Contrasting Views of the Electric Double Layer in Electrochemical CO Reduction: Continuum Models vs Molecular Dynamics.

In the field of electrochemical CO reduction, both continuum models and molecular dynamics (MD) models have been used to understand the electric double layer (EDL). MD often focuses on the region within a few nm of the electrode, while continuum models can span up to the device level (cm). Still, both methods model the EDL, and for a cohesive picture of the CO electrolysis system, the two methods should agree in the regions where they overlap length scales. To this end, we make a direct comparison between state-of-the-art continuum models and classical MD simulations under the conditions of CO reduction on a Ag electrode. For continuum modeling, this includes the Poisson-Nernst-Planck formulation with steric (finite ion size) effects, and in MD the electrode is modeled with the constant potential method. The comparison yields numerous differences between the two modeling methods. MD shows cations forming two adsorbed layers, including a fully hydrated outer layer and a partial hydration layer closer to the electrode surface. The strength of the inner adsorbed layer increases with cation size (Li < Na < K < Cs) and with more negative applied potentials. Continuum models that include steric effects predict CO to be mostly excluded within 1 nm of the cathode due to tightly packed cations, yet we find little evidence to support these predictions from the MD results. In fact, MD shows that the concentration of CO increases within a few Å of the cathode surface due to interactions with the Ag electrode, a factor not included in continuum models. The EDL capacitance is computed from the MD results, showing values in the range of 7-9 μF cm, irrespective of the electrolyte concentration, cation identity, or applied potential. The direct comparison between the two modeling methods is meant to show the areas of agreement and disagreement between the two views of the EDL, so as to improve and better align these models.