Composite body in which first metal-containing particles and second metal-containing particles are supported on carbon material or connected by carbon material, and method for producing same

Patent metadata

Field	Value
Publication number	US-9498774-B2
Application number	US-201514740530-A
Country	US
Kind code	B2
Filing date	Jun 16, 2015
Priority date	Dec 17, 2012
Publication date	Nov 22, 2016
Grant date	Nov 22, 2016

Abstract

The present invention relates to a composite body in which first metal-containing particles and second metal-containing particles are supported on a carbon material or connected by a carbon material, and a method for producing the same. The above composite body can, if the first metal-containing particles exhibit a catalytic activity, be applied as a reaction catalyst and can also be used in various fields such as the manufacture of the adsorbent or the separation membrane.

First claim

The invention claimed is:

1. A method for preparing a composite body in which first size-controlled metal-containing particles and second size-controlled metal-containing particles are supported on a carbon material or connected by a carbon material, the method comprising the following steps:
a first step of mixing a first metal hydrate salt forming a first metal oxide, a second metal hydrate salt forming a second metal oxide, and a porous carbon material particle;
a second step of melt-infiltrating the first metal hydrate salt and the second metal hydrate salt in the pores of the porous carbon material particle at a temperature that can melt the first metal hydrate salt and the second metal hydrate salt;
optionally, a third step of drying the porous carbon material particles in which the first metal hydrate salt and the second metal hydrate salt are melt-infiltrated;
a fourth step of subjecting the resultant carbon material particles to high temperature calcination at a temperature and condition that thermally decompose the first metal hydrate salt, the second metal hydrate salt and the porous carbon material, thereby forming the first metal oxide particles and the second metal oxide particles in which the particle sizes are controlled by the pores of the porous carbon material, while forming a composite body in which the first metal oxide particles and the second metal oxide particles are supported or connected by the carbon material remaining after the thermal decomposition of the porous carbon material; and
optionally, a fifth step of chemically changing the first metal oxide particles, the second metal oxide particles or both of them to the first metal-containing particles or the second metal-containing particles.

2. The method for preparing a composite body according to claim 1 wherein in the fourth step, the first metal oxide particles are separated by the second metal oxide particles, thus inhibiting the first metal oxide particles from sintering.

3. The method for preparing a composite body according to claim 1 wherein a reduction potential of the second metal oxide is higher than a reduction potential of the first metal oxide, and in the fifth step the whole or a surface of the first metal oxide particle is reduced to the first metal by a reduction reaction.

4. The method for preparing a composite body according to claim 1 wherein, in the first step, the porous carbon material particles have an average size of 200 nm to 0.2 μm.

5. The method for preparing a composite body according to claim 1 wherein, in the first step, the porous carbon material particles have an average pore size of 2 to 50 nm.

6. The method for preparing a composite body according to claim 1 wherein, in the first step, the porous carbon material particles have a pore volume of 0.3 cm 3/g or more.

7. The method for preparing a composite body according to claim 1 wherein, in the fourth step, the first metal oxide particles and the second metal oxide particles, each independently, have an average particle size of 2 to 30 nm.

8. The method for preparing a composite body according to claim 1 wherein, in the fourth step, the second metal oxide particles are amorphous.

9. The method for preparing a composite body according to claim 1 wherein, in the fourth step, the second metal oxide particles are selected from the group consisting of silica, alumina, titania, zirconia and a mixture thereof.

10. The method for preparing a composite body according to claim 1 wherein in the fourth step, the high temperature calcination is conducted at a temperature of 300 to 650° C.

11. The method for preparing a composite body according to claim 1 wherein the first metal hydrate salt and the second metal hydrate salt have, each respectively, a melting point between 30 and 100° C.

12. The method for preparing a composite body according to claim 1 wherein the first metal hydrate salt is selected from the group consisting of Cr(NO 3 ) 3 .9H 2 O, Fe(NO 3 ) 3 .9H 2 O, Co(NO 3 ) 2 .6H2O, Ni(NO 3 ) 2 .6H 2 O, Pd(NO 3 ) 2 .2H 2 O, FeCl 3 .6H 2 O, CoCl 2 .6H 2 O, CuCl 2 .2H 2 O, Cr 2 (SO 4 ) 3 .12H 2 O, FeSO 4 .7H 2 O, CoSO 4 .7H 2 O, and NiSO 4 .6H 2 O.

13. The method for preparing a composite body according to claim 1 wherein the second metal hydrate salt is selected from the group consisting of Mg(NO 3 ) 2 .6H 2 O, Al(NO 3 ) 3 .9H 2 O, Zn(NO 3 ) 2 .3H 2 O, Zn(NO 3 ) 2 .6H 2 O, MnCl 2 .4H 2 O, Al 2 (SO 4 ) 3 .18H 2 O, ZnSO 4 .6H 2 O, and ZrO(NO 3 ) 2 .6H 2 O.

14. The method for preparing a composite body according to claim 1 wherein the porous carbon material is selected from the group consisting of activated carbon, activated charcoal, synthetic porous carbon support CMK and a mixture thereof.

15. The method for preparing a composite body according to claim 1 wherein the first metal hydrate salt and the second metal hydrate salt are infiltrated in an amount of 0.3 to 3 grams based on the carbon unit gram thereof, in consideration of the density of each metal salt and the pore volume of the porous carbon material.

16. The method for preparing a composite body according to claim 1 wherein the first step of mixing the first metal hydrate salt, the second metal hydrate salt and the porous carbon material particles is conducted by mechanically grinding them.

17. A composite body, prepared by the method defined in claim 1 , in which first metal-containing particles and second metal-containing particles are supported on a carbon material or connected by a carbon material,
wherein the first metal-containing particles are maintained at intervals between the particles by the second metal-containing particles and the carbon material, and
the first metal-containing particles are contained in an amount of 10 to 50% by weight, the second metal-containing particles are in an amount of 10 to 50% by weight, and the residual carbon material is contained in an amount of 20 to 60% by weight, based on the total amount of the composite body.

18. The composite body according to claim 17 wherein the first metal-containing particles exhibit a catalytic activity and the second metal-containing particles are inert to the catalytic reaction.

19. The composite body according to claim 17 wherein the first metal-containing particles are those in which the surface or the whole of the first metal oxide particles are reduced to a first metal.

20. The composite body according to claim 17 wherein the first metal-containing particles are a crystalline form having a grid structure, and the second metal-containing particles are amorphous.

Assignees

• Korea Energy Research Inst

Inventors

• Park Ji Chan
• Jung Heon
• Lee Ho Tae
• Yang Jung Ii
• Chun Dong Hyun
• Hong Sung Jun

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title