Abstract
From solutions containing 2–17 wt % TiO2 at the molar ratios M/Ti = 1–4, F/Ti = 2–4, and PO43−/Ti = 0.5–10 under mild conditions, fluoro- and oxo(hydroxo) fluorophosphate titanates were isolated: crystalline M2TiF6 (M = K, Rb, Cs) and K2Ti2O2.5F2PO4 · 2H2O, and amorphous K3Ti4O(OH)F7(PO4)3 · 5H2O, Cs2Ti3O2F7PO4 · 6H2O, and CsTi3O3F4PO4 · 3H2O. In a mixture with M2TiF6 and KCl, phosphate-ion-containing crystalline phases of unidentified composition were detected. The phases were studied by elemental, crystal-optical, X-ray powder diffraction, thermal, IR spectroscopic, and electron microscopic analyses. Annealing fluorophosphate titanates gives a mixture of MTiOPO4 and TiO2. All the mentioned alkali metal fluorophosphates contain the tetrahedral ion PO43− and titanium polyhedra with bonds Ti-F and Ti-O; some of them also contain bridging oxygen connecting titanium atoms: Ti-O-Ti; i.e., these substances are polymeric.
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