IP Library Granted Patent US 12,286,711
Granted Patent B2
US 12,286,711 · App. 16/286,467 · Granted Apr 29, 2025

Use of intermediates in solar fuels generation

Inventors: Christoph D. Karp (Pasadena, CA); Alec S. Ho (Pasadena, CA); Xinghao Zhou (Pasadena, CA); Chengxiang Xiang (San Marino, CA); Nathan S Lewis (La Canada Flintridge, CA)
Assignee: California Institute of Technology
C25B1/04C01B3/06C25B1/55C25B9/05C25B9/19C25B9/73C25B15/08H01M8/0606
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Quick Facts
Patent No.
US 12,286,711
App. No.
16/286,467
Granted
Apr 29, 2025
Kind
B2
Abstract

A solar fuels generation system includes a first reactor that contains a first solution in which a charge carrier is reduced to a reduced charge carrier. The system also includes a second reactor that contains a second solution in which the reduced charge carrier reduces protons so as to generate hydrogen gas.

Claims (36)

1. A solar fuels generation system consisting of a first reactor and a second reactor:

the first reactor comprising:

a catholyte solution comprising water, an acid and a charge carrier,

an anolyte solution,

a cathode comprising a material selected from the group consisting of carbon nanotubes, glassy carbon, carbon cloth, mercury and any combination thereof, and

an anode comprising a material selected from the group consisting of FeNiOx, RuOx, CoOx and any combination thereof;

wherein the cathode and anode are separated by a bipolar membrane,

wherein the catholyte and anolyte have different pHs,

wherein the anolyte is in contact with the anode and the catholyte is in contact with the cathode, and

wherein the charge carrier is reduced to a reduced charge carrier; and

the second reactor comprising a molybdenum carbide or Pt catalyst that contains a solution in which the reduced charge carrier from the catholyte solution reduces protons so as to generate hydrogen gas by a chemical reaction having a hydrogen evolution potential of 50 mV to 400 mV and wherein the second reactor is pressurized to 10 (D/59mV) atmospheres, wherein D is the value of the charge carrier redox couple differential in mV.

2. The system of claim 1 , wherein the charge carrier is a vanadium cation.

3. The system of claim 1 , wherein the charge carrier is represented by X i+ wherein X represents an atom or a compound, i+ represents the charge of X where i is an integer and is greater than or equal to 1 and less than or equal to 5.

4. The system of claim 3 , wherein the reduced charge carrier is represented by X (i−j)+ wherein j is an integer and can be 1, 2, 3, or 4 and (i−j) is greater than 0.

5. The system of claim 4 , wherein X represents vanadium, i is 3 and j is 1.

6. The system of claim 5 , wherein the pH of the catholyte solution is less than 1.

7. The system of claim 1 , wherein the charge carrier and the reduced charge carrier are a redox couple and a redox potential for the redox couple is less than a hydrogen evolution potential for evolving the hydrogen gas in the first solution.

8. The system of claim 1 , wherein disassociation of water in the first reactor is a source of protons that enter the catholyte solution during the reduction of the charge carrier.

9. The system of claim 8 , wherein the disassociation of the water occurs in the bipolar membrane.

10. The system of claim 1 , further comprising a bias source that includes one or more components selected from a photoelectrode, a solar cell, and a photovoltaic cell, and

wherein electrons that reduce the charge carrier in the first reactor are excited by light being absorbed by the bias source.

11. The system of claim 1 , wherein the first reactor is a solar fuels generator.

12. The system of claim 1 , wherein the second reactor is pressurized to more than 100 bar during the generation of the hydrogen gas.

13. The system of claim 1 , wherein the reduced charge carrier is oxidized back to the charge carrier during the reduction of the protons by the reduced charge carrier in the second reactor.

14. The system of claim 1 , further comprising:

a storage tank in which the catholyte solution is stored between being transported from the first reactor and being transported into the second reactor.

15. A solar fuel intermediate generator, comprising:

a bias source that includes one or more components selected from a photoelectrode, a solar cell, and a photovoltaic cell;

a catholyte in which a charge carrier is reduced to a reduced charge carrier by electrons excited by absorption of light by the bias source;

the charge carrier and the reduced charge carrier being a redox couple and a redox potential for the redox couple being more negative than a hydrogen evolution potential for the reduced charge carrier reducing protons to hydrogen gas in the catholyte;

a reactor comprising a bipolar separator between the catholyte and an anolyte comprising an anion exchange membrane and a cation exchange membrane; and

an anode in the reactor comprising a material selected from the group consisting of FeNiOx, RuOx, CoOx and any combination thereof, wherein the anolyte is in contact with the anode;

wherein disassociation of water is a source of protons that enter the catholyte during the reduction of the charge carrier and the disassociation of the water occurs in the bipolar separator between the catholyte and an anolyte, and

wherein the catholyte and anolyte have different pHs.

16. The solar fuel generator of claim 15 , wherein the charge carrier and the reduced charge carrier are vanadium cations.

17. The system of claim 9 , wherein the bipolar membrane further comprises a catalyst layer between an anion exchange membrane and a cation exchange membrane of the bipolar membrane.

Assignments (2)
CONFIRMATORY LICENSE Recorded Jun 13, 2019
From: CALIFORNIA INSTITUTE OF TECHNOLOGY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 049459/0387 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 5, 2019
From: KARP, CHRISTOPH D.; HO, ALEC S.; ZHOU, XINGHAO; XIANG, CHENGXIANG; LEWIS, NATHAN S.
To: THE CALIFORNIA INSTITUTE OF TECHNOLOGY
Reel/Frame 050020/0702 →
Continuity (2)
Provisional Application 62635776 · Feb 27, 2018
Related Publication 20190264338A1 · Aug 29, 2019
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