Probing equilibrium of molecular and deprotonated water on TiO2(110)

Abstract

Understanding adsorbed water and its dissociation to surface hydroxyls on oxide surfaces is key to unraveling many physical and chemical processes, yet the barrier for its deprotonation has never been measured. In this study, we present direct evidence for water dissociation equilibrium on rutile-TiO2(110) by combining supersonic molecular beam, scanning tunneling microscopy (STM), and ab initio molecular dynamics. We measure the deprotonation/protonation barriers of 0.36 eV and find that molecularly bound water is preferred over the surface-bound hydroxyls by only 0.035 eV. We demonstrate that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O–H bonds and inducing deprotonation. The developed methodology for studying metastable reaction intermediates prepared with a high-energy molecular beam in the STM can be readily extended to other systems to clarify a wide range of important bond activation processes.