Metal and alloy nanoparticles and synthesis methods thereof

• US 7,335,245 B2
• Filed: 09/17/2004
• Issued: 02/26/2008
• Est. Priority Date: 04/22/2004
• Status: Active Grant

• Current Assignee: Honda Motor Co., Ltd. (Honda Motor Company), The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: Honda Motor Co., Ltd. (Honda Motor Company), The Research Foundation for The State University of New York (State University of New York)
• Inventors: Han, Li, Maye, Mathew M., He, Ting, Luo, Jin, Zhong, Chuan-Jian, Wang, Lingyan, Kariuki, Nancy N.
• Primary Examiner(s): WYSZOMIERSKI, GEORGE P
• Application Number:
  US10/944,461
• Publication Number:
  US 20050235776A1
• Time in Patent Office: 1,257 Days
• Field of Search: 753/51, 753/71, 977/896
• US Class Current: 75/351
• CPC Class Codes: B22F 1/054 Nanosized particles
• CPC Class Codes: B22F 1/145 Chemical treatment, e.g. passivation or decarburisation
• CPC Class Codes: B22F 9/24 starting from liquid metal compounds, e.g. solutions
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: Y10S 977/896 Chemical synthesis, e.g. chemical bonding or breaking

Abstract

The present teachings are directed toward single metal and alloy nanoparticles and synthesis methods for preparing single metal and alloy nanoparticles.

Claims

1. A method of preparing alloy nanoparticles comprising:

contacting at least one first metal-containing component with a reducing agent to form a first reaction mixture;

heating the first reaction mixture to a first temperature;

incorporating at least one second metal-containing component different from the first metal-containing component and at least one capping agent into the first reaction mixture at the first temperature to form a second reaction mixture;

heating the second reaction mixture to a second temperature;

cooling the second reaction mixture; and

precipitating alloy nanoparticles from the cooled second reaction mixture.

2. The method according to claim 1, wherein the second reaction mixture is heated to reflux conditions.

3. The method according to claim 1, further comprising:

contacting the alloy nanoparticles with a support material to form a supported alloy nanoparticles.

4. The method according to claim 3, wherein the support material comprises at least one member selected from the group consisting of carbon, carbon black, carbon fiber, carbon nanotube, inorganic materials, and combinations thereof.

5. The method according to claim 1, wherein a support material is incorporated with the solvent system prior to the contacting step.

6. The method according to claim 1, further comprising one or more of the following:

heating the alloy nanoparticles to a sufficient temperature to remove solvent and form solvent-free alloy nanoparticles;

heating the solvent-free alloy nanoparticles to a sufficient temperature in a sufficiently oxidizing environment to oxidize any capping agents and form decapped alloy nanoparticles; and

heating the decapped alloy nanoparticles to a sufficient temperature in a sufficiently reducing environment to reduce the metals of the decapped alloy nanoparticles.

7. The method according to claim 1, wherein each of the first and the second metal-containing components comprises a metal-containing complex having one or more non-metallic moieties selected from the group consisting of hydroxyls, amines, carbonyls, nitrates, oxides, acetylacetonates, halides, chlorides, alkyl-containing moieties, alkoxy-containing moieties, aryl-containing moieties, nitrosyl-containing moieties, and combinations thereof.

8. The method according to claim 1, wherein each of the first and the second metal-containing components comprises a metal-containing complex containing at least one metal selected from the group consisting of titanium, zirconium, vanadium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, tin, and selenium.

9. The method according to claim 1, wherein the contacting step occurs in a solvent system comprising a high-temperature solvent system that decomposes at a temperature greater than about 300°

C.

10. The method according to claim 9, wherein the high-temperature solvent system comprises one or more component selected from the group consisting of octyl ether, benzyl ether, toluene, tetrahydrofuran, hexane, propanol, water, 1-butanol, diphenylmethane, phenyl ether, ethanol, ethylenediamine, and combinations thereof.

11. The method according to claim 1, wherein the reducing agent comprises one or more reducing agent selected from the group consisting of sodium borohydride, 1,2-hexadecanediol, trimethylaluminum, formic acid, ammonium hydroxide, hydrazine monohydrate, and combinations thereof.

12. The method according to claim 1, wherein contacting at least one first metal-containing component with a reducing agent further comprises reducing by a reducing process selected from the group consisting of sonolysis, boil liquid reduction, reverse micelle, and combinations thereof.

13. The method according to claim 1, wherein the capping agent comprises one or more component selected from the group consisting of a thiol, a polyacrylic acid, oleyl amine, oleic acid, trimethylaluminum, tetraoctylammonium halide, tetraoctylammonium bromide, cetyltrimethylammonium halide, cetyltrimethylammonium chloride, sodium dodecyl sulfate, 2-halopropionic acid, 2-bromopropionic acid, sodium dodecylbenzenesulfonate, 3-aminopropyl-trimethyloxysilane, tetraethyl orthosilicate, poly(ethylene glycol), acetic acid, 1,10-phenanthroline, and combinations thereof.

14. A method of preparing alloy nanoparticles comprising:

contacting at least a first metal-containing component and a second metal-containing component with a reducing agent in a solvent system to form a first reaction mixture;

heating the first reaction mixture to a first temperature;

incorporating at least a third metal-containing component and at least one capping agent to the first reaction mixture at the first temperature to form a second reaction mixture;

heating the second reaction mixture to a second temperature;

cooling the reaction mixture; and

precipitating alloy nanoparticles from the cooled reaction mixture.

15. The method according to claim 14, wherein the second reaction mixture is heated to reflux conditions.

16. The method according to claim 14, further comprising:

contacting the alloy nanoparticles with a support material to form a supported alloy nanoparticles.

17. The method according to claim 16, wherein the support material comprises at least one member selected from the group consisting of carbon, carbon black, carbon fiber, carbon nanotube, inorganic materials, and combinations thereof.

18. The method according to claim 14, wherein a support material is incorporated with the solvent system prior to the contacting step.

19. The method according to claim 14, further comprising one or more of the following:

heating the alloy nanoparticles to a sufficient temperature to remove solvent and form solvent-free alloy nanoparticles;

heating the solvent-free alloy nanoparticles to a sufficient temperature in a sufficiently oxidizing environment to oxidize any capping agent and form decapped alloy nanoparticles; and

heating the decapped alloy nanoparticles to a sufficient temperature in a sufficiently reducing environment to reduce the metals of the decapped alloy nanoparticles.

20. The method according to claim 14, wherein each of the first, the second and the third metal-containing components comprises a metal-containing complex having one or more non-metallic moieties selected from the group consisting of hydroxyls, amines, carbonyls, nitrates, oxides, acetylacetonates, halides, chlorides, alkyl-containing moieties, alkoxy-containing moieties, aryl-containing moieties, nitrosyl-containing moieties, and combinations thereof.

21. The method according to claim 14, wherein each of the first, the second and the third metal-containing components comprises a metal-containing complex containing at least one metal selected from the group consisting of titanium, zirconium, vanadium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, tin, and selenium.

22. The method according to claim 14, wherein the contacting occurs in a solvent system comprising a high-temperature solvent system that decomposes at a temperature greater than about 300°

C.

23. The method according to claim 22, wherein the high-temperature solvent system comprises one or more component selected from the group consisting of octyl ether, benzyl ether, toluene, tetrahydrofuran, hexane, propanol, water, 1-butanol, diphenylmethane, phenyl ether, ethanol, ethylenediamine, and combinations thereof.

24. The method according to claim 14, wherein the reducing agent comprises one or more reducing agent selected from the group consisting of sodium borohydride, 1,2-hexadecanediol, trimethylaluminum, formic acid, ammonium hydroxide, hydrazine monohydrate, and combinations thereof.

25. The method according to claim 14, wherein contacting at least the first and the second metal-containing components with a reducing agent further comprises reducing by a reducing process selected from the group consisting of sonolysis, boil liquid reduction, reverse micelle, and combinations thereof.

26. The method according to claim 14, wherein the capping agent comprises one or more component selected from the group consisting of a thiol, a polyacrylic acid, oleyl amine, oleic acid, trimethylaluminum, tetraoctylammonium halide, tetraoctylammonium bromide, cetyltrimethylammonium halide, cetyltrimethylammonium chloride, sodium dodecyl sulfate, 2-halopropionic acid, 2-bromopropionic acid, sodium dodecylbenzenesulfonate, 3-aminopropyl-trimethyloxysilane, tetraethyl orthosilicate, poly(ethylene glycol), acetic acid, 1,10-phenanthroline, and combinations thereof.