Hybrid Cu0 and Cux+ as Atomic Interfaces Promote High‐Selectivity Conversion of CO2 to C2H5OH at Low Potential

Abstract The mixing of charge states of metal copper catalysts may lead to a much improved reactivity and selectivity toward multicarbon products for CO 2 reduction. Here, an electrocatalyst model composed of copper clusters supported on graphitic carbon nitride (g‐C 3 N 4 ) is proposed; the connecting Cu atoms with g‐C 3 N 4 can be oxidized to Cu x + due to substantial charge transfer from Cu to N atoms, while others stay as Cu 0 . It is revealed that CO 2 can be captured and reduced into *CO on the Cu t 0 site, owing to its zero oxidation state. More importantly, C–C coupling reaction of two *CHO species on the Cu t 0 –Cu b x + atomic interface can occur with a rather low kinetic barrier of 0.57 eV, leading to the formation of the final C 2 product, namely, C 2 H 5 OH. During the whole process, the limiting potential is just 0.68 V. These findings may open a new avenue for CO 2 reduction into high‐value fuels and chemicals.