Solvothermally-Prepared Cu₂ O Electrocatalysts for CO₂ Reduction with Tunable Selectivity by the Introduction of...

The electroreduction of CO₂ to fuels and chemicals is an attractive strategy for the valorization of CO₂ emissions. In this study, a Cu₂ O electrocatalyst prepared by a simple and potentially scalable solvothermal route effectively targeted CO evolution at low-to-moderate overpotentials [with a current efficiency for CO (CE_CO ) of ca. 60 % after 12 h at -0.6 V vs. reversible hydrogen electrode, RHE], and its selectivity was tuned by the introduction of p-block elements (In, Sn, Ga, Al) into the catalyst. SEM, HRTEM, and voltammetric analyses revealed that the Cu₂ O catalyst undergoes extensive surface restructuring (favorable for CO evolution) under the reaction conditions. The modification of Cu₂ O with Sn and In further enhanced the current efficiency (CE) for CO (ca. 75 % after 12 h at -0.6 V). In contrast, the introduction of Al altered the selectivity profile of the catalyst significantly, decreasing the selectivity toward CO but promoting the reduction of CO₂ to ethylene (CE≈7 %), n-propanol, and ethanol (CE≈2 % each) at -0.8 V vs. RHE. This result is related to a decreased reducibility of Al-doped Cu₂ O that might preserve Cu⁺ species (favorable for C₂ H₄ production) under the reaction conditions, which is supported by XRD, X-ray photoelectron spectroscopy, and H₂ temperature-programmed reduction observations.