Influence of an electrified interface on the entropy and energy of solvation of methanol oxidation intermediates on platinum(111) under explicit solvation

Abstract

Liquid water and electric fields play significant roles in phenomena occurring at catalytic and electrocatalytic interfaces; however, how their interplay influences interfacial energetics remains uncertain. Electric fields control the orientations of water molecules, which we hypothesized would influence the solvation thermodynamics of surface species. To explore this hypothesis, we used multiscale simulations involving density functional theory and classical molecular dynamics. We computed the energies and entropies of solvation of surface species on Pt(111), specifically, adsorbed CH₃OH, COH, and CO, which are intermediates in the pathway of methanol oxidation, in the presence of electric fields spanning −0.5 to +0.5 V Å⁻¹. We found that both the energy and entropy of solvation depend on the strength and direction of the field, with the entropy of solvation being significantly impacted. Both the energy and entropy dependence on the field can be ascribed to water molecule orientations. Specifically, more positive fields orient water molecules so that they can more effectively hydrogen bond with surface species, which strengthens the energies of solvation. However, at more negative fields, competition with the surface species causes interfacial water molecules to reorient, which leads to disorder in the water structure and hence increased entropy.