Effect of surface microstructure of TiO₂ film from micro-arc oxidation on its photocatalytic activity: a HRTEM study

Photocatalysis is a reaction that happens on the surface of catalysts around only several atomic layers. Therefore, the microstructure beneath the surface plays a key role for the improvement of photocatalytic property. In this paper, the microstructural variation of the TiO(2) film from micro-arc oxidation (MAO) was characterized by using a high resolution transmission electron microscopy (HRTEM), and the relationship between microstructures and photocatalytic activity was studied. The results revealed that: 1) The microstructural variation from the surface to the interior in the as-prepared film is as follows: an amorphous layer with thickness around 10-20 nm, an intermediate zone consisting of amorphous, anatase and few rutile TiO(2) phases with grain size about 12 nm, then the main structure consisting of anatase and few rutile TiO(2) phases with grain size around 20 nm. This variation was formed due to temperature gradient during MAO. 2) When the TiO(2) film was annealed at 450 °C for 12 h, the amorphous layer disappeared and crystallized into fine anatase grains, and, simultaneously, the grain size in the intermediate layer grew obviously from 12 nm into 18 nm, and the interior portion from 20 nm into 30 nm. 3) The photocatalysis experiments exhibited that photocatalytic activity of the post-annealed TiO(2) film was enhanced to more than twice that of the as-prepared TiO(2) film. Therefore, we propose that the crystallization of amorphous phase beneath the surface plays a key role for the improvement of its photocatalytic property.