The nature of active sites for carbon dioxide electroreduction over oxide-derived copper catalysts

The active sites for CO₂ electroreduction (CO₂R) to multi-carbon (C₂₊) products over oxide-derived copper (OD-Cu) catalysts are under long-term intense debate. This paper describes the atomic structure motifs for product-specific active sites on OD-Cu catalysts in CO₂R. Herein, we describe realistic OD-Cu surface models by simulating the oxide-derived process via the molecular dynamic simulation with neural network (NN) potential. After the analysis of over 150 surface sites through NN potential based high-throughput testing, coupled with density functional theory calculations, three square-like sites for C-C coupling are identified. Among them, Σ3 grain boundary like planar-square sites and convex-square sites are responsible for ethylene production while step-square sites, i.e. n(111) × (100), favor alcohols generation, due to the geometric effect for stabilizing acetaldehyde intermediates and destabilizing Cu-O interactions, which are quantitatively demonstrated by combined theoretical and experimental results. This finding provides fundamental insights into the origin of activity and selectivity over Cu-based catalysts and illustrates the value of our research framework in identifying active sites for complex heterogeneous catalysts.