Enhancing CO2 Electroreduction to Ethanol on Copper–Silver Composites by Opening an Alternative Catalytic Pathway

A fundamental question in the electrochemical CO2 reduction reaction (CO2RR) is how to rationally control the catalytic selectivity. For instance, adding a CO-producing metal like Ag to Cu shifts the latter’s CO2RR selectivity towards C2 products, but the underlying cause of the change is unclear. Herein, we show that CuAg boundaries facilitate the coupling of carbon-containing species to give ethanol, through an otherwise closed pathway. Oxide-derived Cu nanowires mixed with 20 nm Ag particles (Cu:Ag mole ratio of 1:20) reduce CO2 to ethanol with a current density of -4.1 mA/cm2 at -1.1 V vs. RHE and ethanol/ethylene Faradaic efficiency ratio of 1.1. These figures of merit are respectively 5 and 3 times higher than those for pure oxide-derived Cu nanowires. CO2RR using different Ag:Cu ratios and Ag particle sizes reveals that ethanol production scales with CO production on the Ag sites and the abundance of CuAg boundaries, and, very interestingly, without significant modifications to ethylene formation. Computational modelling shows selective ethanol evolution via Langmuir-Hinshelwood *CO + *CHx (x = 1, 2) coupling at CuAg boundaries, and that the formation of energy-intensive CO dimers is circumvented.