The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high –quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies.

Titanium dioxide is the prototypical transition metal oxide photocatalyst. However, the larger than 3 eV bandgap of common bulk phases of TiO₂ limits its light absorption to UV light, making it inefficient for solar energy conversion. Attempts at increasing visible light activity by narrowing the bandgap of TiO₂ through doping have proven difficult, because of defect-induced charge trapping and recombination sites of photo-excited charge carriers. Here, we report the existence of a dopant-free, pure TiO₂ phase with a narrow bandgap. This new pure TiO₂ phase forms on the surface of rutile TiO₂(011) by oxidation of bulk titanium interstitials. We measure a bandgap of only ~2.1 eV for this new phase, matching it closely with the energy of visible light.

The two-dimensional layer of molybdenum disulfide (MoS2) exhibits promising prospects in the applications of optoelectronics and valleytronics. Herein, we report a successful new process for synthesizing wafer-scale MoS2 atomic layers on diverse substrates via magnetron sputtering. Spectroscopic and microscopic results reveal that these synthesized MoS2 layers are highly homogeneous and crystallized; moreover, uniform monolayers at wafer scale can be achieved. Raman and photoluminescence spectroscopy indicate comparable optical qualities of these as-grown MoS2 with other methods. The transistors composed of the MoS2 film exhibit p-type performance with an on/off current ratio of ∼10(3) and hole mobility of up to ∼12.2 cm(2) V(-1) s(-1). The strategy reported herein paves new ways towards the large scale growth of various two-dimensional semiconductors with the feasibility of controllable doping to realize desired p- or n-type devices.