Mesoporous PdAg Nanospheres for Stable Electrochemical CO2 Reduction to Formate

• Published in: Advanced materials (Weinheim) Vol. 32; no. 30
• Main Authors: Zhou, Yuan, Zhou, Rui, Zhu, Xiaorong, Han, Na, Song, Bin, Liu, Tongchao, Hu, Guangzhi, Li, Yafei, Lu, Jun, Li, Yanguang
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01-07-2020
• Subjects: Aqueous solutions; Carbon dioxide; Carbon monoxide poisoning; Dioctadecyl dimethyl ammonium chloride; Electrochemical analysis; electrochemical CO2 reduction; formate; Materials science; mesoporous nanospheres; Nanospheres; Palladium; palladium–silver alloys; Reduction; Selectivity; Silver; stability; Surface stability
• ISSN: 0935-9648; 1521-4095
• DOI: 10.1002/adma.202000992

Palladium is a promising material for electrochemical CO2 reduction to formate with high Faradaic efficiency near the equilibrium potential. It unfortunately suffers from problematic operation stability due to CO poisoning on surface. Here, it is demonstrated that alloying is an effective strategy to alleviate this problem. Mesoporous PdAg nanospheres with uniform size and composition are prepared from the co‐reduction of palladium and silver precursors in aqueous solution using dioctadecyldimethylammonium chloride as the structure‐directing agent. The best candidate can initiate CO2 reduction at zero overpotential and achieve high formate selectivity close to 100% and great stability even at <‐0.2 V versus reversible hydrogen electrode. The high selectivity and stability are believed to result from the electronic coupling between Pd and Ag, which lowers the d‐band center of Pd and thereby significantly enhances its CO tolerance, as evidenced by both electrochemical analysis and theoretical simulations.
Mesoporous PdAg nanospheres can enable electrochemical CO2 reduction to formate with high activity, selectivity, and, most remarkably, excellent stability superior to most previous reports. The great performance is believed to arise from the strong electronic coupling between Pd and Ag upon alloying, which effectively alleviates the CO poisoning on surface.