Water clustering modulates activity and enables hydrogenated product formation during carbon monoxide electroreduction in aprotic media

Water solvation plays a critical role in a wide range of electrochemical transformations, but its role is often convoluted since it is typically used as both solvent and proton source. Here, we experimentally control water speciation and activity using aprotic solvent media during carbon monoxide reduction reaction (CORR). Remarkably, we show that aprotic solvents that support microheterogeneous water-water clusters leads to significant amounts of CORR products (methane and ethylene) with a maximum ethylene Faradaic efficiency of 22% in acetonitrile (χH2O = 0.2); the first report of heterogeneous CORR to C2+ products using water as a proton source in an aprotic solvent. In contrast, microhomogeneous systems – where water integrates into the solvents’ intermolecular binding network and has lower activity – primarily support undesired hydrogen evolution reaction (HER). Insights gained expand our understanding of water activity and nonaqueous electrolyte design for other important transformations reactions beyond CO reduction such as CO2RR and HER.