Metal-carbon composite supported catalyst for hydrogen production using co-evaporation and method of preparing the same

Patent metadata

Field	Value
Publication number	US-9566567-B2
Application number	US-201314030070-A
Country	US
Kind code	B2
Filing date	Sep 18, 2013
Priority date	Sep 24, 2012
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

A metal-carbon composite supported catalyst for hydrogen production using co-evaporation and a method of preparing the same, wherein the catalyst is configured such that a metal-carbon composite having a core-shell structure resulting from co-evaporation is supported on the surface of an oxide-based support coated with carbon, thereby maintaining superior durability without agglomeration even in a catalytic reaction at a high temperature. Because part or all of the surface of metal is covered with the carbon shell, even when the catalyst is applied under severe reaction conditions including high temperatures, long periods of time, acidic or alkaline states, etc., the metal particles do not agglomerate or are not detached, and do not corrode, thus exhibiting high performance and high durability. Therefore, inactivation of the catalyst or the generation of side reactions can be prevented, so that the catalyst can be efficiently utilized in hydrogen production.

First claim

What is claimed is:

1. A method of preparing a metal-carbon composite supported catalyst for hydrogen production, comprising:
(S1) coating a surface of an oxide-based support with carbon to form a carbon layer, and then positioning the support in a reactor;
(S2) providing a metal precursor for forming a metal core and an organic precursor for forming a carbon shell to respective vaporizers, in order to be supplied to the reactor in a vaporized state wherein the metal precursor comprises one or more selected from the group consisting of a platinum precursor, a palladium precursor, a ruthenium precursor, a nickel precursor, a cobalt precursor, a molybdenum precursor and a gold precursor;
(S3) feeding the metal precursor and the organic precursor, which are vaporized, into the reactor containing the oxide-based support having a carbon layer by means of a carrier gas while preventing the precursors from coming into contact with each other prior to introducing each of the vaporized precursors to the reactor; and
(S4) heating the reactor and then maintaining a temperature of the reactor at a predetermined level, thus synthesizing a metal-carbon composite having the core-shell structure including the metal core and the carbon shell, the core-shell structure being supported on the oxide-based support having a carbon layer.

2. The method of claim 1 , wherein (S1) further comprises performing surface treatment using N-doping or ozone after coating the surface of the oxide-based support with carbon.

3. The method of claim 1 , wherein the oxide-based support comprises one or more selected from the group consisting of alumina, silica, titania, zirconia, zeolite and MCM-41.

4. The method of claim 1 , wherein coating the surface of the oxide-based support with carbon in (S1) is performed at 400˜1000° C.

5. The method of claim 1 , wherein coating the surface of the oxide-based support with carbon in (S1) is performed using one or more selected from the group consisting of methane, acetylene, methanol, ethanol, acetone, benzene, toluene and xylene.

6. 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(I) and (1,5-cyclooctadiene) dimethylplatinum(II), the palladium (Pd) precursor is palladium(II) acetate, hexafluoroacetylacetonate palladium(II), or palladium(II) acetylacetonate, the ruthenium (Ru) precursor is ruthenium acetylacetonate, bis(ethylcyclopentadienyl) ruthenium(II), bis(cyclopentadienyl) ruthenium(II), or tris(2,2,6,6-tetramethyl-3,5-heptadionate) ruthenium(III), the nickel (Ni) precursor is nickel(II) acetylacetonate, bis-cyclopentadienyl nickel, or tetrakis trifluorophosphine nickel, the cobalt (Co) precursor is cobalt(II) acetylacetonate, dicarbonylcyclopentadienyl cobalt, cobalt carbonyl, or cyclopentadienyl dicarbonyl-cobalt(I), the molybdenum (Mo) precursor is molybdenum hexacarbonyl or molybdenum(V) chloride, and the gold (Au) precursor is methyl(triphenylphosphine)gold (I).

7. The method of claim 1 , wherein the organic precursor for forming the carbon shell comprises one or more selected from the group consisting of methane, acetylene, methanol, ethanol, acetone, benzene, toluene and xylene.

8. The method of claim 1 , wherein the carrier gas comprises one or more selected from the group consisting of oxygen, hydrogen, argon, helium and nitrogen gases.

9. The method of claim 1 , wherein (S2) comprises maintaining a temperature approximate a boiling point of each of the vaporized precursors for maintaining precursor vaporization.

10. The method of claim 1 , wherein in (S3), the reactor is heated to a temperature of 300° C. or more.

11. The method of claim 1 , wherein in (S3), the reactor is heated to a temperature of 300˜1800° C.

Assignees

• Korea Energy Research Inst

Inventors

• Kim Hee Yeon
• Hong Seok Yong
• Kim Hyun Uk

Classifications

• B01J2235/00

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

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/34

  Mechanical properties · CPC title

• C01B2203/107

  Platinum catalysts · CPC title

• B01J23/44

  Palladium · CPC title