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Chemistry. 2017 Apr 24;23(23):5478-5487. doi: 10.1002/chem.201605294. Epub 2017 Feb 15.

Anatase TiO2 Mesocrystals: Green Synthesis, In Situ Conversion to Porous Single Crystals, and Self-Doping Ti3+ for Enhanced Visible Light Driven Photocatalytic Removal of NO.

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Department of Chemistry, College of Science, Huazhong Agricultural University, No. 1 Shizishan Street, Wuhan, 430070, P. R. China.


Mesocrystals are of great interest for a wide range of applications owing to their unique structural features and properties. The realization of well-defined metal oxide mesocrystals through a facile and green synthetic approach still remains a great challenge. Here, a novel synthesis strategy is reported for the production of spindle-shaped anatase TiO2 mesocrystals with a single-crystal-like structure, which was simply achieved through the one-step hydrolysis reaction of TiCl3 in the green and recyclable media polyethylene glycol (PEG-400) without any additives. Such anatase mesocrystals were constructed from small nanocrystal subunits (≈1.5-4.5 nm in diameter) and formed through oriented aggregation of the nanocrystals pre-formed in the reaction system. Owing to their novel structural characteristics, the as-synthesized anatase mesocrystals could be easily fused in situ into porous single crystals by annealing in air. More significantly, after being annealed in vacuum, Ti3+ sites could be easily induced in the anatase crystal lattice, resulting in the formation of Ti3+ self-doped anatase mesocrystals. The thus-transformed mesocrystals exhibited enhanced visible light activity towards the photocatalytic oxidation of nitric oxide (NO) to NO3- , which could be largely attributed to their intrinsic Ti3+ self-doped nature, as well as high crystallinity and high porosity of the mesocrystalline architecture.


NO; anatase mesocrystals; photocatalysis; porous single crystals; self-doping


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