Upgrading of co to c3 products using multi-metallic electroreduction catalysts with assymetric active sites

Patent metadata

Field	Value
Publication number	US-2022411941-A1
Application number	US-202017779965-A
Country	US
Kind code	A1
Filing date	Nov 24, 2020
Priority date	Nov 25, 2019
Publication date	Dec 29, 2022
Grant date	—

Abstract

The present disclosure relates to electrocatalysts for electroreduction of a carbon-containing gas to produce n-propanol, for example. The electrocatalyst includes a multi-metallic material comprising a primary metal, such as Cu, and a metal dopant, such as Ag, selected and distributed to provide asymmetric active sites that include neighbouring atoms of the primary metal having distinct electronic structures to promote C2-C1 coupling. The electrocatalysts can be bimetallic or bimetallic, for example. The disclosure also relates to manufacturing and using the electrocatalysts, which can be used as a cathodic catalyst to convert CO or CO2 into multi-carbon products.

First claim

1 . An electrocatalyst for electroreduction of a carbon-containing gas to produce C3 products, the electrocatalyst comprising a multi-metallic material comprising a primary metal and a metal dopant selected and distributed to provide asymmetric active sites that include neighbouring atoms of the primary metal having distinct electronic structures to promote C2-C1 coupling.

2 . The electrocatalyst of claim 1 , wherein the primary metal is Cu.

3 . The electrocatalyst of claim 2 , wherein the metal dopant is Ag and the multi-metallic material is a bimetallic material.

4 . The electrocatalyst of claim 1 , wherein the metal dopant comprises Ag and a second dopant metal and the multi-metallic material is a trimetallic material.

5 - 7 . (canceled)

8 . The electrocatalyst of claim 1 , wherein the C3 product is n-propanol.

9 . The electrocatalyst of claim 1 , wherein the multi-metallic material comprises the primary metal doped with the metal dopant using galvanic replacement.

10 . The electrocatalyst of claim 1 , wherein the metal dopant is present in the primary metal in a doping concentration of 2 wt % to 9 wt %, measured with XPS.

11 . (canceled)

12 . The electrocatalyst of claim 1 , wherein the metal dopant is present in the primary metal in a doping concentration of 3wt % to 5 wt %, measured with XPS.

13 - 14 (canceled)

15 . The electrocatalyst of claim 1 , wherein the electrocatalyst is provided in the form of bimetallic or trimetallic nanoparticles.

16 . The electrocatalyst of claim 15 , wherein the bimetallic or trimetallic nanoparticles have an average size between about 20 nm and about 200 nm, measured based on SEM or TM imaging. Claims 17 - 18 (canceled)

19 . The electrocatalyst of claim 16 , wherein the bimetallic or trimetallic nanoparticles are generally spheroid in shape, determined from SEM or TM imaging.

20 . The electrocatalyst of claim 1 , wherein the electrocatalyst is formed as a deposited catalyst layer on a first side of gas diffusion membrane, wherein the deposited catalyst layer is configured to be in direct contact with an electrolyte and wherein a second opposed side of the gas diffusion membrane is configured to be in direct contact with the carbon-containing gas.

21 . An electrocatalyst for electroreduction of a carbon-containing gas to produce a C3 product, the electrocatalyst comprising a bimetallic or trimetallic material comprising a copper (Cu) and at least one metal dopant in a doping concentration of 2 wt % to 9 wt %, measured with XPS.

22 . (canceled)

23 . The electrocatalyst of claim 21 , wherein the metal dopant comprises a primary dopant and a secondary dopant.

24 . The electrocatalyst of claim 23 , wherein the primary dopant is Ag.

25 . The electrocatalyst of claim 24 , wherein the secondary dopant is Ru.

26 - 37 . (canceled)

38 . A method of fabricating an electrocatalyst composed of a primary metal and at least one metal dopant for electroreduction of a carbon containing gas into C3 products, such as n-propanol, comprising galvanic replacement, wherein the electrocatalyst is as defined in claim 1 .

39 . The method of claim 38 , comprising:
providing a layer of Cu particles on a substrate to provide a coated substrate; immersing the coated substrate in an Ag containing aqueous solution to induce doping and form an Ag-doped multimetallic catalyst material supported by the substrate; and removing the coated substrate from the solution, the coated substrate comprising a layer of the Ag-doped multimetallic catalyst material.

40 - 44 . (canceled)

45 . A process for electrochemical production of a C3 multi-carbon compound from a carbon-containing gas, comprising:
contacting the carbon-containing gas and an electrolyte with an electrode comprising the electrocatalyst as defined in claim 1 , such that the carbon-containing gas contacts the electrocatalyst; applying a voltage to provide a current density to cause the carbon-containing gas contacting the electrocatalyst to be electrochemically converted into the C3 multi-carbon compound; and recovering the C3 multi-carbon compound.

46 - 47 . (canceled)

48 . The process of claim 45 , wherein the C3 multi-carbon compound is n-propanol.

49 . (canceled)

50 . The process of claim 45 , wherein the electrolyte comprises KOH.

51 . The process of claim 45 , wherein the carbon-containing gas comprises CO.

52 . The process of claim 45 , wherein the carbon-containing gas comprises CO 2 .

53 . (canceled)

54 . A system for CO and/or CO 2 electroreduction to produce a multi-carbon compound, comprising:
an electrolytic cell configured to receive a liquid electrolyte and CO and/or CO 2 gas; an anode; a cathode comprising an electrocatalyst as defined in claim 1 ; and a voltage source to provide a current density to cause the CO and/or CO 2 gas contacting the electrocatalyst to be electrochemically converted into the multi-carbon compound.

55 . (canceled)

Assignees

• Governing Council Univ Toronto

Inventors

• Wang Xue
• Sargent Edward

Classifications

• C25B9/23

  comprising ion-exchange membranes in or on which electrode material is embedded · CPC title

• C25B3/07 Primary

  Oxygen containing compounds · CPC title

• C25B11/032

  Gas diffusion electrodes · 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

• C25B13/02

  characterised by shape or form · CPC title