Oxygen-Vacancy-Driven Orbital Reconstruction at the Surface of TiO 2 Core–Shell Nanostructures

Oxygen vacancies and their correlation with the electronic structure are crucial to understanding the functionality of TiO 2 nanocrystals in material design applications. Here, we report spectroscopic investigations of the electronic structure of anatase TiO 2 nanocrystals by employing hard and soft X-ray absorption spectroscopy measurements along with the corresponding model calculations. We show that the oxygen vacancies significantly transform the Ti local symmetry by modulating the covalency of titanium–oxygen bonds. Our results suggest that the altered Ti local symmetry is similar to the C 3 v, which implies that the Ti exists in two local symmetries ( D 2 d and C 3 v ) at the surface. The findings also indicate that the Ti distortion is a short-range order effect and presumably confined up to the second nearest neighbors. Such distortions modulate the electronic structure and provi…