Symmetry Breaking Enhancing the Activity of Electrocatalytic CO2 Reduction on an Icosahedron‐Kernel Cluster by Cu Atoms Regulation

Abstract Recently, CO 2 hydrogenation had a new breakthrough resulting from the design of catalysts to effectively activate linear CO 2 with symmetry‐breaking sites. However, understanding the relationship between symmetry‐breaking sites and catalytic activity at the atomic level is still a great challenge. In this study, a set of gold‐copper alloy Au 13 Cu x (x=0–4) nanoclusters were used as research objects to show the symmetry‐controlled breaking structure on the surface of nanoclusters with the help of manipulability of the Cu atoms. Among them, Au 13 Cu 3 nanocluster displays the highest degree of symmetry‐breaking on its crystal structure compared with the other nanoclusters in the family. Where the three copper atoms occupying the surface of the icosahedral kernel unevenly with one copper atom is coordinately unsaturated (CuS 2 motif relative to CuS 3 motif). As expected, Au 13 Cu 3 has an excellent hydrogenation activity of CO 2 , in which the current density is as high as 70 mA cm −2 (−0.97 V) and the maximum FE CO reaches 99 % at −0.58 V. Through the combination of crystal structures and theoretical calculations, the excellent catalytic activity of Au 13 Cu 3 is revealed to be indeed closely related to its asymmetric structure.