Metal nanoparticle-PCP complex and manufacturing method therefor

Patent metadata

Field	Value
Publication number	US-9586196-B2
Application number	US-201214237292-A
Country	US
Kind code	B2
Filing date	Aug 3, 2012
Priority date	Aug 5, 2011
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

Provided is a composite, including a metal nanoparticle inside a porous coordination polymer (PCP), in which the PCP is formed of a metal ion and an organic ligand.

First claim

The invention claimed is:

1. A composite having a core-shell structure in which a core is covered by a shell,
wherein the core comprises a metal nanoparticle, the shell comprises a porous coordination polymer (PCP), and the PCP is formed of a metal ion and an organic ligand,
wherein the PCP forms layers that cover the metal nanoparticle,
wherein the PCP has an average thickness extending from a surface of the composite to the metal nanoparticle of 1 to 200 nm,
wherein the metal nanoparticle comprises a noble metal nanoparticle, and
wherein the organic ligand forming the PCP is selected from the group consisting of
(a) a compound in which two, three, or four carboxyl groups are bonded to an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, pyrene, 1,4-dihydronaphthalene, tetralin, biphenylene, triphenylene, acenaphthylene, and acenaphthene, wherein the ligand is optionally mono-, di-, or trisubstituted by a substituent selected from the group consisting of halogen atoms, a nitro group, an amino group, an acylamino group, a cyano group, a hydroxyl group, methylenedioxy, ethylenedioxy, a linear or branched alkoxy group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms, SH, a trifluoromethyl group, a sulfonic acid group, a carbamoyl group, an alkylamino group, and a dialkylamino group,
(b) an unsaturated divalent carboxylic acid, and
(c) a nitrogen-containing aromatic compound that coordinates through two or more ring nitrogen atoms, wherein the compound is optionally mono-, di-, or trisubstituted by the substituent.

2. A composite having a core-shell structure in which a core is covered by a shell,
wherein the core comprises a metal nanoparticle, the shell comprises a porous coordination polymer (PCP), and the PCP is formed of a metal ion and an organic ligand,
wherein the PCP forms layers that cover the metal nanoparticle,
wherein the PCP has an average thickness extending from a surface of the composite to the metal nanoparticle of 1 to 200 nm,
wherein the metal nanoparticle comprises at least one metal selected from the group consisting of gold, platinum, palladium, nickel, cobalt, manganese, chromium, silver, copper, iron, ruthenium, rhodium, zinc, and an alloy or oxide thereof, and
wherein the organic ligand forming the PCP is selected from the group consisting of
(a) a compound in which two, three, or four carboxyl groups are bonded to an aromatic ring selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, pyrene, 1,4-dihydronaphthalene, tetralin, biphenylene, triphenylene, acenaphthylene, and acenaphthene, wherein the ligand is optionally mono-, di-, or trisubstituted by a substituent selected from the group consisting of halogen atoms, a nitro group, an amino group, an acylamino group, a cyano group, a hydroxyl group, methylenedioxy, ethylenedioxy, a linear or branched alkoxy group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms, SH, a trifluoromethyl group, a sulfonic acid group, a carbamoyl group, an alkylamino group, and a dialkylamino group,
(b) an unsaturated divalent carboxylic acid, and
(c) a nitrogen-containing aromatic compound that coordinates through two or more ring nitrogen atoms, wherein the compound is optionally mono-, di-, or trisubstituted by the substituent.

3. The composite according to claim 1 , wherein the metal nanoparticle has a size of 1 to 200 nm.

4. The composite according to claim 1 , wherein 50% or more of the metal nanoparticle is brought into contact with a gaseous reactant that passes through the PCP layer.

5. A method of producing a compound, comprising contacting the composite of claim 1 with a gaseous substance such that the metal nanoparticle in the composite is subjected to a reaction with the gaseous substance adsorbed by the PCP to produce the compound.

6. The method according to claim 5 , wherein the gas substance comprises hydrogen and nitrogen, the metal nanoparticle comprises an iron-based catalyst, and the produced compound comprises ammonia.

7. The composite according to claim 2 , wherein the metal nanoparticle has a size of 1 to 200 nm.

8. The composite according to claim 7 , wherein 50% or more of the metal nanoparticle is brought into contact with a gaseous reactant that passes through the PCP layer.

9. The composite according to claim 1 , wherein a carboxy group is introduced into the metal nanoparticle via an SH group.

10. A method of producing a compound, comprising contacting the composite of claim 2 with a gaseous substance such that the metal nanoparticle in the composite is subjected to a reaction with the gaseous substance absorbed by the PCP to produce the compound.

11. The method according to claim 10 , wherein the gas substance comprises hydrogen and nitrogen, the metal nanoparticle comprises an iron-based catalyst, and the produced compound comprises ammonia.

Assignees

• Kitagawa Hiroshi
• Kobayashi Hirokazu
• Univ Kyoto

Inventors

• Kitagawa Hiroshi
• Kobayashi Hirokazu

Classifications

• C08K3/08

  Metals · CPC title

• C08K2201/011

  Nanostructured additives · CPC title

• B01J23/70

  of the iron group metals or copper · CPC title

• C07C65/03

  monocyclic and having all hydroxy or O-metal groups bound to the ring · CPC title

• H01M4/92

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