Photoactivity of anatase–rutile TiO2 nanotubes formed by anodization method

Titania (TiO2) nanotubes were prepared by anodizing titanium (Ti) foils in an electrochemical bath consisting of 1 M glycerol with 0.5 wt.% NH4F.The pH of the bath was kept constant at 6 and the anodization voltage was varied from 5 V, 20 V to 30 V. It is found that the morphology of the anodized titanium is a function of anodization voltage with pits-like oxide formed for the sample made at 5 V and samples made at 20 V and 30 V consisted of well-aligned nanotubes growing perpendicularly on the titanium foil. However, the nanotubes formed on the samples made at 30 V were not uniform in terms of the nanotubes' diameter and wall thickness. Regardless of the anodization voltage, as anodised samples were amorphous. The crystal structure evolution was studied as a function of annealing temperatures and was characterised by X-ray diffraction and Raman spectroscopy analyses. Crystallization of the nanotubes to anatase phase occurred at 400 °C while rutile formation occurred at 700 °C. Disintegration of the nanotube arrays was observed at 600 °C and the structure completely vanished at 700 °C. TiO2 nanotube annealed at 400 °C and containing 100% anatase revealed the highest photocatalytic activity for the degradation of methyl orange. Consequently, these results indicate that diameter, wall thickness, crystal structure and degree of crystallinity of the TiO2 nanotube arrays are the important factors influencing the efficiency of the photocatalytic activity.