The increasing use of metallic nanoparticles (NPs) is significantly advancing the field of electrocatalysis. In particular, Cu/Ag bimetallic interfaces are widely used to enhance the electrochemical CO2 reduction reaction (eCO2RR) toward CO and, more recently, C2 products. However, drastic changes in the product distribution and performance when Cu@Ag core-shell configurations are used can often be observed under electrochemical reaction conditions, especially during the first few minutes of the reaction. Possible structural changes that generate these observations remain underexplored; therefore, the structure-property relationship is hardly understood. In this study, we use electron tomography to investigate the structural transformation mechanism of Cu@Ag core-shells NPs during the critical first minutes of the eCO2RR. In this manner, we found that the crystallinity of the Cu seed determines whether the formation of a complete and homogeneous Ag shell is possible. Moreover, by tracking the particles’ transformations, we conclude that modifications of the Cu-Ag interface and Cu2O enrichment at the surface of the NPs are key factors contributing to the product generation changes. These insights provide a better understanding of how bimetallic core-shell NPs transform under electrochemical conditions.
Chemistry of Materials
Centrum Wiskunde & Informatica, Amsterdam (CWI), The Netherlands

Arenas Esteban, D, Pacquets, L, Choukroun, D, Hoekx, S, Kadu, A.A, Schalck, J, … Bals, S. (2023). 3D characterization of the structural transformation undergone by Cu@Ag Core-Shell Nanoparticles following CO2 reduction reaction. Chemistry of Materials, 35(17), 6682–6691. doi:10.1021/acs.chemmater.3c00649