Solvent Effect on Electrochemical CO(2) Reduction Reaction on Nanostructured Copper Electrodes

[Image: see text] The electrochemical reduction of CO(2) (CO(2)RR) is a sustainable alternative for producing fuels and chemicals, although the production of highly desired hydrocarbons is still a challenge due to the higher overpotential requirement in combination with the competitive hydrogen evolution reaction (HER). Tailoring the electrolyte composition is a possible strategy to favor the CO(2)RR over the HER. In this work we studied the solvent effect on the CO(2)RR on a nanostructured Cu electrode in acetonitrile solvent with different amounts of water. Similar to what has been observed for aqueous media, our online gas chromatography results showed that CO(2)RR in acetonitrile solvent is also structure-dependent, since nanocube-covered copper (CuNC) was the only surface (in comparison to polycrystalline Cu) capable of producing a detectable amount of ethylene (10% FE), provided there is enough water present in the electrolyte (>500 mM). In situ Fourier Transform Infrared (FTIR) spectroscopy showed that in acetonitrile solvent the presence of CO(2) strongly inhibits HER by driving away water from the interface. CO is by far the main product of CO(2)RR in acetonitrile (>85% Faradaic efficiency), but adsorbed CO is not detected. This suggests that in acetonitrile media CO adsorption is inhibited compared to aqueous media. Remarkably, the addition of water to acetonitrile has little quantitative and almost no qualitative effect on the activity and selectivity of the CO(2)RR. This indicates that water is not strongly involved in the rate-determining step of the CO(2)RR in acetonitrile. Only at the highest water concentrations and at the CuNC surface, the CO coverage becomes high enough that a small amount of C(2+) product is formed.