CO2 reduction toward methane

Patent metadata

Field	Value
Publication number	US-11993857-B2
Application number	US-202217994966-A
Country	US
Kind code	B2
Filing date	Nov 28, 2022
Priority date	Dec 9, 2019
Publication date	May 28, 2024
Grant date	May 28, 2024

Abstract

An electrode of a chemical cell includes a substrate having a surface, an array of conductive projections supported by the substrate and extending outward from the surface of the substrate, each conductive projection of the array of conductive projections having a semiconductor composition for reduction of carbon dioxide (CO 2 ) in the chemical cell, and a catalyst arrangement disposed along each conductive projection of the array of conductive projections, the catalyst arrangement including a copper-based catalyst and an iron-based catalyst for the reduction of carbon dioxide (CO 2 ) in the chemical cell.

First claim

What is claimed is:

1. An electrode of a chemical cell, the electrode comprising:
a substrate having a surface;
an array of projections supported by the substrate and extending outward from the surface of the substrate; and
a catalyst arrangement disposed along each projection of the array of projections, the catalyst arrangement comprising a copper-based catalyst and an iron-based catalyst for the chemical cell;
wherein the copper-based catalyst comprises a plurality of copper nanoparticles.

2. The electrode of claim 1 , wherein each copper nanoparticle of the plurality of copper nanoparticles is composed of metallic copper.

3. The electrode of claim 1 , wherein the iron-based catalyst comprises a distribution of iron oxide disposed in a co-catalyst arrangement with the copper-based catalyst.

4. The electrode of claim 1 , wherein the copper-based catalyst is disposed between the iron-based catalyst and the projection.

5. The electrode of claim 1 , wherein the copper-based catalyst and the iron-based catalyst are linked by a metallic bond.

6. An electrode of a chemical cell, the electrode comprising:
a substrate having a surface;
an array of projections supported by the substrate and extending outward from the surface of the substrate; and
a catalyst arrangement disposed along each projection of the array of projections, the catalyst arrangement comprising a copper-based catalyst and an iron-based catalyst for the chemical cell;
wherein:
the substrate comprises a semiconductor material; and
the semiconductor material is configured to generate charge carriers upon absorption of solar radiation such that the chemical cell is configured as a photoelectrochemical system.

7. The electrode of claim 6 , wherein the array of projections are configured to extract the charge carriers generated in the substrate.

8. The electrode of claim 1 , wherein each projection of the array of projections comprises a respective nanowire.

9. The electrode of claim 1 , wherein each projection of the array of projections comprises a Group III-V semiconductor material.

10. The electrode of claim 1 , wherein the substrate is planar.

11. The electrode of claim 1 , wherein each projection of the array of projections has a semiconductor composition, the semiconductor composition of the array of projections establishing a Schottky junction with the catalyst arrangement.

12. The electrode of claim 1 , wherein the catalyst arrangement has an iron-to-copper ratio of about 6.3 to 1.

13. The electrode of claim 1 , wherein the copper-based catalyst is partially oxidized.

14. The electrode of claim 1 , wherein the chemical cell is a thermochemical cell.

15. An electrochemical system comprising a working electrode configured in accordance with the electrode of claim 1 , and further comprising:
a counter electrode;
an electrolyte in which the working and counter electrodes are immersed; and
a voltage source that applies a bias voltage between the working and counter electrodes;
wherein the bias voltage establishes a preference for the reduction of carbon dioxide (CO2) at the working electrode toward methane.

16. A photoelectrode for a photoelectrochemical cell, the photoelectrode comprising:
a substrate comprising a light absorbing material, the light absorbing material being configured to generate charge carriers upon illumination;
an array of conductive projections supported by the substrate, each conductive projection of the array of conductive projections being configured to extract the charge carriers from the substrate;
copper-based catalysts disposed across each conductive projection of the array of conductive projections; and
a distribution of an iron-based catalyst disposed adjacent to the copper-based catalysts in a co-catalyst arrangement;
wherein the copper-based catalysts are configured as copper nanoparticles.

17. The photoelectrode of claim 16 , wherein the iron-based catalyst comprises iron oxide.

18. The photoelectrode of claim 16 , wherein each conductive projection of the array of conductive projections comprises a respective nanowire.

19. The photoelectrode of claim 16 , wherein the copper-based catalysts are composed of metallic copper.

20. The photoelectrode of claim 16 , wherein each conductive projection of the array of conductive projections comprises a Group III-V semiconductor material.

21. A photoelectrochemical system comprising a working photocathode configured in accordance with the photoelectrode of claim 16 , and further comprising:
a counter electrode;
an electrolyte in which the working photocathode and the counter electrode are immersed; and
a voltage source that applies a bias voltage between the working photocathode and the counter electrode;
wherein the bias voltage establishes a preference for the reduction of carbon dioxide (CO2) at the working electrode toward methane.

22. A method of fabricating an electrode of an electrochemical system, the method comprising:
growing an array of projections on a substrate; and
depositing a catalyst arrangement along each projection of the array of projections, the catalyst arrangement comprising a copper-based catalyst and an iron-based catalyst;
wherein the copper-based catalyst comprises a plurality of copper nanoparticles.

23. The method of claim 22 , wherein depositing the catalyst arrangement comprises implementing a number of electrodeposition cycles.

24. The method of claim 23 , wherein the number of electrodeposition cycles is about 10 cycles.

25. The method of claim 23 , wherein implementing the number of electrodeposition cycles comprises immersing the array of projections in a solution, the solution comprising a copper precursor and an iron precursor.

Assignees

• Univ Michigan Regents

Inventors

• Ou Pengfei
• Song Jun
• Zhou Baowen
• Mi Zetian

Classifications

• C25B3/26 Primary

  of carbon dioxide · CPC title

• B01J23/72

  Copper · CPC title

• B01J23/745

  Iron · CPC title

• C25B3/03 Primary

  Acyclic or carbocyclic hydrocarbons · CPC title

• C25B3/21

  Photoelectrolysis · CPC title