Gerhardtite as a Precursor to an Efficient CO-to-Acetate Electroreduction Catalyst

• Published in: Journal of the American Chemical Society Vol. 145; no. 44; pp. 24338 - 24348
• Main Authors: Wu, Zhi-Zheng, Zhang, Xiao-Long, Yang, Peng-Peng, Niu, Zhuang-Zhuang, Gao, Fei-Yue, Zhang, Yu-Cai, Chi, Li-Ping, Sun, Shu-Ping, DuanMu, Jing-Wen, Lu, Pu-Gan, Li, Ye-Cheng, Gao, Min-Rui
• Format: Journal Article
• Language: English
• Published: American Chemical Society 08.11.2023
• Subjects: acetates; adsorption; catalysts; copper; electrochemistry; gerhardtite; irradiation
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.3c09255

Carbon–carbon coupling electrochemistry on a conventional copper (Cu) catalyst still undergoes low selectivity among many different multicarbon (C2+) chemicals, posing a grand challenge to achieve a single C2+ product. Here, we demonstrate a laser irradiation synthesis of a gerhardtite mineral, Cu2(OH)3NO3, as a catalyst precursor to make a Cu catalyst with abundant stacking faults under reducing conditions. Such structural perturbation modulates electronic microenvironments of Cu, leading to improved d-electron back-donation to the antibonding orbital of *CO intermediates and thus strengthening *CO adsorption. With increased *CO coverage on the defect-rich Cu, we report an acetate selectivity of 56 ± 2% (compared to 31 ± 1% for conventional Cu) and a partial current density of 222 ± 7 mA per square centimeter in CO electroreduction. When run at 400 mA per square centimeter for 40 h in a flow reactor, this catalyst produces 68.3 mmol of acetate throughout. This work highlights the value of a Cu-containing mineral phase in accessing suitable structures for improved selectivity to a single desired C2+ product.