Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule–metal catalyst interfaces

Electrochemical conversion of CO2 into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Here we present a cooperative catalyst design of molecule–metal catalyst interfaces with the goal of producing a reaction-intermediate-rich local environment, which improves the electrosynthesis of ethanol from CO2 and H2O. We implement the strategy by functionalizing the copper surface with a family of porphyrin-based metallic complexes that catalyse CO2 to CO. Using density functional theory calculations, and in situ Raman and operando X-ray absorption spectroscopies, we find that the high concentration of local CO facilitates carbon–carbon coupling and steers the reaction pathway towards ethanol. We report a CO2-to-ethanol Faradaic efficiency of 41% and a partial current density of 124 mA cm−2 at −0.82 V versus the reversible hydrogen electrode. We integrate the catalyst into a membrane electrode assembly-based system and achieve an overall energy efficiency of 13%. Electrochemical conversion of CO2 into liquid fuels, powered by renewable electricity, offers one means to address the need for the storage of intermittent renewable energy. Now, Sargent and co-workers present a cooperative catalyst design of molecule–metal interfaces to improve the electrosynthesis of ethanol from CO2 by producing a reaction-intermediate-rich local environment.