Aerobic electrocatalytic oxidation of hydrocarbons

Patent metadata

Field	Value
Publication number	US-12410528-B2
Application number	US-202118002661-A
Country	US
Kind code	B2
Filing date	Jun 17, 2021
Priority date	Jun 22, 2020
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

This invention is directed to a method of oxygenating hydrocarbons with molecular oxygen, O 2 , as oxidant under electrochemical reducing conditions, using polyoxometalate compounds containing copper such as Q 10 [Cu 4 (H 2 O) 2 (B-α-PW 9 O 34 ) 2 ] or Q 13 {[Cu(H 2 O)] 3 [(A-α-PW 9 O 34 ) 2 (NO 3 ) − ]} or solvates thereof as catalysts, wherein Q are each independently selected from alkali metal cations, alkaline earth metal cations, transition metal cations, NH 4 + , H + or any combination thereof.

First claim

What is claimed is:

1. A method for the preparation of oxygenated hydrocarbon products from a hydrocarbon under electrochemical reducing conditions, comprising the step of (a) contacting a hydrocarbon with molecular oxygen and with a polyoxometalate catalyst of the general formula (1):
Q i [X j M k Cu l W m O n ]

or a solvate thereof;
wherein:
i is between 0-50;
j is between 0-4;
k is 0;
1 is between 1-5;
m is between 10-20;
n is between 50-100;
each of Q is independently selected from alkali metal cation, alkaline earth metal cation, transition metal cation, NH4 + and H + ;
each of X is independently P, As, Si, B or Al;
each of M is independently Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru, Rh, Pd, Ag, Re, Os, Ir or Pt;
wherein said contacting step (a) is conducted in an electrochemical cell, said electrochemical cell comprises a cathode, an anode and the polyoxometalate catalyst and wherein a voltage is applied to said cell, thereby generating oxygenated hydrocarbon products;
wherein in step (a) one or more of the Cu atoms in the polyoxometalate catalyst is reduced by applied electrochemical reducing conditions to form reduced Cu atoms;
subsequent contact of the polyoxometalate catalyst with the reduced Cu atoms, with the molecular oxygen and the hydrocarbon, the hydrocarbon oxygenates to obtain the oxygenated hydrocarbon products; and following the oxygenation of the hydrocarbons, the reduced Cu atoms in the polyoxometalate catalyst are reoxidized to their original oxidation state.

2. The method of claim 1 , wherein Q is an alkali metal cation comprising Li, Na, K, Rb or Cs.

3. The method of claim 1 , wherein at least one of Q is K + or Na + .

4. The method of claim 1 , wherein M is Mn, Fe, Co, Ni or Cu.

5. The method of claim 1 , wherein Q i is Q 10 or Q 13 .

6. The method of claim 5 , wherein Q 10 is {K 7 Na 3 } 10+ or Q 13 is {K 12 H} 13+ .

7. The method of claim 1 , wherein said molecular oxygen is a gas composition comprising O 2 , or pure O 2 .

8. The method of claim 7 , wherein said gas composition comprising O 2 comprises air, diluted air, concentrated air, a mixture of O 2 and inert gas, a mixture of O 2 and said hydrocarbon or any mixture thereof.

9. The method of claim 1 , wherein said polyoxometalate catalyst is a polyoxometalate of formula (4):
Q 10 Cu 4 (H 2 O) 2 (B-α-PW 9 O 34 )  (4)

or a solvate thereof.

10. The method of claim 1 , wherein said polyoxometalate catalyst is dissolved in a solvent to form a solvate thereof.

11. The method of claim 10 , wherein said solvent is selected from water, acetone, acetic acid, acetonitrile or any combination thereof.

12. The method of claim 1 , wherein said polyoxometalate catalyst is not dissolved in a solvent.

13. The method of claim 1 , wherein said hydrocarbon comprises substituted or unsubstituted C 1 -C 10 alkenes, C 1 -C 10 alkanes, arenes or any combination thereof.

14. The method of claim 13 , wherein said C 1 -C 10 alkanes comprises methane, ethane, propane or isobutane.

15. The method of claim 13 , wherein said C 1 -C 10 alkenes comprises ethylene, maleic acid or propylene.

16. The method of claim 13 , wherein said arene is benzene.

17. The method of claim 1 , wherein said oxygenated hydrocarbon products comprise carbon-carbon bond cleavage products, carbon-hydrogen bond oxygenation products, carbon-carbon bond addition products, epoxides or any combination thereof.

18. The method of claim 17 , wherein said carbon-carbon bond cleavage products comprise aldehyde and/or hydrate thereof, ketone, a-oxo carboxylic acid or carboxylic acid.

19. The method of claim 17 , wherein said carbon-hydrogen bond oxygenation products are selected from a-hydroxy carboxylic acid, «-hydroxy aldehyde, and/or hydrate thereof, alcohol, aldehyde, ketone, epoxide, diol, hydroxyarene, dihydroxy arene and carboxylic acid.

20. The method of claim 1 , wherein said step is conducted at a temperature of between 2 and 100° C.

21. The method of claim 20 , wherein said temperature is room temperature.

22. The method of claim 1 , wherein the cathode comprises a carbon-based material, a metal or a metal oxide.

23. The method of claim 22 , wherein the carbon-based material cathode comprises carbon nitrides, glassy carbon, graphite or carbon fibers; the metal and metal oxide cathode comprise titanium, molybdenum or platinum.

24. The method of claim 1 , wherein the anode comprises platinum or an electrode based on cobalt, manganese, iron, nickel compounds, molybdenum sulfides, ruthenium oxide, iridium oxide, pyrochlores or combinations thereof.

25. The method of claim 1 , wherein the electrochemical cell consists of a platinum wire as reference electrode, a platinum wire as the anode and a platinum net as the cathode.

26. The method of claim 1 , wherein the electrochemical cell is a continuous flow reactor.

27. The method of claim 1 , wherein j is 2 and m is 18, thus the polyoxometalate catalyst is represented by the following formula:
Q i [X 2 Cu l W 18 O n ].

Assignees

• Yeda Res & Dev

Inventors

• Neumann Ronny
• Kaufman Yehonatan

Classifications

• C25B3/23

  Oxidation (halogenation C25B3/27) · CPC title

• C25B11/077

  the compound being a non-noble metal oxide · CPC title

• C25B11/065

  Carbon · CPC title

• C25B15/027

  Temperature · CPC title

• C25B11/081

  the element being a noble metal · CPC title