Polyoxometalate compound and method for producing same, sintered body of polyoxometalate compound, and reaction catalyst

Patent metadata

Field	Value
Publication number	US-2021122636-A1
Application number	US-201917254939-A
Country	US
Kind code	A1
Filing date	Jul 3, 2019
Priority date	Jul 4, 2018
Publication date	Apr 29, 2021
Grant date	—

Abstract

Disclosed is a polyoxometalate compound including a metal-substituted polyoxometalate. The metal-substituted polyoxometalate includes a polyoxometalate having defect sites, a substituting metal atom introduced into the defect sites, and an organic ligand. The substituting metal atom is divalent platinum or palladium. The organic ligand may be a bidentate ligand having an aliphatic heterocycle containing two nitrogen atoms coordinately bonded to the substituting metal atom. One substituting metal atom is introduced into one defect site.

First claim

1 . A polyoxometalate compound comprising a metal-substituted polyoxometalate and a counter ion thereof,
wherein the metal-substituted polyoxometalate comprises: a polyoxometalate having one or more defect sites; a substituting metal atom introduced into the defect sites; and an organic ligand coordinately bonded to the substituting metal atom, wherein the substituting metal atom is divalent platinum or palladium, wherein the organic ligand is a bidentate ligand comprising an aliphatic heterocycle comprising two nitrogen atoms coordinately bonded to the substituting metal atoms, and wherein the one substituting metal atom is introduced into each of the one or more defect sites.

2 . A method for producing the polyoxometalate compound according to claim 1 , comprising:
in a reaction solution comprising a polyoxometalate having one or more defect sites and a metal complex having a central metal and an organic ligand, reacting the polyoxometalate with the metal complex to generate a metal-substituted polyoxometalate, wherein the metal-substituted polyoxometalate comprises: the polyoxometalate; a substituting metal atom that is the central metal introduced into the defect sites; and the organic ligand coordinately bonded to the substituting metal atom, wherein the central metal and the substituting metal atom are divalent platinum or palladium, wherein the organic ligand is a bidentate ligand comprising an aliphatic heterocycle comprising two nitrogen atoms coordinately bonded to the one central metal or the one substituting metal atom, and wherein, in the metal-substituted polyoxometalate, the one substituting metal atom is introduced into each of the one or more defect sites.

3 . The method according to claim 2 ,
wherein the organic ligand is N,N′-dimethylpiperazine.

4 . A polyoxometalate compound comprising a metal-substituted polyoxometalate and a counter ion thereof,
wherein the metal-substituted polyoxometalate comprises: a polyoxometalate having one or more defect sites; a first substituting metal atom that is introduced into the defect site; a first organic ligand coordinately bonded to the first substituting metal atom; a second substituting metal atom introduced into the defect site; and a second organic ligand coordinately bonded to the second substituting metal atom, wherein the first substituting metal atom is a divalent platinum atom and the second substituting metal atom is divalent palladium, or the first substituting metal atom is divalent palladium and the second substituting metal atom is divalent platinum, and wherein one of the first substituting metal atom and one of the second substituting metal atom are introduced into each of the one or more defect sites.

5 . A method for producing the polyoxometalate compound according to claim 4 , comprising:
in a reaction solution comprising a mononuclear type polyoxometalate compound comprising a metal-substituted polyoxometalate comprising a first substituting metal atom and a counter ion thereof, and a metal complex comprising a central metal, reacting the mononuclear type polyoxometalate compound with the metal complex to generate a binuclear type polyoxometalate compound comprising the first substituting metal atom and a second substituting metal atom that is the central metal, wherein the metal-substituted polyoxometalate of the mononuclear type polyoxometalate compound comprises: a polyoxometalate having one or more defect sites; the first substituting metal atom introduced into the defect site; and a first organic ligand coordinately bonded to the first substituting metal atom, wherein the metal complex comprises the central metal and a second organic ligand coordinately bonded to the central metal, wherein the first substituting metal atom is divalent platinum and the central metal and the second substituting metal atom are divalent palladium, or the first substituting metal atom is palladium and the central metal and the second substituting metal atom are divalent platinum, wherein, in the mononuclear type polyoxometalate compound, one of the first substituting metal atom is introduced into each of the one or more defect sites, and wherein, in the binuclear type polyoxometalate compound, one of the first substituting metal atom and one of the second substituting metal atom are introduced into each of the one or more defect sites.

6 . The method according to claim 5 ,
wherein the first organic ligand is two ammonia ligands, two alkylamine ligands having 1 to 3 carbon atoms, or one ethylenediamine ligand, coordinately bonded to one of the first substituting metal atoms.

7 . A method for producing a polyoxometalate compound, comprising:
in a reaction solution comprising a polyoxometalate comprising one or more defect sites, and a metal complex comprising a central metal and an organic ligand, reacting the polyoxometalate with the metal complex to generate a metal-substituted polyoxometalate, wherein the metal-substituted polyoxometalate comprises: the polyoxometalate; a substituting metal atom that is the central metal introduced into the defect sites; and the organic ligand coordinately bonded to the substituting metal atom, wherein the central metal and the substituting metal atom are divalent platinum or palladium, wherein the organic ligand is two ammonia ligands, two alkylamine ligands having 1 to 3 carbon atoms, or one ethylenediamine ligand, coordinately bonded to one of the central metals or one of the substituting metal atoms, wherein, in the metal-substituted polyoxometalate, the one substituting metal atom is introduced into each of the one or more defect sites, and wherein the metal-substituted polyoxometalate is generated in the reaction solution at 25° C. or lower.

8 . A reaction catalyst comprising a polyoxometalate compound comprising a metal-substituted polyoxometalate and a counter ion thereof,
wherein the metal-substituted polyoxometalate comprises: a polyoxometalate comprising one or more defect sites; a substituting metal atom introduced into the defect sites; and an organic ligand coordinately bonded to the substituting metal atom, wherein the substituting metal atom is divalent platinum or palladium, and wherein the one substituting metal atom is introduced into each of the one or more defect sites.

9 . A reaction catalyst comprising the polyoxometalate compound according to claim 1 .

10 . A sintered body of a polyoxometalate compound comprising a metal-substituted polyoxometalate and a counter ion thereof,
wherein the metal-substituted polyoxometalate comprises: a polyoxometalate comprising one or more defect sites, a substituting metal atom introduced into the defect sites, and an organic ligand coordinately bonded to the substituting metal atom, wherein the substituting metal atom is divalent platinum or palladium, and wherein the one substituting metal atom is introduced into each of the one or more defect sites.

11 . The sintered body of a polyoxometalate compound according to claim 1 .

12 . The sintered body according to claim 10 ,
wherein the sintered body comprises: the substituting metal atom; and a transition metal atom derived from the polyoxometalate, and a molar ratio between the substituting metal atom and the transition metal atom is 1:11.

13 . A reaction catalyst comprising the sintered body of a polyoxometalate compound according to claim 10 .

14 . The reaction catalyst according to claim 8 , the reaction catalyst being a photocatalyst for allowing hydrogen to be generated from water, a hydrogenation reaction catalyst, an exhaust gas

Assignees

• Univ Shizuoka Nat Univ Corp

Inventors

• Kato Chika

Classifications

• B01J2235/10

  Infrared [IR] · CPC title

• B01J2235/05

  Nuclear magnetic resonance [NMR] · CPC title

• Y02E60/36

  Hydrogen production from non-carbon containing sources, e.g. by water electrolysis · CPC title

• B01J2531/828

  Platinum · CPC title

• B01J2531/824

  Palladium · CPC title