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A metastable "high-pressure" phase known as α-PbO 2 -type TiO 2 or TiO 2 -II is prepared via a single-step synthesis using a laminar premixed stagnation flame. Three other TiO 2 polymorphs, namely anatase, rutile and TiO 2 -B phases, can also be obtained by tuning the oxygen/fuel ratio. TiO 2 -II is observed as a mixture with rutile under oxygen-lean flame conditions. To the best of our knowledge, this is the first time that this phase has been identified in flame-synthesised TiO 2 . The formation of TiO 2 -II in an atmospheric pressure flame cannot be explained thermodynamically and is hypothesised to be kinetically driven through the oxidation and solid-state transformation of a sub-oxide TiO 2- x  intermediate. In this scenario, rutile is nucleated from the metastable TiO 2 -II phase instead of directly from a molten/amorphous state. Mixtures containing three-phase heterojunctions of anatase, rutile, and TiO 2 -II nanoparticles as prepared here in slightly oxygen-lean flames might be important in photocatalysis due to enhanced electron-hole separation.

Polymorphism of nanocrystalline TiO2 prepared in a stagnation flame: formation of the TiO2-II phase

Polymorphism of nanocrystalline TiO₂ prepared in a stagnation flame: formation of the TiO₂-II phase