Preparation of uniform nanoparticles of ultra-high purity metal oxides, mixed metal oxides, metals, and metal alloys

• US 8,211,388 B2
• Filed: 02/16/2007
• Issued: 07/03/2012
• Est. Priority Date: 02/16/2006
• Status: Active Grant

• Current Assignee: Brigham Young University (The Church of Jesus Christ of Latter-Day Saints)
• Original Assignee: Brigham Young University (The Church of Jesus Christ of Latter-Day Saints)
• Inventors: Woodfield, Brian F., Liu, Qingyuan, Liu, Shengfeng, Boerio-Goates, Juliana, Smith, Stacey Janel
• Primary Examiner(s): Le, Hoa (Holly)
• Application Number:
  US11/707,840
• Publication Number:
  US 20080032132A1
• Time in Patent Office: 1,964 Days
• Field of Search: 753/43, 753/92, 977/840, 977/896
• US Class Current: 423/1
• CPC Class Codes: B22F 1/054 Nanosized particles
• CPC Class Codes: B22F 2009/043 by ball milling
• CPC Class Codes: B22F 2009/045 by other means than ball or jet milling
• CPC Class Codes: B22F 2009/049 by pulverising at particular temperature
• CPC Class Codes: B22F 2999/00 Aspects linked to processes or compositions used in powder metallurgy
• CPC Class Codes: B22F 9/04 starting from solid material, e.g. by crushing, grinding or milling C22C1/1084 takes precedence; crushing, grinding or milling, in general, see the relevant subclasses, e.g. B02C
• CPC Class Codes: B22F 9/20 starting from solid metal compounds
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 13/322 of elements or compounds in the solid state
• CPC Class Codes: C01F 17/218 Yttrium oxides or hydroxides
• CPC Class Codes: C01F 17/224 Oxides or hydroxides of lanthanides
• CPC Class Codes: C01F 7/308 Thermal decomposition of nitrates
• CPC Class Codes: C01G 1/02 Oxides
• CPC Class Codes: C01G 19/02 Oxides
• CPC Class Codes: C01G 23/0536 by hydrolysing chloride-containing salts
• CPC Class Codes: C01G 25/00 Compounds of zirconium
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01G 29/00 Compounds of bismuth
• CPC Class Codes: C01G 3/02 Oxides; Hydroxides
• CPC Class Codes: C01G 49/06 Ferric oxide [Fe2O3]
• CPC Class Codes: C01G 49/08 : Ferroso-ferric oxide [Fe3O4]
• CPC Class Codes: C01G 5/02 : Halides
• CPC Class Codes: C01G 51/00 : Compounds of cobalt
• CPC Class Codes: C01G 51/04 : Oxides; Hydroxides
• CPC Class Codes: C01G 53/00 : Compounds of nickel
• CPC Class Codes: C01G 53/006 : Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen nickelates C01G53/40
• CPC Class Codes: C01G 53/04 : Oxides; Hydroxides
• CPC Class Codes: C01G 55/002 : Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen C01G55/007 takes precedence
• CPC Class Codes: C01G 9/02 : Oxides; Hydroxides
• CPC Class Codes: C01P 2002/72 : by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/88 : by thermal analysis data, e.g. TGA, DTA, DSC
• CPC Class Codes: C01P 2004/04 : obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/51 : Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/52 : highly monodisperse size distribution
• CPC Class Codes: C01P 2004/64 : Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: Y10S 977/84 : Manufacture, treatment, or detection of nanostructure
• CPC Class Codes: Y10S 977/896 : Chemical synthesis, e.g. chemical bonding or breaking
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]

Abstract

In preferred embodiments, metal nanoparticles, mixed-metal (alloy) nanoparticles, metal oxide nanoparticles and mixed-metal oxide nanoparticles are provided. According to embodiments, the nanoparticles may possess narrow size distributions and high purities. In certain preferred embodiments, methods of preparing metal nanoparticles, mixed-metal nanoparticles, metal oxide nanoparticles and mixed-metal nanoparticles are provided. These methods may provide tight control of particle size, size distribution, and oxidation state. Other preferred embodiments relate to a precursor material that may be used to form nanoparticles. In addition, products prepared from such nanoparticles are disclosed.

Claims

1. A method of forming nanoparticles comprising:

providing at least one metal salt;

providing at least one base, wherein the at least one base comprises an ammonium salt;

mixing the at least one metal salt and the at least one base to form a precursor material, wherein the metal salt and base ions are not completely solvated; and

heating the precursor material to a pre-determined temperature, at a pre-determined rate, in a pre-determined atmosphere, and for a pre-determined length of time, wherein the nanoparticles have an average particle size, wherein the average particle size is between about 1 nm and about 100 nm, a size distribution, wherein the size distribution is within about 1% to about 15% of the average particle size, and a substantially pre-determined stoichiometry.

2. The method according to claim 1, wherein the nanoparticles comprise at least one compound selected from the group consisting of a metal, a metal oxide, a mixed-metal, and a mixed-metal oxide.

3. The method according to claim 2, wherein the metal of the metal salt is selected from the group consisting of alkali metals, alkali earth metals, transition metals, lanthanide series metals, actinide series metals, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, and polonium.

4. The method according to claim 1, wherein the atmosphere is an inert atmosphere.

5. The method according to claim 1, wherein the atmosphere is a reductive atmosphere.

6. The method according to claim 1, further comprising the step of drying the precursor material at a pre-determined temperature and for a pre-determined length of time.

7. The method according to claim 1, wherein the atmosphere is an oxidative atmosphere.

8. The method according to claim 1, wherein the at least one metal salt and the at least one base are mixed in the solid state substantially free of solvent and solvent molecules.

9. The method according to claim 1, wherein the at least one base comprises ammonium carbonate, ammonium bicarbonate, ammonium sesquicarbonate, ammonium hydroxide or ammonium nitrate.

10. The method according to claim 1, wherein the step of providing at least one metal salt comprises the step of providing two or more metal salts, and wherein the molar ratio of the metals of the two or more metal salts is substantially equal to the molar ratio of the metals in the nanoparticles.

11. A method according to claim 1, wherein the at least one metal salt comprises a compound selected from the group consisting of metal chloride, metal acetate, metal oxalate, metal citrate, metal sulfate, metal nitrate and hydrates thereof.

12. A method according to claim 1, wherein water is added to the precursor mixture to facilitate mixing or to ensure reaction completion.

13. A method of forming nanoparticles comprising:

providing at least one metal salt;

providing at least one base comprising an ammonium salt;

mixing the at least one metal salt and the at least one base to form a precursor material, wherein the metal salt and base ions are not completely solvated; and

heating the precursor material, wherein the nanoparticles have an average particle size, wherein the average particles size is between about 1 nm and about 100 nm, and a size distribution, wherein the size distribution is within about 1% to about 30% of the average particle size, and wherein the heating releases gaseous by-products.

14. A method according to claim 13, wherein the at least one metal salt and the at least one base are mixed in the solid state substantially free of solvent and solvent molecules.

15. A method according to claim 13, wherein the at least one base comprises ammonium carbonate, ammonium bicarbonate, ammonium sesquicarbonate, ammonium hydroxide or ammonium nitrate.

16. A method according to claim 13, wherein the at least one base comprises ammonium bicarbonate.

17. A method according to claim 13, wherein the heating is performed in an inert atmosphere or a reductive atmosphere or an oxidative atmosphere.

18. A method according to claim 13, wherein the nanoparticles comprise at least one compound selected from the group consisting of a metal, a metal oxide, a mixed-metal, and a mixed-metal oxide.

19. A method according to claim 13, wherein the at least one metal of the at least one metal salt is selected from the group consisting of alkali metals, alkali earth metals, transition metals, lanthanide series metals, actinide series metals, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, and polonium.

20. A method according to claim 13, wherein the at least one metal salt comprises a compound selected from the group consisting of metal chloride, metal acetate, metal oxalate, metal citrate, metal sulfate, metal nitrate and hydrates thereof.

21. A method according to claim 13, wherein the molar ratio of the metal salt to base comprises a number in a range from about 0.01 to about 5.

22. A method according to claim 13, wherein the size distribution is within about 1% to about 10% of the average particle size.

23. A method according to claim 13, wherein the step of providing a metal salt comprises the step of providing two or more metal salts, and wherein the molar ratio of the metals of the two or more metal salts is substantially equal to the molar ratio of the metals in the nanoparticles.

24. A method according to claim 13, further comprising the step of providing water prior to or during the step of mixing to facilitate mixing or to ensure reaction completion.

25. A method according to claim 13, wherein the at least one metal salt is in an anhydrous form.

26. A method according to claim 13, wherein the at least one metal salt is in a hydrated form.

27. A method according to claim 13, wherein the at least one metal salt includes a mixture of metal salts.