Origin of Charge Trapping in TiO/Reduced Graphene Oxide Photocatalytic Composites: Insights from Theory.

Composites of titanium dioxide (TiO) and reduced graphene oxide (RGO) have proven to be much more effective photocatalysts than TiO alone. However, little attention has been paid so far to the chemical structure of TiO/RGO interfaces and to the role that the unavoidable residual oxygen functional groups of RGO play in the photocatalytic mechanism. In this work, we develop models of TiO rutile (110)/RGO interfaces by including a variety of oxygen functional groups known to be present in RGO. Using hybrid density functional theory calculations, we demonstrate that the presence of oxygen functional groups and the formation of interfacial cross-links (Ti-O-C covalent bonds and strong hydrogen bonds between TiO and RGO) have a major effect on the electronic properties of RGO and RGO-based composites. The electronic structure changes from semimetallic to semiconducting with an indirect band gap, with the lowest unoccupied band positioned below the TiO conduction band and largely localized on RGO oxygen and carbon orbitals, with some contributions of RGO-bonded Ti atoms. We suggest that this RGO-based lowest unoccupied band acts as a photoelectron trap and the indirect nature of the band gap hinders electron-hole recombination. These results can explain the experimentally observed extended lifetimes of photoexcited charge carriers in TiO/RGO composites and the enhancement of photocatalytic efficiency of these composites.