Electronic Effects Determine the Selectivity of Planar Au-Cu Bimetallic Thin Films for Electrochemical CO ₂ Reduction

Au-Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO ₂ was investigated. The uniform planar morphology served as a platform to evaluate the electronic effect isolated from morphological effects while minimizing geometric contributions. The catalytic selectivity and activity of Au-Cu alloys was found to be correlated with the variation of electronic structure that was varied with tunable composition. Notably, the d-band center gradually shifted away from the Fermi level with increasing Au atomic ratio, leading to a weakened binding energy ofCO, which is consistent with low CO coverage observed in CO stripping experiments. The decrease in theCO binding strength results in the enhanced catalytic activity for CO formation with the increase in Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au-Cu surfaces compared to those on the pure Cu surface, where the surface oxophilicity could be critical to tuning the binding strength ofOCHO. These results imply that the altered electronic structure could explain the decreased formation of HCOO ^- on the Au-Cu alloys. In general, the formation of CO and HCOO ^- as main CO ₂ reduction products on planar Au-Cu alloys followed the shift of the d-band center, which indicates that the electronic effect is the major governing factor for the electrocatalytic activity of CO ₂ reduction on Au-Cu bimetallic thin films.