Core-shell type nanoparticles comprising crystalline metal-oxide shell and method for preparing the same

• US 8,343,577 B2
• Filed: 10/05/2010
• Issued: 01/01/2013
• Est. Priority Date: 12/06/2005
• Status: Active Grant

• Current Assignee: LG Chem Limited (LG Corporation)
• Original Assignee: LG Chem Limited (LG Corporation)
• Inventors: Kim, Sang Ho, Lee, Woo Ram, Lim, Young Soo
• Primary Examiner(s): Le, Hoa (Holly)
• Application Number:
  US12/898,388
• Publication Number:
  US 20110020650A1
• Time in Patent Office: 819 Days
• Field of Search: 428403-406, 427212-217
• US Class Current: 427/216
• CPC Class Codes: B01J 13/02 Making microcapsules or microballoons for medical preparations A61K9/50
• CPC Class Codes: B22F 1/054 Nanosized particles
• CPC Class Codes: B22F 1/0545 Dispersions or suspensions of nanosized particles
• CPC Class Codes: B22F 1/056 Submicron particles having a size above 100 nm up to 300 nm
• CPC Class Codes: B22F 1/107 containing organic material comprising solvents, e.g. for slip casting
• CPC Class Codes: B22F 1/16 Metallic particles coated with a non-metal coated with lubricating or binding agents or with organic material B22F1/10
• CPC Class Codes: B22F 2998/00 Supplementary information concerning processes or compositions relating to powder metallurgy
• CPC Class Codes: B22F 2998/10 Processes characterised by the sequence of their steps
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01G 23/053 Producing by wet processes, e.g. hydrolysing titanium salts
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: Y10S 977/778 within specified host or matrix material, e.g. nanocomposite films
• CPC Class Codes: Y10S 977/81 Of specified metal or metal alloy composition
• CPC Class Codes: Y10S 977/811 Of specified metal oxide composition, e.g. conducting or semiconducting compositions such as ITO, ZnOx
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2993 Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Abstract

Disclosed herein are core-shell type nanoparticles comprising nanoparticle cores made of a metal or semiconductor, and shells made of crystalline metal oxide formed on the surfaces of the nanoparticle cores, as well as a preparation method thereof. According to the disclosed invention, the core-shell nanoparticles, consisting of metallic or semiconductor cores and crystalline metal oxide shells, can be prepared by epitaxially growing metal oxide on the surfaces of the metallic or semiconductor nanoparticle cores. By virtue of the crystalline metal oxide shells, the core nanoparticle made of metal or semiconductor can ensure excellent chemical and mechanical stability, and the core-shell nanoparticles can show new properties resulting from the interaction between the metal cores and the metal oxide crystal shells.

Claims

1. A method for preparing core-shell type nanoparticles, the method comprising the steps of:

a) dispersing, in a mixed solvent of water and a first organic solvent, nanoparticle cores made of a material selected from the group consisting of the metals of Groups 3-15 of the periodic table, lanthanide metals, actinide metals, alloys of two or more of the metals, and semiconductor compounds; and

b) dropping a metal oxide precursor dissolved in a second organic solvent into the solution prepared in step a), thereby forming core-shell type nanoparticles comprising shells made of crystalline metal oxide formed on the surfaces of the nanoparticle cores,

wherein the rate of dropping in step b) is 5 μ

l/sec to 1 ml/sec per 100 mg of the nanoparticle cores.

2. The method according to claim 1, wherein the crystalline metal oxide shells are formed at a temperature of 5-40°

C.

3. The method according to claim 1, wherein the volume ratio of water and the first organic solvent is controlled to 1:

3 to 1;

10000, such that reaction rate is adjusted to an extent that the hydrolysis of the metal oxide precursor can be completed within 1-60 minutes.

4. The method according to claim 1, wherein the first or the second organic solvent is selected from the group consisting of alcohols, amides, and nitrites.

5. The method according to claim 1, wherein the metal oxide precursor is selected from the group consisting of alkoxides, carboxylates, and halides of metal.

6. The method according to claim 1, wherein carboxylic acid, β

-diketone, or a mixture thereof is added during step a) or b) as an additive for controlling reaction rate.

7. The method according to claim 1, wherein the rate of the dropping in step b) is low enough that the metal oxide can uniformly form the shells on the surfaces of the nanoparticle cores while it can epitaxially grow into crystals.

8. A method for preparing core-shell type nanoparticles, the method comprising the steps of:

a) dispersing nanoparticle cores made of a material selected from the group consisting of the metals of Groups 3-15 of the periodic table, lanthanide metals, actinide metals, alloys of two or more of the metals and semiconductor compounds, and dissolving a metal oxide precursor in a first organic solvent; and

b) dropping a mixed solvent of water and a second organic solvent into the solution prepared in step a), thereby forming core-shell type nanoparticles comprising shells made of crystalline metal oxide formed on the surfaces of the nanoparticle cores, p1 wherein the rate of dropping in step b) is 5 μ

l/sec to 1 ml/sec per 100 mg of the nanoparticle cores.

9. The method according to claim 8, wherein the crystalline metal oxide shells are formed at a temperature of 5-40°

C.

10. The method according to claim 8, wherein the volume ratio between water and the second organic solvent is controlled to 1:

3 to 1;

10000, such that the hydrolysis of the metal oxide precursor can be completed within 1-60 minutes.

11. The method according to claim 8, wherein the first or the second organic solvent is selected from the group consisting of alcohols, amides, and nitriles.

12. The method according to claim 8, wherein the metal oxide precursor is selected from the group consisting of alkoxides, carboxylates, and halides of metal.

13. The method according to claim 8, wherein carboxylic acid, β

-diketone, or a mixture thereof is added during step a) or b) as an additive for controlling reaction rate.