Nanostructured oxides and hydroxides and methods of synthesis therefor

• US 6,162,530 A
• Filed: 11/17/1997
• Issued: 12/19/2000
• Est. Priority Date: 11/18/1996
• Status: Expired due to Fees

• Current Assignee: Rutgers University, University of Connecticut (State of Connecticut)
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Kear, Bernard H., Chen, Huimin, Xiao, Tongsan D., Strutt, Peter R., Wang, Donald M.
• Primary Examiner(s): RAIMUND, CHRISTOPHER W
• Application Number:
  US08/971,817
• Time in Patent Office: 1,128 Days
• Field of Search: 428/292.1, 428/372, 428/401, 428/364, 428/402
• US Class Current: 428/292.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 13/34 by oxidation or hydrolysis of sprayed or atomised solutions
• CPC Class Codes: C01G 1/02 Oxides
• CPC Class Codes: C01G 23/04 Oxides; Hydroxides
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01G 3/02 Oxides; Hydroxides
• CPC Class Codes: C01G 31/02 Oxides
• CPC Class Codes: C01G 39/02 Oxides; Hydroxides
• CPC Class Codes: C01G 41/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/00 Compounds of manganese
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 49/02 Oxides; Hydroxides C01G49/0018 takes precedence
• CPC Class Codes: C01G 51/04 Oxides; Hydroxides
• CPC Class Codes: C01G 53/00 Compounds of nickel
• CPC Class Codes: C01G 53/04 Oxides; Hydroxides
• CPC Class Codes: C01G 9/02 Oxides; Hydroxides
• CPC Class Codes: C01P 2002/01 depicted by a TEM-image
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2004/03 : obtained by SEM
• CPC Class Codes: C01P 2004/04 : obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/10 : extending in one dimension, e.g. needle-like
• CPC Class Codes: C01P 2004/12 : with a cylindrical shape
• CPC Class Codes: C01P 2004/16 : Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
• CPC Class Codes: C01P 2004/32 : Spheres
• CPC Class Codes: C01P 2004/50 : Agglomerated particles
• CPC Class Codes: C01P 2004/61 : Micrometer sized, i.e. from 1-100 micrometer
• 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 2006/11 : Powder tap density
• 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: C01P 2006/17 : Pore diameter distribution
• CPC Class Codes: C01P 2006/20 : Powder free flowing behaviour
• CPC Class Codes: C04B 35/62231 : based on oxide ceramics
• CPC Class Codes: Y10T 428/249924 : Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
• CPC Class Codes: Y10T 428/2913 : Rod, strand, filament or fiber
• CPC Class Codes: Y10T 428/2927 : including structurally defined particulate matter
• CPC Class Codes: Y10T 428/298 : Physical dimension
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]

Abstract

A chemical synthetic route is disclosed for nanostructured materials that is scalable to large volume production, comprising spray atomization of a reactant solution into a precursor solution to form a nanostructured oxide or hydroxide precipitate. The precipitate is then heat-treated followed by sonication, or sonicated followed by heat treatment. This route yields nanostructured doped and undoped nickel hydroxide, manganese dioxide, and ytrria-stabilized zirconia. Unusual morphological superstructures may be obtained, including well-defined cylinders or nanorods, as well as a novel structure in nickel hydroxide and manganese dioxide, comprising assemblies of nanostructured fibers, assemblies of nanostructured fibers and agglomerates of nanostructured particles, and assemblies of nanostructured fibers and nanostructured particles. These novel structures have high percolation rates and high densities of active sites, rendering them particularly suitable for catalytic applications.

Claims

1. A nanostructured oxide or hydroxide synthesized by:

providing an aqueous starting solution and an aqueous reactant solution;

co-atomizing the aqueous reactant solution into the aqueous starting solution, thereby precipitating a nanostructured oxide or hydroxide powder from the mixture of the aqueous starting and reactant solutions;

heat treating the nanostructured oxide or hydroxide powder to produce a heat-treated nanostructured oxide or hydroxide; and

ultrasonicating the heat-treated nanostructured oxide or hydroxide, wherein the ultrasonicated nanostructured oxide or hydroxide is in the form of a random, interconnected open-weave assembly of fibers, the fibers having diameters of less than about 100 nm.

2. The nanostructured oxide or hydroxide of claim 1, wherein

the nanostructured oxide or hydroxide comprises nickel, manganese, yttrium, zirconium, aluminum, silicon, magnesium, cobalt, vanadium, molybdenum, zinc, silver, titanium, iron, cobalt, copper, tungsten, or other rare earth metal.

3. The nanostructured oxide or hydroxide of claim 1, wherein

the nanostructured oxide or hydroxide is nickel hydroxide, nickel hydroxide doped with at least one of aluminum, cobalt, cadmium, manganese, or zinc, manganese oxide, manganese oxide doped with at least one of cobalt, iron, or platinum, yttrium oxide, zirconium oxide, or yttria-stabilized zirconium oxide.

4. The nanostructured oxide or hydroxide of claim 1, wherein

the nanostructured fibers have an aspect ratio greater than about 10.

5. The nanostructured oxide or hydroxide of claim 1, wherein

the nanostructured fibers are spaced between about 0.5 to 200 nm apart from each other.

6. The nanostructured oxide or hydroxide of claim 5, wherein

the nanostructured fibers are spaced from about 5 to 50 nm apart.

7. The nanostructured oxide or hydroxide of claim 1, wherein

the porosity of the nanostructured fiber assembly is greater than about 60 volume percent.

8. The nanostructured oxide or hydroxide of claim 7, wherein

the porosity of the nanostructured fiber assembly is greater than about 80 volume percent.

9. The nanostructured oxide or hydroxide of claim 1, further comprising

nanostructured particles, wherein the nanostructured particles have diameters of less than about 100 nm.

10. The nanostructured oxide or hydroxide of claim 9, wherein

the nanostructured particles have diameters in the range from about 1 to 100 nm.

11. The nanostructured oxide or hydroxide of claim 10, wherein

the nanostructured particles are in the form of agglomerates, wherein the agglomerates have diameters in the range from about 0.1 to 200 microns.

12. The nanostructured oxide or hydroxide of claim 11, wherein

the agglomerates are porous, the pores having diameters in the range from about 0.5 to 20 nm.

13. The nanostructured oxide or hydroxide of claim 11, wherein

the agglomerates of nanostructured particles comprise from about 60 to 90 percent by volume of the total nanostructured oxide or hydroxide.

14. The nanostructured oxide or hydroxide of claim 9, comprising

manganese dioxide or nickel hydroxide.

15. A composition of matter, comprising

nanostructured particulate or fibrous nickel hydroxide, wherein the nickel hydroxide particles or fibers have diameters of less than about 100 nm.

16. The composition of claim 15,

the nanostructured nickel hydroxide is doped with at least one metal.

17. The composition of claim 16, wherein

the at least one metal is cobalt, aluminum, platinum, copper, titanium, tungsten, an alkali metal, a noble metal, or a semi-conducting metal.

18. A composition of matter, comprising

nanostructured particulate or fibrous manganese dioxide, wherein the manganese dioxide particles or fibers have diameters of less than about 100 nm.

19. The composition of claim 18,

the nanostructured manganese dioxide is doped with at least one metal.

20. The composition of claim 19, wherein

the at least one metal is cobalt, aluminum, platinum, copper, titanium, tungsten, an alkali metal, a noble metal, or a semi-conducting metal.

21. A composition of matter, comprising

nanostructured fibrous zirconium oxide, wherein the zirconium oxide fibers have diameters of less than about 100 nm, and the fibers are in the form of a random, interconnected open-weave assembly.

22. The composition of claim 21,

the nanostructured zirconium oxide further comprises nanostructured yttrium oxide.

23. Nanostructured composite materials, comprising

at least one random interconnected open-weave assembly of nanostructured fibers, wherein the nanostructured fibers have diameters of less than about 100 nm;

and

at least one agglomerate of nanostructured particles adjacent or partially or completely within the at least one assembly, wherein the nanostructured particles have diameters of less than about 100 nm.

24. The nanostructured composite materials of claim 23, wherein

the nanostructured fibers have an aspect ratio greater than about 10.

25. The nanostructured composite materials of claim 23, wherein

the nanostructured fibers are spaced between about 0.5 to 200 nm apart from each other.

26. The nanostructured composite materials of claim 25, wherein

the nanostructured fibers are spaced about 5 and 50 nm apart.

27. The nanostructured composite materials of claim 23, wherein

the porosity of the at least one nanostructured fiber assembly is greater than about 60 volume percent.

28. The nanostructured composite materials of claim 23, wherein

the porosity of the nanostructured fiber assembly is greater than about 80 volume percent.

29. The nanostructured oxide or hydroxide of claim 28, wherein

the fibers have diameters of less than about 50 nm.

30. The nanostructured composite materials of claim 23, wherein

the agglomerates of nanostructured particles have diameters in the range from about 0.1 to 200 microns.

31. The nanostructured composite materials of claim 23, wherein

the agglomerates of nanostructured particles comprise from about 60 to 90 percent by volume of the nanostructured material.

32. The nanostructured composite materials of claim 23, comprising oxides or hydroxides of nickel, manganese, yttrium, zirconium, aluminum, silicon, magnesium, cobalt, vanadium, molybdenum, zinc, silver, titanium, vanadium, iron, cobalt, copper, tungsten, or other rare earth metals.

33. The nanostructured composite materials of claim 23, comprising

manganese dioxide or nickel hydroxide.

34. The nanostructured composite materials of claim 23, wherein

the composites have a high percolation rate and a high density of active sites.

35. Nanostructured composite materials, comprising

at least one random, interconnected open-weave assembly of nanostructured fibers, wherein the nanostructured fibers have diameters of less than about 100 nm;

and

nanostructured particles adjacent or partially or completely within the at least one assembly, wherein the nanostructured particles have diameters of less than about 100 nm.

36. The nanostructured composite materials of claim 35, wherein

the nanostructured fibers have an aspect ratio greater than about 10.

37. The nanostructured composite materials of claim 35, wherein

the nanostructured fibers are spaced between about 0.5 to 200 nm apart from each other.

38. The nanostructured composite materials of claim 35, wherein

the nanostructured fibers are spaced about 5 and 50 nm apart.

39. The nanostructured composite materials of claim 35, wherein

the porosity of the at least one nanostructured fiber assembly is greater than about 60 volume percent.

40. The nanostructured composite materials of claim 35, wherein

the porosity of the nanostructured fiber assembly is greater than about 80 volume percent.

41. The nanostructured composite materials of claim 35, wherein

the composites have a high percolation rate and a high density of active sites.

42. Nanostructured materials, comprising

at least one random, interconnected open-weave assembly of nanostructured fibers, wherein the nanostructured fibers have diameters of less than about 100 nm.

43. The nanostructured materials of claim 42, wherein

the nanostructured fibers have an aspect ratio greater than about 10.

44. The nanostructured materials of claim 42, wherein

the nanostructured fibers are spaced between about 0.5 to 200 nm apart from each other.

45. The nanostructured materials of claim 42, wherein

the nanostructured fibers are spaced about 5 and 50 nm apart.

46. The nanostructured materials of claim 42, wherein

the porosity of the at least one nanostructured fiber assembly is greater than about 60 volume percent.

47. The nanostructured materials of claim 42, wherein

the porosity of the nanostructured fiber assembly is greater than about 80 volume percent.

48. The nanostructured materials of claim 42, wherein

the composites have a high percolation rate and a high density of active sites.

49. The nanostructured materials of claim 42, wherein

the composites have a high percolation rate and a high density of active sites.

50. The nanostructured materials of claim 42, comprising

an oxide or hydroxide of nickel, manganese, yttrium, zirconium, aluminum, silicon, magnesium, cobalt, vanadium, molybdenum, zinc, silver, titanium, iron, cobalt, copper, tungsten, other rare earth metals, or a combination thereof.

51. A composition of matter, comprising

nanostructured, particulate or fibrous zirconium oxide, wherein the zirconium oxide further comprises nanostructured yttrium oxide, and wherein the particles or fibers have diameters of less than about 100 nm, and the fibers are in the form of a random, interconnected open-weave assembly.