Steering the Reconstruction of Oxide-Derived Cu by Secondary Metal for Electrosynthesis of <i>n</i>-Propanol from CO

Abstract

As fuel and an important chemical feedstock, <i>n</i>-propanol is highly desired in electrochemical CO₂/CO reduction on Cu catalysts. However, the precise regulation of the Cu localized structure is still challenging and poorly understood, thus hindering the selective <i>n</i>-propanol electrosynthesis. Herein, by decorating Au nanoparticles (NPs) on CuO nanosheets (NSs), we present a counterintuitive transformation of CuO into undercoordinated Cu sites locally around Au NPs during CO reduction. In situ spectroscopic techniques reveal the Au-steered formation of abundant undercoordinated Cu sites during the removal of oxygen on CuO. First-principles accuracy molecular dynamic simulation demonstrates that the localized Cu atoms around Au tend to rearrange into disordered layer rather than a Cu (111) close-packed plane observed on bare CuO NSs. These Au-steered undercoordinated Cu sites facilitate CO binding, enabling selective electroreduction of CO into <i>n</i>-propanol with a high Faradaic efficiency of 48% in a flow cell. This work provides new insight into the regulation of the oxide-derived catalysts reconstruction with a secondary metal component.