One-step fabrication of highly self-hydroxylated TiO2 mesocrystals and photocatalytic behavior towards water splitting

Abstract

TiO2 mesocrystals have been considered as an efficient photocatalyst due to the effective charge transport. Introducing hydroxyls in TiO2 is respected to reduce the energy barrier of hydrogen formation. Herein, a simple one-step fabrication of highly self-hydroxylated TiO2 mesocrystals (MCs) for enhancing photocatalytic hydrogen evolution is proposed. TiO2 single crystals (SCs), polycrystals (PCs) and MCs are obtained via regulating the pH of the precursor during hydrothermal treatment. Results indicate that the moderate alkaline condition is favorable for the synthesis of highly self-hydroxylated TiO2 MCs. Compared with SCs, PCs and commercial P25 TiO2 nanoparticles, MCs exhibit the best photocatalytic activity in H2 evolution. Specifically, the maximum hydrogen evolution rate under solar light illumination (22.8 mmol/h/g) is 10.5 times higher than that of P25. Moreover, the MCs exhibit excellent catalytic stability and the hydrogen evolution rate can be maintained at 20.8 mmol/h/g under solar illumination after five cycles of reactions. The highly self-hydroxylated TiO2 MCs are constructed from crystallographically oriented nanocrystals with abundant hydroxyls. The unique superstructure and large surface area of MCs enable the effective charge separation and transport. Moreover, the high density of hydroxyls can reduce the recombination rate of photo-generated free charges and energy barrier for hydrogen formation while facilitate light absorption. The synthesis of highly self-hydroxylated TiO2 MCs and the underlying mechanism offer interesting insights for modifying the structure and properties of TiO2 towards high-performance hydrogen evolution.