The location of excess electrons on H2O/TiO2(110) surface and its role in the surface reactions

Abstract

ABSTRACTExcess electrons play a key role in many of the properties of Titanium dioxide (TiO2). Understanding their behaviour is important for improving the performance of TiO2 in energy-related applications. Here, we describe a DFT + U study of the locations of the unpaired electron (UPE) on rutile TiO2(110) (R-TiO2(110)) surface and H2O/R-TiO2(110) surface. Our results show that the subsurface are preferred with R-TiO2(110) surface. In contrast to previous studies, we find that the UPE tends to migrate to the surface H2O-Ti5c (the five-coordinated titanium (Ti5c) at surface with H2O adsorption) with the increasing of H2O coverage and UPE concentration. In addition, we have shown that the UPE plays an important role in the O-H bond dissociation and other important elementary reactions in photo-catalytic H2O dissociation on R-TiO2(110) such as H, OH and H2 desorption. Specifically, it enhances the O-H bond dissociation, as well as H and H2 desorption from bridging hydroxyl and Ti5c-OH (the Ti5c with OH adsorption), but hinders the OH and H desorption from Ti5c. We believe our results afford a further understanding of the adsorbent dependent UPE migration, and the role of UPE in the surface reactions.