In Situ STEM Determination of the Atomic Structure and Reconstruction Mechanism of the TiO₂ (001) (1 × 4) Surface

Abstract

The widely studied anatase TiO2 (001) surface usually shows a (1 × 4) reconstruction, which may directly influence its physical and chemical properties. Although various atomic models are proposed, the debates regarding the models and the formation mechanism of such reconstruction remain until now due to the lack of direct experimental evidence at the atomic level. Herein, we report the atomic-scale determination of the atomic structure and the reconstruction mechanism of the TiO2 (001) (1 × 4) surface by in situ spherical aberration corrected scanning transmission electron microscopy (STEM) at elevated temperature. The atomic features of the reconstructed surface are unambiguously identified in our experiments, providing a solid evidence to verify the ad-molecule model, which was predicted by the calculations 15 years ago. Furthermore, the mysterious reconstruction route is revealed by our real time STEM images, which involves a new metaphase of the (001) surface. These results are expected to help resolve current dispute concerning the reconstruction models and understand the true performances of the anatase TiO2 (001) surface.