How the hydroxylation state of the (110)-rutile TiO₂ surface governs its electric double layer properties

The hydroxylation state of an oxide surface is a central property of its solid/liquid interface and its corresponding electrical double layer. This study integrated both a reactive force field (ReaxFF) and a non-reactive potential into a hierarchical framework within molecular dynamics (MD) simulations to reveal how the hydroxylation state of the (110)-rutile TiO2 surface affects the electrical double layer properties. The simulation results obtained in the ReaxFF framework have shown that, while water dissociation occurs only at the under-coordinated Ti5c sites on the pristine TiO2 surface, the presence of point defects on the surface facilitates water dissociation at the oxygen vacancy sites, leading to two protonated oxygen bridge atoms for each vacancy site. As a consequence of enhanced water dissociation at the vacancy sites, water dissociation is quenched at the under-coordinated Ti5c sites resulting in two competitive hydroxylation mechanisms on the (110)-TiO2 surface. Using non-reactive MD simulations with hydroxylation states derived from the ReaxFF analysis, we demonstrate that water dissociation at the vacancy sites is a central mechanism governing the structuring of water near the interface. While the structuring of water near the interface is the main contribution to the electric field, water dissociation at the vacancy site enhances the adsorption of the electrolyte ions at the interface. The adsorbed ions lead to an increase of the effective surface charge as well as surface (zeta) potentials which are in the range of experimental observations. Our work provides a hierarchical multiscale simulation approach, covering a series of results with in-depth discussion for atomic/molecular level understanding of water dissociation and its effect on electric double layer properties of TiO2 to advance water splitting.