UC Santa Barbara

Coadsorbed water is often unavoidable in electrochemistry and low-temperature catalysis. In addition, water influences the adsorption of biomolecules on surfaces. We use ab initio DFT molecular dynamics and ground-state calculations to study the adsorption of HCl and catechol on the rutile TiO2(110) surface and at a water-rutile interface. We find that a coadsorbed water film reduces the adsorption energy of both catechol and HCl significantly because water molecules must be displaced from the surface before catechol or HCl can adsorb. The adsorption energy of catechol (or HCl) at the water-rutile interface can be estimated as the adsorption energy in vacuum minus the energy to remove two water molecules (respectively, one water molecule) from the rutile surface in vacuum and place them in liquid water. This estimate predicts the effect of a surface water film on adsorption without the need of molecular dynamics.