Elucidating Molecular Interactions in Glycerol Adsorption at the Metal–Water Interface with Density Functional Theory

Glycerol is an extremely versatile platform molecule for chemical and fuel production, as evidenced by successful demonstrations in electrochemical and thermochemical processes, where key catalytic chemistries occur at the solid-liquid interface. Despite the remarkable progress made in enriching the first-principles-based computational tool set to reveal and characterize solvent structures in the past decade, techniques for realistic and efficient molecular-level modeling to study aqueous-phase glycerol chemistry are still far from mature. Many aqueous-phase catalytic systems are deemed too complex for routine modeling because of their highly correlated structures at the heterogeneous solid-liquid interface. This invited feature article merges recent developments in quantum mechanical solvation models and oxygenated hydrocarbon conversion chemistry by revisiting the molecular interactions of adsorbed glycerol and its dehydrogenation intermediates at the water-metal interface. Explicit participation of water through the establishment of water-adsorbate, water-water, and water-metal interactions on Pt(111) was investigated using density functional theory. In periodic models, the adsorption favors networklike structures with adsorbates as nodal points linked by coadsorbed water molecules. We also showed that these adsorption patterns actually preserve the original bond-order-based scaling relationship framework established without the consideration of solvent. This behavior can be exploited to improve computational efficiency for future analysis of catalytic polyol conversions in the aqueous-phase environment.