Hydrocarbon oxidation by water oxidation electrocatalysts in non-aqueous solvents

Patent metadata

Field	Value
Publication number	US-2018044804-A1
Application number	US-201715675065-A
Country	US
Kind code	A1
Filing date	Aug 11, 2017
Priority date	Aug 12, 2016
Publication date	Feb 15, 2018
Grant date	—

Abstract

Provided herein are processes and systems for oxidation of a hydrocarbon reactant to generate an oxidized hydrocarbon product; said process comprising: contacting a water oxidation electrocatalyst with said hydrocarbon reactant and water in the presence of a non-aqueous solvent; wherein an anodic bias is applied to said water oxidation electrocatalyst, thereby generating said oxidized hydrocarbon product; and wherein said water oxidation electrocatalyst comprises one or more transition metals other than Ru. Optionally, said water is provided in said non-aqueous solvent at a concentration less than or equal to 0.5 vol. %. Optionally, the magnitude of said anodic bias is selected to generate said oxidized hydrocarbon product characterized by selected product distribution.

First claim

1 . A process for oxidation of a hydrocarbon reactant to generate an oxidized hydrocarbon product; said process comprising:
contacting a water oxidation electrocatalyst with said hydrocarbon reactant and water in the presence of a non-aqueous solvent; wherein an anodic bias is applied to said water oxidation electrocatalyst, thereby generating said oxidized hydrocarbon product; and wherein said water oxidation electrocatalyst comprises one or more transition metals other than Ru.

2 . The process of claim 1 , wherein said water is provided in said non-aqueous solvent at a concentration less than or equal to 0.5 vol. %.

3 . The process of claim 1 , further comprising applying an anodic bias to said water oxidation electrocatalyst, wherein the magnitude of said anodic bias is selected to generate said oxidized hydrocarbon product characterized by said a selected product distribution.

4 . The process of claim 1 , wherein said water oxidation electrocatalyst does not comprise Ru.

5 . The process of claim 1 , wherein said water oxidation electrocatalyst comprises an inorganic catalyst.

6 . The process of claim 1 , wherein said water oxidation electrocatalyst is a metal oxide or a metal hydroxide and wherein said metal oxide or metal hydroxide comprises one or more earth abundant metals.

7 . (canceled)

8 . (canceled)

9 . The process of claim 1 , wherein said water oxidation electrocatalyst is a nanostructured layered double hydroxide solid, a perovskite, a polyoxometalate, or a metal-organic framework.

10 . (canceled)

11 . (canceled)

12 . (canceled)

13 . (canceled)

14 . The process of claim 1 , wherein said water oxidation electrocatalyst is not an organometallic catalyst.

15 . The process of claim 1 , wherein said water oxidation electrocatalyst is a heterogeneous catalyst.

16 . (canceled)

17 . (canceled)

18 . The process of claim 1 , wherein said water oxidation electrocatalyst is provided in the form of nanoparticles.

19 . (canceled)

20 . (canceled)

21 . (canceled)

22 . The process of claim 1 , wherein said hydrocarbon reactant comprises a substituted or unsubstituted: C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 5 -C 10 aryl, C 5 -C 10 heteroaryl, C 1 -C 10 acyl, C 1 -C 10 hydroxyl, C 1 -C 10 alkoxy, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 5 -C 10 alkylaryl, C 3 -C 10 arylene, C 3 -C 10 heteroarylene, C 2 -C 10 alkenylene, C 3 -C 10 cylcoalkenylene, C 2 -C 10 alkynylene, ammonium ion, or any combination thereof.

23 . (canceled)

24 . The process of claim 1 , wherein said oxidized hydrocarbon product comprises an alcohol, an ether, an epoxide, a ketone, a carboxylic acid, an aldehyde, an acid chloride, an organic acid anhydride, or a combination thereof.

25 . (canceled)

26 . (canceled)

27 . The process of claim 1 , wherein said water is provided in said non-aqueous solvent at a concentration selected from the range of 0.1 vol. % to 5 vol. %.

28 . The process of claim 1 , wherein said water is characterized by a pH that is greater than 7.

29 . (canceled)

30 . The process of claim 1 , wherein said non-aqueous solvent is a polar aprotic solvent.

31 . The process of claim 1 , wherein said non-aqueous solvent is oxidatively stable under an applied voltage greater than 1.5 V vs. normal hydrogen electrode (NHE).

32 . (canceled)

33 . The process of claim 1 , wherein said contacting step is carried out in the presence of a supporting electrolyte that is provided in said non-aqueous solvent.

34 . The process of claim 33 , wherein said supporting electrolyte is oxidatively stable under an applied voltage greater than 1.5 V vs. normal hydrogen electrode (NHE).

35 . (canceled)

36 . (canceled)

37 . (canceled)

38 . The process of claim 1 , wherein said anodic bias is selected from the range of 0.5 V to 5 V vs. normal hydrogen electrode (NHE).

39 . The process of claim 1 , wherein said water oxidation electrocatalyst is immobilized on an anode.

40 . (canceled)

41 . The process of claim 1 , wherein a cathode is provided in contact with said non-aqueous solvent.

42 . (canceled)

43 . The process of claim 1 , wherein said hydrocarbon reactant comprises a C—H bond, wherein said C—H bond is oxidized to a C—O bond or a C═O.

44 . The process of claim 1 , wherein said non-aqueous solvent has a dielectric constant greater than 10, a dipole moment greater than 1.5 debye, or both.

45 . (canceled)

46 . The process of claim 22 , wherein said hydrocarbon reactant comprises a phosphate ion, a hexafluorophosphate ion, an amine, an imine, a carbonyl, an ether, a nitrile, or a combination of these functional groups.

47 . The process of claim 1 , wherein said anodic bias is applied for a reaction time selected to generate said oxidized hydrocarbon product characterized by said a selected product distribution.

48 . A flow-through system for oxidation of a hydrocarbon reactant to generate an oxidized hydrocarbon product, said system comprising:
a non-aqueous solvent; said hydrocarbon reactant provided in said non-aqueous solvent; water provided in said non-aqueous solvent; a working electrode at least partially provided in a non-aqueous solvent; a water oxidation electrocatalyst immobilized on said working electrode and in contact with said oxidized hydrocarbon product and said water; and a counter electrode at least partially provided in said non-aqueous solvent and electrically connected to said working electrode; wherein:
an anodic bias is applied to said working electrode, thereby generating said oxidized hydrocarbon product;
said non-aqueous solvent continuously flows through said system; and
wherein said water oxidation electrocatalyst comprises one or more transition metals other than Ru.

49 . The system of claim 48 , further comprising a reference electrode.

50 . The system of claim 48 , wherein said water oxidation electrocatalyst does not comprise Ru.

Assignees

• California Inst Of Techn

Inventors

• Hunter Bryan M
• Gray Harry B

Classifications

• C25B11/0478 Primary

  Chemistry & Metallurgy · mapped topic

• C25B3/02

  Chemistry & Metallurgy · mapped topic

• C25B11/0415

  Chemistry & Metallurgy · mapped topic

• C25B11/0405

  Chemistry & Metallurgy · mapped topic

• C25B11/057

  consisting of a single element or compound · CPC title