Mesoporous oxide of zirconium

1. A process for making a mesoporous oxide of zirconium, the process comprising:

forming a precipitate comprising an ionic porogen which is a halide salt selected from the group consisting of ammonium halide, tetramethyl ammonium halide, tetraethyl ammonium halide and combinations thereof and a hydrous oxide of zirconium from a reaction mixture comprising a zirconium starting material selected from the group consisting of zirconium tetrachloride, zirconium oxychloride octahydrate and combination thereof, a base selected from the group consisting of ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and combinations thereof and a solvent selected from group the consisting of ethanol, n-propanol, i-propanol, dimethyl acetamide, alcoholic ammonium halide, aqueous ammonium halide and combinations thereof, wherein the zirconium starting material or the solvent, or both, are a source of the anion for the ionic porogen and the base is the source of the cation for the ionic porogen; and

removing the ionic porogen from the precipitate to recover a mesoporous oxide of zirconium having a pore volume of at least about 0.25 cc/g and an average pore diameter of at least about 100 Å.

2. The process of claim 1 wherein the ionic porogen is removed by calcining.

3. The process of claim 1 wherein the mesoporous oxide is crystalline.

4. The process of claim 1 wherein the oxide of zirconium further comprises a dopant.

5. The process of claim 4 wherein the dopant is a transition metal, a Group IIA, IIIA, IVA, or VA metal.

6. The process of claim 4 wherein the dopant is Ge, P, As, Sb, Bi, Ni, Cu, Al, Zr, Hf, Si, Nb, Ta, Fe, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, or In.

7. The process of claim 1 wherein the halide of the halide salt, the alcoholic ammonium halide or the aqueous ammonium halide is chloride, bromide or iodide or combinations thereof.

8. The process of claim 1 wherein the reaction mixture is formed by the steps, in order, of combining the base and the solvent to form a solution or a mixture and adding the zirconium starting material to the solution or mixture.

9. The process of claim 1 wherein the reaction mixture is formed by combining the zirconium starting material and the solvent to form a solution or a mixture and adding the base to the solution or mixture.

10. The process of claim 1 wherein more than about 50 weight percent of the halide salt precipitates from the reaction mixture, the weight percent based on the total amount of the halide salt that can form from the reaction mixture.

11. The process of claim 1 wherein more than about 70 weight percent of the halide salt precipitates from the reaction mixture, the weight percent based on the total amount of the halide salt that can form from the reaction mixture.

12. The process of claim 1 wherein more than about 90 weight percent of the halide salt precipitates from the reaction mixture, the weight percent based on the total amount of the halide salt that can form from the reaction mixture.

13. A process for making a mesoporous oxide of zirconium the process comprising:

forming a mixture of a solid hydrolyzed starting material comprising zirconium and a liquid medium;

adding a sufficient quantity of a halide salt to the mixture to saturate the liquid medium of the mixture and form a solid comprising a hydrolyzed intermediate comprising zirconium having pores containing the saturated liquid medium; and

removing the saturated liquid medium from the solid to recover a mesoporous oxide of zirconium having a pore volume of at least about 0.25 cc/g and an average pore diameter of at least about 100 Å.

14. The process of claim 13 wherein the liquid medium is the liquid portion of the mixture which comprises a solvent.

15. The process of claim 13 wherein the liquid medium comprises a dissolved salt.

16. The process of claim 14 wherein the solvent is ethanol, n-propanol, i-propanol, dimethyl acetamide, alcoholic ammonium halide or aqueous ammonium halide or combinations thereof.

17. The process of claim 13 wherein the halide is chloride, bromide or iodide or combinations thereof.

18. The process of claim 13 wherein the halide salt is ammonium halide, tetramethyl ammonium halide or tetraethyl ammonium halide or combinations thereof.

19. The process of claim 13 wherein the halide salt is ammonium chloride.

20. The process of claim 13 wherein the step of removing the saturated liquid medium comprises drying and calcining.

21. The process of claim 13 wherein the mesoporous oxide is crystalline.

22. The process of claim 13 wherein the oxide of zirconium further comprises a dopant.

23. The process of claim 22 wherein the dopant is a transition metal, a Group IIA, IIIA, IVA, or VA metal.

24. The process of claim 23 wherein the dopant is Ge, P, As, Sb, Bi, Ni, Cu, Al, Zr, Hf, Si, Nb, Ta, Fe, Sn, Co, Zn, Mo, W, V, Cr, Mn, Mg, Ca, Sr, Ba, Ga, or In.

25. The process of claim 13 wherein the hydrolyzed starting material comprising zirconium is derived from zirconium tetrachloride, zirconium oxychloride octahydrate or combination thereof.

26. The process of claims 1 or 13 wherein the mesoporous oxide of zirconium comprises ZrO 2 having a surface area at least about 70 m 2 /g, a pore volume of at least about 0.25 cc/g, and an average pore diameter of at least about 100 Å.