Polyoxometalates comprising noble metals and post-transition metals and metal clusters thereof

Patent metadata

Field	Value
Publication number	US-11241677-B2
Application number	US-201816490270-A
Country	US
Kind code	B2
Filing date	Jan 25, 2018
Priority date	Mar 8, 2017
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

The invention relates to polyoxometalates represented by the formula (An)m+[M′M12X8OyRzHq]m− or solvates thereof, corresponding supported polyoxometalates, and processes for their preparation, as well as corresponding metal clusters, optionally in the form of a dispersion in a liquid carrier medium or immobilized on a solid support, and processes for their preparation, as well as their use in reductive conversion of organic substrate.

First claim

The invention claimed is:

1. A polyoxometalate represented by the formula
(A n ) m+ [M′M 12 X 8 O y ] m−

or solvates thereof, wherein
each A independently represents a cation and is selected from the group consisting of Li, K, Na and combinations thereof,
n is the number of cations, wherein n=8 or 12,
all M are independently selected from the group consisting of Pd and Pt, and each M has d 8 valence electron configuration,
M′ is selected from the group consisting of Ge, Sn, and Pb,
y is a number from 32 to 40, and
m is a number representing the total positive charge m+ of n cations A and the corresponding negative charge m− of [M′M 12 X 8 O y ], wherein m=8 or 12.

2. The polyoxometalate according to claim 1 , represented by the formula
(A n ) m+ [M′M 12 X 8 O y ] m− .w H 2 O

wherein w represents the number of attracted water molecules per [M′M 12 X 8 O y ], and ranges from 1 to 100.

3. The polyoxometalate according to claim 1 , wherein the polyoxometalate is in the form of particles.

4. A process for a preparation of the polyoxometalate according to claim 1 , said process comprising:
(a) reacting at least one source of M and at least one source of M′ with a X-containing starting material to form a salt of [M′M 12 X 8 O y ] or solvates thereof,
(b) optionally adding at least one salt of A to the reaction mixture of step (a) to form the polyoxometalate (A n ) m+ [M′M 12 X 8 O y ] m− or solvates thereof, and
(c) recovering the polyoxometalate or solvates thereof,
wherein
solvates are water is associated with the polyoxometalate,
the at least one source of M is platinum chloride, palladium nitrate, palladium sulphate, palladium chloride or palladium acetate,
the at least one source of M′ is SnCl 4 , Sn(CH 3 COO) 4 , SnBr 4 , Sn(NO 3 ) 4 , GeCl 4 , PbCl 4 , or Pb(CH 3 COO) 4 ,
the X-containing starting material is an oxide of X or a salt of PO 4 3− ,
the pH of the aqueous solution in step (a) ranges from 2 to 14, and
the reaction mixture in step (a) is heated to a temperature of from 20° C. to 100° C.

5. The process according to claim 4 , wherein the at least one source of M is palladium nitrate, palladium sulphate, palladium chloride, or palladium acetate, the at least one source of M′ is germanium (IV) chloride or tin(IV) chloride, and the X-containing starting material is P 2 O 5 or a salt of PO 4 3− .

6. A supported polyoxometalate comprising the polyoxometalate according to claim 1 on a solid support.

7. A process for a preparation of a supported polyoxometalate comprising the polyoxometalate according to claim 1 , said process comprising a step of contacting the polyoxometalate according to claim 1 with a solid support.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Ma Tian
• Kortz Ulrich
• Yang Peng
• Lin Zhengguo
• Ayass Wassim W

Classifications

• C07C2523/44

  Palladium · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C01P2002/86

  by NMR- or ESR-data · CPC title

• B01J37/348

  Electrochemical processes, e.g. electrochemical deposition or anodisation · CPC title

• B01J27/1856 Primary

  with platinum group metals · CPC title