Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof

Patent metadata

Field	Value
Publication number	US-10711021-B2
Application number	US-201514950791-A
Country	US
Kind code	B2
Filing date	Nov 24, 2015
Priority date	Jul 3, 2013
Publication date	Jul 14, 2020
Grant date	Jul 14, 2020

Abstract

Catalysts prepared from abundant, cost effective metals, such as cobalt, nickel, chromium, manganese, iron, and copper, and containing one or more neutrally charged ligands (e.g., monodentate, bidentate, and/or polydentate ligands) and methods of making and using thereof are described herein. Exemplary ligands include, but are not limited to, phosphine ligands, nitrogen-based ligands, sulfur-based ligands, and/or arsenic-based ligands. In some embodiments, the catalyst is a cobalt-based catalyst or a nickel-based catalyst. The catalysts described herein are stable and active at neutral pH and in a wide range of buffers that are both weak and strong proton acceptors. While its activity is slightly lower than state of the art cobalt-based water oxidation catalysts under some conditions, it is capable of sustaining electrolysis at high applied potentials without a significant degradation in catalytic current. This enhanced robustness gives it an advantage in industrial and large-scale water electrolysis schemes.

First claim

We claim:

1. A method of oxidizing an organic compound comprising one or more carbon-hydrogen bonds, the method comprising contacting the organic compound to be oxidized with an oxidant selected from the group consisting of a chemical oxidant, an electrochemical oxidant, and combinations thereof and a catalyst having the chemical formula;
MY a (CO) b O c (OH) d (H 2 O) e
wherein
M is a d-block transition metal that forms stable carbonyl complexes selected from the group consisting of Cr, Mn, Co, Ni, Cu, Rh, Ir, and combinations thereof;
Y is a monodentate ligand, a bidentate ligand, or a combination thereof;
a is any value from 0.5 to 1;
b is any value from 0 to 3;
c is any value from 1 to 4; and
d is any value from 0 to 4; and
e is any value from 0 to 6,
to oxidize a carbon-hydrogen bond in the organic compound; and
wherein the catalyst is prepared according to a method comprising:
thermolysis of a solution comprising the d-block transition metal and the monodentate ligand, the bidentate ligand, or combinations thereof with stirring under reflux under an inert atmosphere;
allowing the resulting reaction mixture to cool followed by exposure to ambient atmosphere;
washing the reaction mixture; and
drying the washed reaction mixture to obtain the catalyst.

2. The method of claim 1 , wherein M is cobalt.

3. The method of claim 1 , wherein M is nickel.

4. The method of claim 1 , wherein the M is chromium.

5. The method of claim 1 , wherein the M is copper.

6. The method of claim 1 , wherein the M is manganese.

7. The method of claim 1 , wherein the M is rhodium.

8. The method of claim 1 , wherein the M is iridium.

9. The method of claim 1 , wherein b is from 0 to 2.

10. The method of claim 1 , wherein c is from 1.5 to 3.

11. The method of claim 1 , wherein Y is charged.

12. The method of claim 1 , wherein Y is uncharged.

13. The method of claim 12 , wherein Y is a phosphorus ligand.

14. The method of claim 13 , wherein the phosphorus ligand is selected from the group consisting of dialkyl phosphines, trialkyl phosphine, alkyl diaryl phosphines, triaryl phosphines, and combinations thereof.

15. The method of claim 14 , wherein the phosphorus ligand is an alkyl diaryl phosphine.

16. The method of claim 15 , wherein the alkyl diaryl phosphine is selected from the group consisting of 1,2-Bis(diphenylphosphino)ethane, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene, triphenylphosphine, (Oxydi-2,1-phenylene)bis(diphenylphosphine), and combinations thereof.

17. The method of claim 12 , wherein the ligand is a nitrogen ligand.

18. The method of claim 17 , wherein the nitrogen ligand is a N-heterocycle.

19. The method of claim 18 , wherein the N-heterocycle is selected from the group consisting of 2,2′-bipyridine, 3,3′-bipyridine, and combinations thereof.

20. The method of claim 12 , wherein the nitrogen ligand is a secondary amine, tertiary amine, or combinations thereof.

21. The method of claim 20 , wherein the secondary amine, tertiary amine, or combinations thereof are substituted with alkyl and/or aryl groups.

22. The method of claim 1 , wherein the ligand is a sulfur ligand.

23. The method of claim 22 , wherein the sulfur ligand is selected from the group consisting of S-heterocycles, alkyl and/or aryl thioethers, or combinations thereof.

24. The method of claim 12 , wherein the ligand is an arsenic ligand.

25. The method of claim 24 , wherein the arsenic ligand is selected from the group consisting of As-heterocycles, tertiary arsine with alkyl and/or aryl substituents, and combinations thereof.

26. The method of claim 1 , wherein the oxidant is a chemical oxidant.

27. The method of claim 26 , wherein the chemical oxidant is selected from the group consisting of potassium hydrogen peroxysulfate, hydrogen peroxide, oxygen, ozone, and combinations thereof.

28. The method of claim 1 , wherein the oxidant is an electrochemical oxidant.

29. The method of claim 1 , wherein the oxidant comprises a combination of a chemical oxidant and an electrochemical oxidant.

30. The method of claim 1 , wherein Y is a bidentate ligand.

Assignees

• Univ Yale

Inventors

• Bloomfield Aaron J
• Sheehan Stafford W
• Collom Samuel L
• Crabtree Robert H
• Anastas Paul T

Classifications

• C25B3/23

  Oxidation (halogenation C25B3/27) · CPC title

• C25B11/073

  characterised by the electrocatalyst material · CPC title

• C25B3/25

  Reduction · CPC title

• B01J31/2273 Primary

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• Y02E60/50

  Fuel cells · CPC title