Abstract

The effect of tetraalkylammonium cation (TAA + ) chain length on CO 2 electroreduction is investigated on an Ag electrode in a DMF solution. Linear sweep voltammetric (LSV) studies show that the onset potentials of CO 2 reduction move to increasingly negative potentials upon increasing the alkyl chain length of the tetraalkylammonium cation of the supporting electrolyte. Density functional theory (DFT) computations indicate that the onset potential of CO 2 reduction is dependent on the strength of ion pairing between TAA + cation and the electrogenerated CO 2 . − . CO 2 disturbance experiments reveal that the peak current of CO 2 reduction is determined by the quantity of TAA + cation adsorbed on the Ag surface. • The assessment of the effects of TAA + cations on CO 2 reduction is established. • The onset potential of CO 2 reduction is dependent on the strength of ion pairing. • The peak current of CO 2 reduction is determined by the quantity of the adsorbed TAA + cation.

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