Electrochemical oxidation of organic molecules

Patent metadata

Field	Value
Publication number	US-2021371991-A1
Application number	US-201917277063-A
Country	US
Kind code	A1
Filing date	Sep 24, 2019
Priority date	Sep 24, 2018
Publication date	Dec 2, 2021
Grant date	—

Abstract

A system and method for oxidizing organic molecules as an oxygen-atom source using an electrochemical process is described.

First claim

What is claimed is:

1 . A method of generating an oxidized substrate comprising:
contacting an anode including an oxygen atom transfer catalyst composition with a substrate; contacting the anode with an oxygen atom source; and applying a voltage to the anode and a cathode to produce an oxidized substrate.

2 . The method of claim 1 , wherein the oxygen atom transfer catalyst composition includes a metal oxides, metal hydroxide, metal phosphate, metal borate, metal sulfide, metal phosphide, or metal nitride, or combinations thereof.

3 . The method of claim 1 , wherein the oxygen atom transfer catalyst composition includes a manganese oxide, a titanium oxide, a copper oxide, a zinc oxide, a cobalt oxide, a cobalt phosphide, an iron oxide, a nickel oxide, an iridium oxide, a platinum oxide, or a chromium oxide.

4 . The method of claim 1 , wherein the oxygen atom transfer catalyst composition includes a metal including rhenium, iridium, platinum, silver, gold, ruthenium, rhodium, or palladium.

5 . The method of claim 1 , wherein the oxygen atom transfer epoxidation catalyst includes single atoms of one element of Re, Ir, Pt, Au, Ru, Rh, or Pd supported on a nanostructured material containing an oxide or metal nanoparticle including Ti, Cr, Mn, Fe, Co, Ni, Cu, or Zn.

6 . The method of claim 1 , wherein the oxidized substrate is produced at a Faradaic yield of at least 20%, at least 30% or at least 40%.

7 . The method of claim 1 , wherein the oxygen atom source is water without the need to generate a soluble oxidant from the water.

8 . The method of claim 1 , wherein the cathode includes a hydrogen generation catalyst.

9 . The method of claim 8 , wherein hydrogen gas is produced at the cathode.

10 . The method of claim 9 , wherein hydrogen gas is produced at a Faradaic yield of at least 70%, at least 80% or at least 90%.

11 . The method of claim 1 , wherein the cathode includes an oxygen reduction catalyst.

12 . The method of claim 1 , wherein oxygen is introduced at the cathode and water is produced.

13 . The method of claim 1 , wherein a hydrogenation reaction of an organic substrate is conducted at the cathode.

14 . The method of claim 1 , wherein the substrate is an olefin that is oxidized to form an epoxide or ketone.

15 . The method of claim 1 , wherein the substrate is a ketone that is oxidized to form an ester.

16 . The method of claim 1 , wherein the substrate contains a C—H bond oxidized to form a product containing a carbon-oxygen bond, such as an alcohol, aldehyde, ketone, or carboxylic acid.

17 . The method of claim 1 , wherein the oxidized substrate is an epoxide, an ester, a ketone, an alcohol or an aldehyde.

18 . The method of claim 1 , wherein the substrate is supplied to the anode at a concentration of 5 mM, 10 mM, 15 mM, 20 mM, 25 mM, 30 mM, 35 mM, 40 mM, 50 mM, 60 mM, 70 mM, 80 mM, 90 mM, 100 mM, 200 mM, 250 mM, 300 mM, 350 mM, 400 mM, 450 mM, 500 mM, 1 M, 2 M, 4 M, 6 M, 8 M, or 10 M.

19 . The method of claim 1 , wherein the oxygen atom source is supplied at a concentration of 0.1 M, 0.25 M, 0.5 M, 1 M, 2 M, 4 M, 6 M, 8 M, 10 M, 12 M, 14 M, 16 M, 18 M or 20 M.

20 . The method of claim 1 , wherein the voltage is between about 0.2V and 9.0V, between about 0.4V and 5V, or between about 0.6V and 2.0V.

21 . The method of claim 1 , wherein the voltage is 0.5V, 0.6V, 0.7V, 0.8V, 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, 1.4V, 1.6V, 1.7V, 1.8V or 1.9V.

22 . The method of claim 1 , wherein the cathode includes a noble metal, nickel-molybdenum-zinc alloys, cobalt phosphide, or nickel phosphide.

23 . The method of claim 1 , wherein the method is carried out substantially at room temperature.

24 . A method of manufacturing an oxygen atom transfer catalyst comprising:
depositing particles of an oxygen atom transfer catalyst composition on an electrode surface.

25 . The method of claim 24 , wherein the oxygen atom transfer catalyst composition is a metal oxides, metal hydroxide, metal phosphate, metal borate, metal sulfide, metal phosphide, or metal nitride, or combinations thereof.

26 . The method of claim 24 , wherein the particles are nanoparticles.

27 . The method of claim 24 , wherein the electrode surface is a surface of carbon paper.

28 . A system for forming an oxidized substrate and an oxygen atom source comprising:
a housing; a cathode within the housing; an anode including an oxygen atom transfer catalyst composition within the housing; and a voltage supply configured to apply a voltage to the anode and the cathode.

29 . The system of claim 28 , further comprising a substrate inlet to the housing configured to contact the substrate with the anode.

30 . The system of claim 28 , further comprising a first outlet of the housing to release the epoxidized substrate from the housing.

31 . The system of claim 30 , further comprising a second outlet of the housing to release hydrogen.

32 . The system of claim 28 , wherein an oxygen atom source includes water.

33 . The system of claim 28 , wherein the anode includes carbon.

34 . The system of claim 28 , wherein the cathode includes a hydrogen catalyst composition.

35 . The system of claim 28 , wherein the oxygen atom transfer catalyst composition includes a metal oxides, metal hydroxide, metal phosphate, metal borate, metal sulfide, metal phosphide, or metal nitride, or combinations thereof.

36 . The system of claim 28 , wherein the oxygen atom transfer catalyst composition includes a manganese oxide, a titanium oxide, a chromium oxide, a copper oxide, a zinc oxide, a cobalt oxide, a cobalt phosphide, an iron oxide, a nickel oxide, an iridium oxide, a platinum oxide, or a chromium oxide.

Assignees

• Massachusetts Inst Technology

Inventors

• Manthiram Karthish
• Jin Kyoungsuk
• Maalouf Joseph
• Williams Kindle
• Chung Minju

Classifications

• Y02E60/36

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

• H01M4/9016

  Oxides, hydroxides or oxygenated metallic salts · CPC title

• H01M4/96

  Carbon-based electrodes · CPC title

• H01M8/18

  Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells · CPC title

• C25B11/091

  consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds · CPC title