Sn Dopants with Synergistic Oxygen Vacancies Boost CO₂ Electroreduction on CuO Nanosheets to CO at Low Overpotential

Abstract

Using the electrochemical CO₂ reduction reaction (CO₂RR) with Cu-based electrocatalysts to achieve carbon-neutral cycles remains a significant challenge because of its low selectivity and poor stability. Modulating the surface electron distribution by defects engineering or doping can effectively improve CO₂RR performance. Herein, we synthesize the electrocatalyst of V_o-CuO(Sn) nanosheets containing oxygen vacancies and Sn dopants for application in CO₂RR-to-CO. Density functional theory calculations confirm that the incorporation of oxygen vacancies and Sn atoms substantially reduces the energy barrier for *COOH and *CO intermediate formation, which results in the high efficiency, low overpotential, and superior stability of the CO₂RR to CO conversion. This electrocatalyst possesses a high Faraday efficiency (FE) of 99.9% for CO at a low overpotential of 420 mV and a partial current density of up to 35.22 mA cm^-2 at -1.03 V versus reversible hydrogen electrode (RHE). The FE_CO of V_o-CuO(Sn) could retain over 95% within a wide potential area from -0.48 to -0.93 V versus RHE. Moreover, we obtain long-term stability for more than 180 h with only a slight decay in its activity. Therefore, this work provides an effective route for designing environmentally friendly electrocatalysts to improve the selectivity and stability of the CO₂RR to CO conversion.