Sonochemical synthesis of titanium-containing oxides
View Patent ↗A titanium halide, preferably titanium tetrachloride, is reacted with suitable reductant, preferably an alkali metal or alkaline earth metal, under ultrasonic excitation in a liquid reaction medium to form nanometer size particles of titanium which may incorporate unreacted reductant. The nanosized titanium particles may be a precursor for nanosized titanium oxide which is formed by oxidizing the titanium, preferably with a low molecular weight alcohol. When the titanium particles incorporate unreacted reductant the oxidation reaction will yield nanometer sized titanates. The nanosized particles, whether titanium oxide or titanates may be extracted by first filtering them from the reaction medium, followed by washing with water to remove any water-soluble reaction products followed by spray drying.
1. A method for forming nanometer-size particles of a titanium-containing oxide, comprising the steps of:
adding a reductant to a liquid reaction medium maintained at a pre-determined temperature and contained in a reaction vessel under a dry inert gas atmosphere:
sonicating the mixture of reductant and liquid reaction medium to finely disperse and uniformly distribute the reductant throughout the reaction medium;
adding a titanium halide to the dispersion of reductant and liquid reaction medium to form a first reaction mixture while sonicating the first reaction mixture;
holding the first reaction mixture for a time sufficient to enable substantially-complete reaction between the reductant and the titanium halide and form a first reaction product mixture comprising nanometer-size particles of titanium;
adding an oxidant to the first reaction product mixture to form a second reaction mixture comprising the titanium particles while sonicating the second reaction mixture;
holding the second reaction mixture for a time sufficient to enable substantially-complete reaction between the oxidant and the titanium particles to form a second reaction product mixture comprising a nanometer-size particles of a titanium-containing oxide; and
separating the particles of titanium-containing oxide from the remainder of the second reaction product mixture.
2. The method of claim 1 , wherein the reductant comprises at least one of the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, and barium.
3. The method of claim 1 wherein the liquid reaction medium is at least one of the group consisting of decane, dodecane, decalin, tetralin and hexadecane.
4. The method of claim 1 wherein the oxidant is a low molecular weight alcohol of the group consisting of methanol, ethanol and propanol.
5. The method of claim 1 wherein the titanium halide is at least one of the group consisting of titanium tetrachloride, titanium tetrabromide and titanium tetraiodide.
6. The method of claim 1 wherein the titanium-containing oxide substantially comprises titanium dioxide.
7. The method of claim 1 wherein the titanium-containing oxide is a titanate.
8. The method of claim 1 wherein the predetermined temperature is between 20° C. and 200° C.
9. The method of claim 1 wherein the reductant is present in molar excess with respect to the titanium halide.
10. The method of claim 1 wherein separating the particles of titanium-containing oxide from the remainder of the second reaction product comprises:
filtering the second reaction product mixture to separate the mixture into a liquid fraction and a first solid fraction;
washing the solid fraction to dissolve all water-soluble reaction products;
filtering the resulting solid-containing aqueous solution and retaining a second solid fraction;
repeating the previous washing and filtering steps until substantially all water-soluble reaction products have been removed; and
re-dispersing the solid fraction and spray-drying the dispersion.