Electronic effects determine the selectivity of planar Au-Cu bimetallic thin films for electrochemical CO2 reduction

Au-Cu bimetallic thin films with controlled composition were fabricated by magnetron sputtering co-deposition, and their performance for the electrocatalytic reduction of CO2 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 the Au atomic ratio, leading to a weakened binding energy of *CO, which is consistent with low CO coverage observed in CO stripping experiments. The decrease of the *CO binding strength results in the enhanced catalytic activity for CO formation with the increase of Au content. In addition, it was observed that copper oxide/hydroxide species are less stable on Au-Cu surfaces compared to those on pure Cu surface, where the surface oxophilicity could be critical to tuning the binding strength of *OCHO. These results imply that the altered electronic structure could explain the decreased formation of HCOO─ on these alloys. In general, the formation of CO and HCOO─ as main CO2 reduction products on planar Au-Cu alloys followed the shift of d-band center, which indicates the electronic effect is the major governing factor for the electrocatalytic activity of CO2 reduction on Au-Cu bimetallic thin films.