Metal-carbon hybrid composite having nitrogen-doped carbon surface and method for manufacturing the same

Patent metadata

Field	Value
Publication number	US-9700877-B2
Application number	US-201514726816-A
Country	US
Kind code	B2
Filing date	Jun 1, 2015
Priority date	Jun 2, 2014
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

Disclosed are a metal-carbon hybrid composite having a nitrogen-doped carbon surface and a method of manufacturing the same. More particularly, the present invention relates to a method of manufacturing a metal-carbon hybrid composite, wherein the surface of carbon for the metal-carbon hybrid composite may be doped with nitrogen in a single step using a co-vaporization process, and to a metal-carbon hybrid composite having a nitrogen-doped carbon surface manufactured by the method.

First claim

What is claimed is:

1. A method of manufacturing a metal-carbon hybrid composite having a nitrogen-doped carbon surface, comprising:
(S1) vaporizing a metal precursor in a first vaporizer, and an organic material precursor for forming a carbon skeleton and a nitrogen compound precursor in a second vaporizer;
(S2) heating a reactor in which synthesis is to be carried out to a final reaction temperature; and
(S3) supplying the metal precursor and, the organic material precursor and the nitrogen compound precursor, which were vaporized in S1, into the reactor in S2 via a carrier gas in a non-contact manner, and allowing the precursors to stand for a predetermined period of time, thus synthesizing a metal-carbon hybrid composite having a nitrogen-doped carbon surface, configured such that a metal is partially or completely covered with a carbon layer, wherein a surface of the carbon layer includes defects formed by nitrogen doping using co-vaporization,
wherein the metal precursor comprises at least one selected from the group consisting of a platinum precursor, a palladium precursor, a ruthenium precursor, a nickel precursor, a cobalt precursor, a molybdenum precursor, a gold precursor, a cerium precursor, and a tungsten precursor,
wherein the organic material precursor for forming a carbon skeleton is a liquid precursor selected from the group consisting of methanol, ethanol, acetone, benzene, toluene, and xylene, or the organic material precursor for forming a carbon skeleton is a gas precursor selected from methane and acetylene, and
wherein the nitrogen compound precursor comprises at least one selected from the group consisting of ammonia and pyridine.

2. The method of claim 1 ,
wherein the platinum (Pt) precursor is selected from the group consisting of (trimethyl)methylcyclopentadienyl platinum, platinum(II) acetylacetonate, tetrakis(trifluorophosphine) platinum(0), tetrakis(triphenylphosphine)platinum(0), platinum(II) hexafluoroacetylacetonate, trimethyl(methylcyclopentadienyl) platinum(IV), and (1,5-cyclooctadiene)dimethylplatinum(II),
the palladium (Pd) precursor is selected from the group consisting of palladium(II) acetate, hexafluoroacetylacetonato-palladium(II), and palladium(II) acetylacetonate,
the ruthenium (Ru) precursor is selected from the group consisting of ruthenium acetylacetonate, bis(ethylcyclopentadienyl)ruthenium(II), bis(cyclopentadienyl)ruthenium(II), and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)ruthenium(III),
the nickel (Ni) precursor is selected from the group consisting of nickel(11) acetylacetonate, bis-cyclopentadienyl nickel, and tetrakis trifluorophosphine nickel,
the cobalt (Co) precursor is selected from the group consisting of cobalt(II) acetylacetonate, dicarbonylcyclopentadienyl cobalt, cobalt carbonyl, and cyclopentadienyl dicarbonyl-cobalt(I),
the molybdenum (Mo) precursor is selected from the group consisting of molybdenum hexacarbonyl, and molybdenum(V) chloride,
the gold (Au) precursor is methyl(triphenylphosphine)gold(I),
the cerium precursor is selected from the group consisting of tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium(IV), cerium nitrate, cerium dipivaloylmethanate, and cerium(III) chloride, and
the tungsten precursor is selected from the group consisting of tungsten hexacarbonyl, and tungsten(IV) chloride.

3. The method of claim 1 , wherein in S2, the reactor is heated to a temperature of 400° C. or higher.

4. The method of claim 1 , wherein in S3, a temperature of a connector for connecting the vaporizers to the reactor is maintained at a temperature near boiling points of the vaporized precursors.

5. The method of claim 1 , wherein the carrier gas is oxygen, hydrogen, argon, helium, or nitrogen gas.

6. A metal-carbon hybrid composite having a nitrogen-doped carbon surface manufactured by the method of claim 1 , configured such that a metal is partially or completely covered with a carbon layer, wherein a surface of the carbon layer includes defects formed by nitrogen doping using co-vaporization.

7. The metal-carbon hybrid composite of claim 6 , wherein the composite is provided in a core-shell structure, an embedded structure, a capsule structure, or a coated structure.

8. A method of manufacturing a metal-carbon hybrid composite having a nitrogen-doped carbon surface, comprising:
(S1) locating a support in a reactor;
(S2) vaporizing a metal precursor in a first vaporizer, an organic material precursor for forming a carbon skeleton and a nitrogen compound precursor in a second vaporizer;
(S3) heating a reactor in which synthesis is to be carried out to a final reaction temperature; and
(S4) supplying the metal precursor and, the organic material precursor, and the nitrogen compound precursor, which were vaporized in S2, into the reactor in S3 via a carrier gas in a non-contact manner, and allowing the precursors to stand for a predetermined period of time, thus synthesizing a metal-carbon hybrid composite having a nitrogen-doped carbon surface, configured such that a metal is partially or completely covered with a carbon layer, and the composite is loaded on the support, wherein a surface of the carbon layer includes defects formed by nitrogen doping using co-vaporization,
wherein the metal precursor comprises at least one selected from the group consisting of a platinum precursor, a palladium precursor, a ruthenium precursor, a nickel precursor, a cobalt precursor, a molybdenum precursor, a gold precursor, a cerium precursor, and a tungsten precursor,
wherein the organic material precursor for forming a carbon skeleton is a liquid precursor selected from the group consisting of methanol, ethanol, acetone, benzene, toluene, and xylene, or the organic material precursor for forming a carbon skeleton is a gas precursor selected from methane and acetylene, and
wherein the nitrogen compound precursor comprises at least one selected from the group consisting of ammonia and pyridine.

9. The method of claim 8 , wherein the support is selected from the group consisting of carbon paper, activated carbon, carbon black, alumina powder, an alumina sheet, silica powder, titania powder, zirconia powder, zeolite, and nickel or aluminum foil.

10. The method of claim 8 , wherein in S3, the reactor is heated to a temperature of 400° C. or higher.

11. The method of claim 8 , wherein the carrier gas is oxygen, hydrogen, argon, helium, or nitrogen gas.

12. A metal-carbon hybrid composite having a nitrogen-doped carbon surface manufacture by the method of claim 8 , configured such that a metal is partially or completely covered with a carbon layer, and the composite is loaded on a support, wherein a surface of the carbon layer includes defects formed by nitrogen doping using co-vaporization.

13. The metal-carbon hybrid composite of claim 12 , wherein the composite is provided in a core-shell structure, an embedded structure, a capsule structure, or a coated structure.

14. The metal-carbon hybrid composite of claim 12 , wherein the support is selected from the group consisting of carbon paper, activated carbon, carbon black, alumina powder, an alumina sheet, silica powder, titania powder, zirconia powder, zeolite, and nickel or aluminum foil.

Assignees

• Korea Energy Research Inst

Inventors

• Kim Hee-Yeon
• Kwon Guk-Hyeon

Classifications

• H01M4/9041

  Metals or alloys (H01M4/92 takes precedence) · CPC title

• H01M4/92 Primary

  Metals of platinum group (H01M4/94 {, H01M4/9058} take precedence) · CPC title

• B01J27/24 Primary

  Nitrogen compounds · CPC title

• B01J23/38

  of noble metals · CPC title

• C01B32/00

  Carbon; Compounds thereof (C01B21/00, C01B23/00 take precedence; percarbonates C01B15/10; carbon black C09C1/48) · CPC title