Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO2 Revealed by In Situ X‐Ray Spectroscopy

• Published in: Advanced sustainable systems (Online) Vol. 7; no. 5
• Main Authors: Velasco‐Vélez, Juan‐Jesús, Poon, Jeffrey, Gao, Dunfeng, Chuang, Cheng‐Hao, Bergmann, Arno, Jones, Travis E., Haw, Shu‐Chih, Chen, Jin‐Ming, Carbonio, Emilia, Mom, Rik V., Ivanov, Danail, Arrigo, Rosa, Cuenya, Beatriz Roldan, Knop‐Gericke, Axel, Schlögl, Robert
• Format: Journal Article
• Language: English
• Published: 01.05.2023
• Subjects: CO2RR; copper alloys; electrocatalysis; energy conversion; in situ spectroscopy
• ISSN: 2366-7486; 2366-7486
• DOI: 10.1002/adsu.202200453

Advanced in situ X‐ray absorption spectroscopy characterization of electrochemically co‐electrodeposited bi‐element copper alloy electrodes shows that zinc yields the formation of a stable cationic Cu species during the electroreduction of CO2 at high cathodic polarization. In contrast, the formation/stabilization of cationic Cu species in copper oxides, or doping Cu with another element, like Ni, is not possible. It is found that the pure and mixed Cu:Zn electrodes behave similarly in term of electrocatalytic selectivity to multi‐carbon products. At higher Zn concentrations the electrode behaves like the pure Zn catalyst, which indicates that the Cu cationic species do not have a significant influence on the selectivity to multi‐carbon products. It is found that in the non‐monotonically distribution of products is dominated in term of surface energy in which copper prefers the surface. Otherwise, this work highlights the importance of in situ characterization to uncover the mechanisms mediating the catalytic reactions in contrast to ex situ or post mortem analysis, which can be a source of misinterpretation. Advanced in situ X‐ray absorption spectroscopy characterization ofelectrochemically co‐electrodeposited copper/zinc alloy shows the formation of stablecationic copper species during the electroreduction of carbon dioxide. Meanwhile, the copper cationic species are not formed in other co‐electrodeposited alloys as copper/nickel. The non‐monotonically distribution of products indicates no influence of the cationic copper species in the reaction pathway.