Mesoporous oxide of titanium

• US 20060257312A1
• Filed: 03/30/2006
• Published: 11/16/2006
• Est. Priority Date: 11/23/2004
• Status: Active Grant

• Current Assignee: The Chemours Company TT, LLC (The Chemours Company)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Torardi, Carmine
• Granted Patent: US 7,988,947 B2
• Time in Patent Office: Days
• US Class Current: 423/610
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 23/047 Titanium dioxide
• CPC Class Codes: C01G 23/053 Producing by wet processes, e.g. hydrolysing titanium salts
• CPC Class Codes: C01G 23/0536 by hydrolysing chloride-containing salts
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01G 27/02 Oxides
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/14 Pore volume
• CPC Class Codes: C01P 2006/16 Pore diameter
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]

Abstract

This invention pertains to mesoporous oxide of titanium and processes of making mesoporous oxide of titanium particularly crystalline oxide of titanium.

Claims

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

precipitating an ionic porogen and a hydrolyzed compound comprising titanium; and

removing the ionic porogen from the precipitate to recover a mesoporous oxide of titanium, the amount of ionic porogen and the precipitating conditions being effective for producing a mesoporous oxide of titanium having a pore volume of at least about 0.5 cc/g and an average pore diameter of at least about 200 Å

.

2. The process of claim 1 wherein the ionic porogen is a halide salt.

3. The process of claim 1 wherein the ionic porogen is ammonium chloride.

4. The process of claim 2 wherein the halide salt is ammonium halide, tetramethyl ammonium halide or tetraethyl ammonium halide or mixtures thereof.

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

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

7. The process of claim 1 wherein the oxide of titanium further comprises a dopant.

8. The process of claim 1 wherein the hydrolyzed compound comprising titanium is derived from titanium tetrachloride, titanium oxychloride or mixture thereof.

9. The process of claim 1 wherein at least 2 moles of the ionic porogen precipitates for each mole of the hydrolyzed compound comprising titanium that precipitates.

10. The process of claim 8 wherein the ionic porogen is a halide salt and at least 3 moles of the halide salt precipitates for each mole of the hydrolyzed compound comprising titanium that precipitates.

11. The process of claim 8 wherein the ionic porogen is a halide salt and at least 4 moles of the halide salt precipitates for each mole of the hydrolyzed compound comprising titanium that precipitates.

12. A process for making a mesoporous oxide of titanium, comprising:

precipitating an ionic porogen and a hydrous oxide of titanium from a reaction mixture comprising a titanium starting material, a base and a solvent, wherein the titanium 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, the precipitating being carried out under conditions effective for recovering a mesoporous oxide of titanium having a pore volume of at least about 0.5 cc/g and an average pore diameter of at least about 200 Å

after removing the ionic porogen from the precipitate.

13. The process of claim 12 wherein the ionic porogen is a halide salt.

14. The process of claim 12 wherein the ionic porogen is ammonium chloride.

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

16. The process of claim 12 wherein the ionic porogen is removed by calcining.

17. The process of claim 12 wherein the mesoporous oxide is crystalline.

18. The process of claim 12 wherein the oxide of titanium further comprises a dopant.

19. The process of claim 12 wherein the titanium starting material is titanium tetrachloride, titanium oxychloride, or mixture thereof.

20. The process of claim 12 wherein the base is ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, tetramethyl ammonium hydroxide or tetraethyl ammonium hydroxide or mixture thereof.

21. The process of claim 12 wherein the solvent is ethanol, n-propanol, i-propanol, dimethyl acetamide, alcoholic ammonium halide and aqueous ammonium halide or mixture thereof.

22. The process of claim 12 wherein the reaction mixture is formed by the steps, in order, of contacting the base and the solvent to form a solution or a mixture and adding the titanium starting material to the solution or mixture.

23. The process of claim 12 wherein the reaction mixture is formed by contacting the titanium starting material and the solvent to form a solution or a mixture and adding the base to the solution or mixture.

24. The process of claim 13 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.

25. The process of claim 19 wherein the ionic porogen is a halide salt and 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.

26. The process of claim 19 wherein the ionic porogen is a halide salt and 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.

27. A process for making a mesoporous oxide of titanium, the process comprising:

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

adding a sufficient quantity of a halide salt to the mixture to saturate the liquid medium of the mixture;

recovering the solid from the saturated liquid medium, the solid comprising a hydrolyzed intermediate comprising titanium having pores containing the saturated liquid medium; and

removing the saturated liquid medium from the solid to recover a mesoporous oxide of titanium having a pore volume of at least about 0.5 cc/g and an average pore diameter of at least about 200 Å

.

28. The process of claim 27 wherein the liquid medium is the liquid portion of the mixture which comprises a solvent.

29. The process of claim 27 wherein the liquid medium comprises a dissolved salt.

30. The process of claim 28 wherein the solvent is ethanol, n-propanol, i-propanol, dimethyl acetamide, alcoholic ammonium halide and aqueous ammonium halide or mixture thereof.

31. The process of claim 27 wherein the halide salt is ammonium halide, tetramethyl ammonium halide or tetraethyl ammonium halide or mixture thereof.

32. The process of claim 27 wherein the halide salt is ammonium chloride.

33. The process of claim 27 wherein the step of removing the saturated liquid medium comprises drying and calcining.

34. The process of claim 27 wherein the mesoporous oxide is crystalline.

35. The process of claim 27 wherein the hydrolyzed starting material comprising titanium is derived from titanium tetrachloride, titanium oxychloride or a mixture thereof.

36. A composition of matter comprising mesoporous oxide of titanium having a microstructure characterized by a surface area of at least about 70 m²/g, a pore volume of least about 0.5 cc/g, and an average pore diameter of least about 200 Å

.

37. The composition of matter of claim 36 further comprising a treatment with silica, alumina or both.

38. A protective coating composition comprising the oxide of titanium of claim 37.

39. The composition of matter of claim 36 further comprising a treatment with an organic coating agent.

40. A thermoplastic composition comprising the oxide of titanium of claim 39.

41. A catalyst composition comprising the composition of matter of claim 36.

42. A nanoparticle precursor comprising the composition of matter of claim 36.

43. An optical device comprising the composition of matter of claim 36.

44. A photovoltaic cell comprising the composition of matter of claim 36.

45. A lithium battery anode comprising the composition of matter of claim 36.