Operando insights into correlating CO coverage and Cu–Au alloying with the selectivity of Au NP-decorated Cu2O nanocubes during the electrocatalytic CO2 reduction†

Electrochemical reduction of CO₂ (CO₂RR) is an attractive technology to reintegrate the anthropogenic CO₂ back into the carbon cycle driven by a suitable catalyst. This study employs highly efficient multi-carbon (C₂₊) producing Cu₂O nanocubes (NCs) decorated with CO-selective Au nanoparticles (NPs) to investigate the correlation between a high CO surface concentration microenvironment and the catalytic performance. Structure, morphology and near-surface composition are studied via operando X-ray absorption spectroscopy and surface-enhanced Raman spectroscopy, operando high-energy X-ray diffraction as well as quasi in situ X-ray photoelectron spectroscopy. These operando studies show the continuous evolution of the local structure and chemical environment of our catalysts during reaction conditions. Along with its alloy formation, a CO-rich microenvironment as well as weakened average CO binding on the catalyst surface during CO₂RR is detected. Linking these findings to the catalytic function, a complex compositional interplay between Au and Cu is revealed in which higher Au loadings primarily facilitate CO formation. Nonetheless, the strongest improvement in C₂₊ formation appears for the lowest Au loadings, suggesting a beneficial role of the Au–Cu atomic interaction for the catalytic function in CO₂RR. This study highlights the importance of site engineering and operando investigations to unveil the electrocatalyst's adaptations to the reaction conditions, which is a prerequisite to understand its catalytic behavior.