Understanding Adsorption of Organics on Pt(111) in the Aqueous Phase: Insights from DFT Based Implicit Solvent and Statistical Thermodynamics Models.

Adsorption of organics in the aqueous phase is an area which is experimentally difficult to measure, while computational techniques require extensive configurational sampling of the solvent and adsorbate. This is exceedingly computationally demanding, which excludes its routine use. If implicit solvent could be applied instead, this would dramatically reduce the computational cost as configurational sampling of solvent is not needed. Here, using statistical thermodynamic arguments and DFT calculations with implicit solvent models, we show that semiquantitative values for the free energy and entropy change of adsorption in the aqueous phase (Δ G ads solv and Δ S ads solv ) for small organics can be calculated, for a range of coverages. We parametrize the soft sphere based solute dielectric cavity to an approximated free energy of solvation for a single Pt atom at the (111) facet, forming upper and lower bounds based on the entropy of water at the aqueous metal interface (Δ G solv (Pt) = -4.35 to -7.18 kJ mol -1 ). This captures the decrease in Δ G ads solv compared to the free energy of adsorption in the vacuum phase (Δ G ads vac ), while solvent models with electron density based cavities fail to do so. For a range of oxygenated aromatics, the adsorption energetics using horizontal gas phase geometries significantly overestimate Δ G ads solv compared to experiment by ∼100 kJ mol -1 , but they agree with ab initio MD simulations using similar geometries. This suggests oxygenated aromatic compounds adsorb perpendicular to the metallic surface, while the Δ G ads solv for vertical geometries of furfural and cyclohexanol agree to within 20 kJ mol -1 of experimental studies. The proposed techniques provide an inexpensive toolset for validation and prediction of adsorption energetics on solvated metallic surfaces, which could be further validated by the future availability of more experimental measurements for the aqueous entropy/free energy of adsorption.