TiBALDH as a precursor for biomimetic TiO2 synthesis: stability aspects in aqueous media

Titanium(iv) bis(ammonium lactate)dihydroxide (TiBALDH) is a commercially available reagent frequently used to synthesize TiO₂. Particularly, for the biomimetic synthesis of TiO₂, TiBALDH is the preferred precursor because it can be mixed in aqueous solutions with no apparent hydrolysis or condensation reactions. Thus, proteins or other biomolecules can be used as a template in aqueous systems for the synthesis of TiO₂ from TiBALDH. Nevertheless, there is evidence that TiBALDH is in equilibrium with TiO₂, and even, the principal structure of the complex has been suggested as [Ti₄O₄(lactate)₈]⁸⁻. Since that chemical equilibrium depends on the polarity of the solvent, in this work we explored a diversity of media to test the chemical stability of TiBALDH and its equilibrium with TiO₂ at room temperature. TiBALDH (2.078 M) contains particles of 18.6 ± 7.3 nm in size, if it is diluted with deionized water, the particles reach a size of 5.2 ± 1.7 nm, which suggest that intermolecular interactions form polymers of titanium lactate complexes reversibly, reaching equilibrium after 10 hours. Typical buffer systems were tested; TiBALDH reacted rapidly only with phosphate groups, even if the source came from DNA. Therefore, phosphate buffer must be avoided in biomineralization TiO₂ synthesis. In solutions of TiBALDH at basic pH, condensation reactions are promoted to form a gel containing anatase nanoparticles, but if the solutions are acidic, monodisperse anatase nanoparticles of ∼5 nm were observed. The results show that the commercial reagent TiBALDH contains many species of titanium lactate complexes in equilibrium with TiO₂, and it is affected by the concentration, time, pH, and several ions. This peculiar behavior must be taken into account when this precursor is used and it could be useful to develop novel synthesis routes of macrostructures with biomolecules in aqueous systems.

Factors affecting TiO₂ biomineralization using TiBALDH as precursor.