. We report here that oxide-derived copper crystals enclosed by six {100} and eight {111} facets can reduce CO2 to multicarbon products with a high Faradaic efficiency of 74.9 ± 1.7% at a commercially relevant current density of 300 mA cm–2 in 1 M KHCO3 (pH ∼ 8.4). By combining the experimental and computational studies, we uncovered that Cu(100)/Cu(111) interfaces offer a favorable local electronic structure that enhances *CO adsorption and lowers C–C coupling activation energy barriers, performing superior to Cu(100) and Cu(111) surfaces, respectively. On this catalyst, no obvious degradation was observed at 300 mA cm–2 over 50 h of continuous operation.