Stoichiometric Study on Ion Composition of a Precursor in Chemical Bottom-Up Synthesis for Peroxo-Titanate.

Layered alkali titanates of the lepidocrocite type are gaining enormous interest in various fields owing to their unique properties. These materials are mainly synthesized through a hydrothermal alkali treatment. However, this method uses a highly concentrated alkali solution, which has high environmental impacts and is therefore unsuitable for mass synthesis. Herein, we propose an efficient method for the large-scale synthesis of layered sodium titanate structures (Na 2- x H x Ti 2 O 5 ) using a recently reported bottom-up chemical process. The effects of the Na:Ti molar ratio in the peroxo-titanium complex ion precursor on the products are investigated through stoichiometric calculations for a molar ratio range of 10:1-1:1. The optimal ratio for the complete ionization of TiH 2 (which is the starting material) to form the peroxo-titanium complex ion is found to be 1.1:1. The amount of alkali raw material required is 99.6% lower than that required in the traditional hydrothermal method. The crystal structures and morphologies of the samples are almost identical regardless of the Na:Ti molar ratio. The precursor-derived peroxo bonds narrow the energy band gaps of the layered titanates even when the amount of titanium ions dissolved in the precursor increases. The proposed method is not only an efficient synthetic route for mass production but also has potential applications in the development of photofunctional materials.