Electroreduction of CO2 on Cu Clusters: The Effects of Size, Symmetry, and Temperature

Abstract Copper is a potential electrocatalyst for CO 2 electroreduction, although controlling the selectivity towards hydrocarbons and CO is still a major challenge. It is known that Cu nanoparticles show a better performance for CO 2 electro‐reduction than bulk Cu. However, the roles of the size and symmetry of the Cu clusters as well as the temperature in the CO 2 ‐reduction process remain elusive, which hinders the development of advanced catalysts. In this study, the density functional theory (DFT) method is applied to investigate these factors. We find that the decrease of icosahedron Cu clusters’ size but the increase of truncated octahedron Cu clusters’ size contributes to the selectivity of CO 2 reduction. In addition, the symmetry of Cu clusters modulates the selectivity of CO 2 reduction at room temperature: the (111)‐like surfaces prefer to produce hydrocarbons but the synergistic effect between (100)‐ and (111)‐ like ones favors the formation of CO, which are in reasonable agreement with the experimental measurements that distinct products are detected on different Cu nanoparticles during CO 2 reduction. We also note that the increase of temperature is favorable to CO production. Our findings not only contribute to a thorough understanding of CO 2 reduction on Cu clusters, but also provide clues for designing catalysts in future experiments.