Competition between H and CO for Active Sites Governs Copper‐Mediated Electrosynthesis of Hydrocarbon Fuels

The dynamics of carbon monoxide on Cu surfaces was investigated during CO reduction, providing insight into the mechanism leading to the formation of hydrogen, methane, and ethylene, the three key products in the electrochemical reduction of CO2. Reaction order experiments were conducted at low temperature in an ethanol medium affording high solubility and surface‐affinity for carbon monoxide. Surprisingly, the methane production rate is suppressed by increasing the pressure of CO, whereas ethylene production remains largely unaffected. The data show that CH4 and H2 production are linked through a common H intermediate and that methane is formed through reactions among adsorbed H and CO, which are in direct competition with each other for surface sites. The data exclude the participation of solution species in rate‐limiting steps, highlighting the importance of increasing surface recombination rates for efficient fuel synthesis. Understanding hydrocarbon electrosynthesis: Copper can catalyze the reduction of CO2 and CO to hydrocarbons, but does so inefficiently and with poor selectivity. Kinetic measurements indicate that methane and hydrogen formation proceeds via rate‐limiting recombination of surface‐bound intermediates. Tuning the reaction rates between surface‐bound H and CO species, which compete for active sites, is essential for more efficient catalysis.