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ACS Appl Mater Interfaces. 2011 Jul;3(7):2472-8. doi: 10.1021/am200363p. Epub 2011 Jun 7.

Anatase TiO₂ crystal facet growth: mechanistic role of hydrofluoric acid and photoelectrocatalytic activity.

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  • 1Centre for Clean Environment and Energy, and Griffith School of Environment, Griffith University, Gold Coast Campus, QLD 4222, Australia.


This work reports a facile hydrothermal approach to directly grow anatase TiO(2) crystals with exposed {001} facets on titanium foil substrate by controlling pH of HF solution. The mechanistic role of HF for control growth of the crystal facet of anatase TiO(2) crystals has been investigated. The results demonstrate that controlling solution pH controls the extent of surface fluorination of anatase TiO(2), hence the size, shape, morphology, and {001} faceted surface area of TiO(2) crystals. The theoretical calculations reveal that {001} faceted surface fluorination of anatase TiO(2) can merely occur via dissociative adsorption of HF molecules under acidic conditions while the adsorption of Na(+)F(-) is thermodynamically prohibited. This confirms that the presence of molecular form of HF but not F(-) is essential for preservation of exposed {001} facets of anatase TiO(2). Anatase TiO(2) crystals with exposed {001} facets can be directly fabricated on titanium foil by controlling the solution pH ≤ 5.8. When pH is increased to near neutral and beyond (e.g., pH ≥ 6.6), the insufficient concentration of HF ([HF] ≤ 0.04%) dramatically reduces the extent of surface fluorination, leading to the formation of anatase TiO(2) crystals with {101} facets and titanate nanorods/nanosheets. The anatase TiO(2) nanocrystals with exposed {001} facets exhibits a superior photoelectrocatalytic activity toward water oxidation. The findings of this work clarify the mechanistic role of HF for controlling the crystal facet growth, providing a facile means for massive production of desired nanostructures with high reactive facets on solid substrates for other metal oxides.

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