The photoreactivity of TiO2 nanotube arrays (TiNT) is mainly related to the light absorption and photogenerated charge carriers separation efficiencies. Recently, engineering of the crystal facets has gained increasing attention because of its exceptional ability to extend the photoresponse toward visible light and to separate photogenerated charges. Here, TiNT with high crystallinity and percentage of exposed {001} facets was synthesized using a two-step anodization process in ethylene glycol based electrolyte containing 2 wt% of water and 0.27 M NH4F. Decreasing the potential of the second anodization (from 50 to 20 V) resulted in an increase in crystallinity, crystallite size, and percentage of exposed {001} facets. Because trap states limit the photoreactivity performance of TiNT by facilitating the recombination of photogenerated electron/hole pairs, correlation between crystallinity, preferential crystalline orientation, gap states characteristics (density and location), and photoreactivity performance was investigated. TiNT with a high percentage of {001} exposed facets, consisting mainly of shallow gap states with low density, significantly improve photoelectrochemical water oxidation and photocatalytic efficiencies.

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