Vapor-phase hydrothermal synthesis of rutile TiO₂ nanostructured film with exposed pyramid-shaped (111) surface and superiorly photoelectrocatalytic performance.

Rutile TiO2 nanostructured film with exposed pyramid-shaped (111) surface was successfully fabricated using metal titanium foil as substrate through a facile vapor-phase hydrothermal method. The fabricated rutile TiO2 film was composed of vertically aligned rod-like structures with diameters ranged from 400 to 700 nm and thickness of ca. 2.0 μm. The obtained rutile TiO2 film as photoanode exhibited excellent photoelectrocatalytic activity toward water oxidation and rhodamine B decolorization under UV illumination, which was more than 3.5 and 1.2 times of that obtained by highly ordered anatase TiO2 nanotube array film photoanode under the same experimental conditions, respectively. The excellent photoelectrocatalytic performance of the rutile TiO2 film photoanode could be due to the superior photoelectron transfer property and the high oxidative capability of {111} crystal facets. The superior photoelectron transfer capability of the photoanodes was manifested by the inherent resistance (R0) of the photoanodes using a simple photoelectrochemical method. The calculated R0 values were 50.5 and 86.2 Ω for the rutile TiO2 nanostructured film and anatase TiO2 nanotube array film, respectively. Lower R0 value of the rutile TiO2 photoanode indicated a superior photoelectron transfer capability owing to good single crystal property of the rod-like rutile nanostructure. Almost identical valence band level (1.94 eV) of the rutile TiO2 nanostructured film and anatase TiO2 nanotube array film (meaning a similar oxidation capability) further confirmed the significant role of photoelectron transfer capability and exposed high-energy {111} crystal facets for improved photoelectrocatalytic performance of the rutile TiO2 nanostructured film photoanode.