Operando Insight into the Correlation between the Structure and Composition of CuZn Nanoparticles and Their Selectivity for the Electrochemical CO₂ Reduction

Bimetallic CuZn catalysts have been recently proposed as alternatives in order to achieve selectivity control during the electrochemical reduction of CO₂ (CO₂RR). However, fundamental understanding of the underlying reaction mechanism and parameters determining the CO₂RR performance is still missing. In this study, we have employed size-controlled (∼5 nm) Cu₁₀₀–ₓZnₓ nanoparticles (NPs) supported on carbon to investigate the correlation between their structure and composition and catalytic performance. By tuning the concentration of Zn, a drastic increase in CH₄ selectivity [∼70% Faradaic efficiency (F.E.)] could be achieved for Zn contents from 10 to 50, which was accompanied by a suppression of the H₂ production. Samples containing a higher Zn concentration displayed significantly lower CH₄ production and an abrupt switch in the selectivity to CO. Lack of metal leaching was observed based on quasi in situ X-ray photoelectron spectroscopy (XPS). Operando X-ray absorption fine structure (XAFS) spectroscopy measurements revealed that the alloying of Cu atoms with Zn atoms takes place under reaction conditions and plays a determining role in the product selectivity. Time-dependent XAFS analysis showed that the local structure and chemical environment around the Cu atoms continuously evolve during CO₂RR for several hours. In particular, cationic Zn species initially present were found to get reduced as the reaction proceeded, leading to the formation of a CuZn alloy (brass). The evolution of the Cu–Zn interaction with time during CO₂RR was found to be responsible for the change in the selectivity from CH₄ over Cu-ZnO NPs to CO over CuZn alloy NPs. This study highlights the importance of having access to in depth information on the interplay between the different atomic species in bimetallic NP electrocatalysts under operando reaction conditions in order to understand and ultimately tune their reactivity.