New insights for titanium(iv) speciation in acidic media based on UV-visible and 31P NMR spectroscopies and molecular modeling

Abstract

Titanium chemistry in aqueous acidic media has been extensively investigated over the last decades. Hydrolyzed species such as Ti(OH)³⁺, TiO²⁺, Ti(OH)₂²⁺ or Ti(OH)₃⁺ have been identified and their equilibria have been studied in nitric and perchloric acid. A predominance of the divalent cations was found for low pH (i.e., pH <2). Nonetheless, recent literature reports the existence of small titanium oxo-clusters in aqueous acidic media for large titanium(IV) concentration (typically., >0.1 mol L⁻¹), as stable precursors for the formation of condensed titanium dioxide. The present paper reconsiders firstly previous knowledge about the speciation of titanium(IV) in non-complexing acidic media by giving evidence for the presence of polynuclear hydrolyzed species, even at very low Ti(IV) concentration (i.e., typically <0.1 mmol L⁻¹). UV-visible absorbance spectra recorded for diluted nitric acid solutions (a model of non-complexing acidic medium) containing titanium(IV) were compared to time-dependent density functional theory (TD-DFT) predicted excitation energies. Experimental and predicted maximal absorbance wavelengths showed significantly improved matches when polynuclear species were considered in TD-DFT calculation. Then, 0.1–12.7 mol L⁻¹ phosphoric acid solutions containing titanium(IV) were studied by means of spectroscopic techniques (UV-visible, NMR) in order to identify qualitatively the presence of titanium(IV) complexes and to link this speciation to the acid concentration. Two different titanium(IV) orthophosphate complexes, potentially polynuclear, were detected, and the presence of free titanium(IV) is also expected for low phosphoric acid concentration (i.e., <0.1 mol L⁻¹). A general complexation scheme for a large range of H₃PO₄ concentration was thus formulated.