The Effect of the Tetraalkylammonium Cation in the Electrochemical CO 2 Reduction Reaction on Copper Electrode.

Aprotic organic solvents such as acetonitrile offer a potential solution to promote electrochemical CO 2 reduction over the competing hydrogen evolution reaction. Tetraalkylammonium cations (TAA + ) are widely used as supporting electrolytes in organic media due to their high solubility and conductivity. The alkyl chain length of TAA + cations is known to influence electron transfer processes in electrochemical systems by the adsorption of TAA + , causing modifications of the double layer. In this work, we elucidate the influence of the cation chain length on the mechanism and selectivity of the CO 2 RR reaction under controlled dry and wet acetonitrile conditions on copper cathodes. We find that the hydrophobic hydration character of the cation, which can be tuned by the chain length, has an effect on product distribution, altering the reaction pathway. Under dry conditions, smaller cations (TEA + ) preferentially promote oxalate production via dimerization of the CO 2 ·- intermediate, whereas formate is favored in the presence of water via protonation reaction. Larger cations (TBA + > TPA + > TEA + ) favor the generation of CO regardless of water content. In situ FTIR analysis showed that TBA + cations are able to stabilize adsorbed CO more effectively than TEA + , explaining why larger cations generate a higher proportion of CO. Our findings also suggest that higher cation concentrations suppress hydrogen evolution, particularly with larger cations, highlighting the role of cation chain length size and hydrophobic hydration shell.