Mediating CO2 Electroreduction Activity and Selectivity over Atomically Precise Copper Clusters

Abstract Atomically precise copper clusters are highly desirable catalysts for electrocatalytic CO 2 reduction reaction (CO 2 RR) and provide an ideal platform for elaborating structure–activity relationships. However, systematic comparative studies of Cu cluster isomers for electrocatalytic CO 2 RR are lacking because they are challenging to synthesize. A group of structurally precise Cu 8 cluster isomers with different core structures (cube‐ and ditetrahedron‐shaped) were developed and investigated for highly active and selective CO 2 reduction. Electrocatalytic measurements showed that the ditetrahedron‐shaped Cu 8 cluster exhibited a higher FE HCOOH (≈92 %) at −1.0 V and higher selectivity than the cube‐shaped cluster. Theoretical investigations revealed different levels of competitiveness with the hydrogen evolution reaction on the respective core‐shaped Cu 8 clusters and decreased free energies for the adsorbed HCOO* intermediates on the ditetrahedron‐shaped Cu 8 clusters.