In all cases, the cations were found to stabilize CO 2 and COOH intermediates by at least 0.5 eV and 0.4 eV respectively (Figure (a): DFT and AIMD). This is consistent with previous works and indicates that the cation greatly aids in activating CO 2 and keeping it adsorbed on the surface. In particular, the O-C-O bond angle decreases from the 180°in the gas phase to around 135°in presence of the cation, which further facilitates the first proton-coupled electron transfer (PCET) to form COOH. Additionally, we have tested the influence of potential on binding energies of surface intermediates using Grand Canonical DFT using VASP-sol++ for the Ag(111)-K + system. Except for CO 2 , we see that the binding energies of reaction intermediates in the CO pathway shift within 0.17 eV across a 1.5 V potential range (Figure ). The CO 2 binding energy shifts with a slope of 0.44 eV/V, in-line with greater number of excess electrons needed to maintain the fixed potential as compared to the clean slab. The implications of these shifts on CO current densities is discussed in the following section.