Copper sulfide derived nanoparticles supported on carbon for the electrochemical reduction of carbon dioxide

Abstract

The electrocatalytic reduction of CO₂ to produce sustainable fuels and chemicals is attracting great attention. Cu-based catalysts can lead to the production of a range of different molecules, and interestingly the product selectivity strongly depends on the preparation history, although it is not fully understood yet why. We report a novel strategy that allowed us to prepare Cu nanoparticle on carbon catalysts with similar morphologies, but prepared by in-situ reduction of either supported CuS, Cu₂S or CuO nanoparticles. For the first time the evolution of the Cu species was followed under CO₂ and H⁺ reduction conditions using in-situ X-ray absorption spectroscopy. Excellent electrochemical contact between the Cu-based nanoparticles, the carbon support and the carbon-paper substrate was observed, resulting in metallic Cu as the predominant phase under typical electrochemical CO₂ reduction conditions. Even covering less than 4% of the H₂ producing carbon support with Cu-sulfide derived nanoparticles allowed to steer the selectivity to a maximum of 12% Faradaic efficiency for the production of formate. Clear differences between the catalysts derived from CuS, Cu₂S or CuO nanoparticles were observed, which was ascribed to the presence of residual sulfur in the catalysts.