Electrochemical flow-cell for hydrogen production and nicotinamide dependent target reduction, and related methods and systems

• US 10,151,037 B2
• Filed: 09/22/2015
• Issued: 12/11/2018
• Est. Priority Date: 01/12/2009
• Status: Active Grant

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Inventors: Hoeprich, Jr., Paul D., Kim, Sangil
• Primary Examiner(s): Kessel, Maris R
• Assistant Examiner(s): Allen, Joshua L
• Application Number:
  US14/861,750
• Publication Number:
  US 20160083858A1
• Time in Patent Office: 1,176 Days
• Field of Search: 205351, 205637
• CPC Class Codes: C25B 1/02 Hydrogen or oxygen
• CPC Class Codes: C25B 11/073 characterised by the electrocatalyst material
• CPC Class Codes: C25B 13/02 characterised by shape or form
• CPC Class Codes: C25B 13/08 based on organic materials
• CPC Class Codes: C25B 15/08 Supplying or removing reactants or electrolytes; Regeneration of electrolytes
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: C25B 9/00 Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Abstract

Methods and systems for hydrogen production or production of a reduced target molecule are described, wherein a nicotinamide co-factor dependent membrane hydrogenase or a nicotinamide co-factor dependent membrane enzyme presented on a nanolipoprotein adsorbed onto an electrically conductive supporting structure, which can preferably be chemically inert, is contacted with protons or a target molecule to be reduced and nicotinamide cofactors in presence of an electric current and one or more electrically driven redox mediators. Methods and systems for production of hydrogen or a reduced target molecule are also described wherein a membrane-bound hydrogenase enzyme or enzyme capable or reducing a target molecule is contacted with protons or the target molecule, a nicotinamide co-factor and a nicotinamide co-factor dependent membrane hydrogenase presented on a nanolipoprotein particle for a time and under condition to allow hydrogen production or production of a reduced target molecule in presence of an electrical current and of an electrically driven redox mediator.

Claims

1. A system for hydrogen production, the system comprising

a nanolipoprotein particle presenting a nicotinamide co-factor dependent membrane hydrogenase,

at least two opposing electrodes comprising a first electrode and a second electrode opposing the first electrode, and

an electrically conductive supporting structure between said first electrode and said second electrode,

wherein the nanolipoprotein particles are immobilized to the electrically conductive supporting structure and

wherein the nanolipoprotein particle, the at least two opposing electrodes and the electrically conductive supporting structure are in a configuration adapted to produce hydrogen.

2. The system according to claim 1, the system further comprising:

a voltage generator, connected to the first and second electrode.

3. The system according to claim 2, wherein the voltage generator is configured to create an electric potential of 500 mV between the first and second electrodes.

4. The system according to claim 1, further comprising an ion exchange membrane between the electrically conductive supporting structure and the second electrode.

5. The system according claim 1, wherein the electrically conductive supporting structure is chemically inert.

6. The system according to claim 1, wherein the electrically conductive supporting structure is an electrically conductive porous supporting structure.

7. The system according to claim 6, wherein the electrically conductive porous supporting structure comprises graphite beads having a diameter less than or equal to 400 μ

m.

8. The system according to claim 6, wherein the electrically conductive porous supporting structure is a mesoporous structure.

9. The system according to claim 8, wherein the mesoporous structure comprises a three-dimensional mesoporous carbon network structure.

10. The system according to claim 9, wherein the mesoporous structure further comprises graphitic carbon material.

11. The system according to claim 8, wherein the mesoporous structure is a graphitic carbon aerogel.

12. The system according to claim 1, further comprising an oxygen removal system configured to remove dissolved oxygen from a buffer solution containing reagents and flowing through the system.

13. The system according to claim 12, wherein the oxygen removal system comprises an argon gas bubbler.

14. The system of claim 1, further comprising a conduit and at least one pump configured to recycle a buffer solution over the electrically conductive supporting structure.

15. A method to produce hydrogen, the method comprising

combining protons, a nicotinamide co-factor and a nicotinamide co-factor dependent membrane hydrogenase presented on a nanolipoprotein particle immobilized on an electrically conductive supporting structure for a time and under condition to allow hydrogen production in presence of an electrical current and of an electrically driven redox mediator,

the combining performed in the system of claim 1.

16. The method of claim 15, wherein the nicotinamide co-factor dependent membrane hydrogenase is a [Ni/Fe] hydrogenase from Allochromatium vinosum, Methanosarcina barkeri, Escherichia coli, and Rhodospirillum rubrum Desulfomicrobium baculatum and Ralstonia species.

17. The method according to claim 16, wherein the nicotinamide co-factor dependent membrane hydrogenase is a [Ni/Fe] hydrogenase from Pyrococcus Furiosus.

18. The method according to claim 15, wherein the nicotinamide co-factor is nicotinamide adenine dinucleotide phosphate.

19. The method according to claim 15, wherein the electrically driven redox mediator comprises a metallic redox mediator.

20. The method according to claim 15, wherein the combining is performed by contacting a solution comprising the protons, the nicotinamide co-factor and the electrically driven/recycled redox mediator with the electrically conductive supporting structure in presence of the electric current.

21. The method according to claim 15, wherein the electrical current is less than 10 milliamps.

22. A system for hydrogen production, the system comprising

a nicotinamide co-factor dependent membrane hydrogenase presented on a nanolipoprotein particle;

and

an electrochemical flow cell comprising a first electrode and a second electrode, an electrically conductive supporting structure

wherein the electrochemical flow cell is configured to receive a solution in a space between the first electrode and the second electrode, and

wherein the electrically conductive supporting structure is configured to immobilize the nicotinamide co-factor dependent membrane hydrogenase presented on the nanolipoprotein particle and to be exposed to the solution in the electrochemical flow cell in a configuration adapted to produce hydrogen.

23. The system according to claim 22, wherein the electrochemical flow cell comprises the nanolipoprotein particle immobilized on the electrically conductive supporting structure.

24. The system according to claim 22, wherein the electrochemical flow cell further comprises an ion exchange membrane between said first and second electrodes.

25. A method to produce a hydrogen, the method comprising:

providing a solution containing protons, nicotinamide co-factors and one or more electrically driven redox mediators into the electrochemical flow cell of the system of claim 22; and

applying a voltage across the first electrode and the second electrode of the electrochemical flow cell.

26. The method according to claim 25, further comprising capturing hydrogen gas generated in the electrochemical flow cell.

27. The method according to claim 25, further comprising removing dissolved oxygen from the solution prior to the providing the solution through the electrochemical flow cell.

28. A method to produce hydrogen, the method comprising:

contacting protons, a nicotinamide co-factor and a nicotinamide co-factor dependent membrane hydrogenase presented on a nanolipoprotein particle for a time and under condition to allow hydrogen production in presence of an electrical current and of an electrically driven redox mediator, the contacting performed in the system of claim 22.

29. The method according to claim 28, wherein the electrically driven redox mediator is a metallic electrically recycled redox mediator.

30. The method according to claim 29, wherein the metallic electrically recycled redox mediator is (pentamethylcyclopentadienyl-2,2′

-bipyridine hydrogen) rhodium (I).

31. The method according to claim 28, wherein the nicotinamide co-factor is nicotinamide adenine dinucleotide phosphate.

32. The method according to claim 28, wherein the nicotinamide co-factor dependent membrane hydrogenase is a [Ni/Fe] hydrogenase from Allochromatium vinosum, Methanosarcina barkeri, Escherichia coli, and Rhodospirillum rubrum Desulfomicrobium baculatum and Ralstonia species.

33. The method according to claim 32, wherein the nicotinamide co-factor dependent membrane hydrogenase is a [Ni/Fe] hydrogenase from Pyrococcus Furiosus.

34. A system for hydrogen production, the system comprising:

a nicotinamide co-factor,

a nicotinamide co-factor dependent membrane hydrogenase presented on a nanolipoprotein particle,

at least two opposing electrodes for providing an electric current, and

an electrically driven redox mediator for simultaneous combined or sequential use together with the at least two opposing electrodes configured to provide electrons to the nicotinamide co-factor,

wherein the nicotinamide co-factor dependent membrane hydrogenase are immobilized on an electrically conductive substrate and

wherein the nicotinamide co-factor, the nicotinamide co-factor dependent membrane hydrogenase and electrically driven redox mediator are in a configuration adapted to produce hydrogen.

35. The system according to claim 34, wherein the electrically driven redox mediator is a metallic electrically recycled redox mediator.

36. The system according to claim 35, wherein the metallic electrically recycled redox mediator is (pentamethylcyclopentadienyl-2,2′

-bipyridine hydrogen) rhodium (I).

37. The system according to claim 35, wherein the nicotinamide co-factor is nicotinamide adenine dinucleotide phosphate.

38. The system according to claim 37, wherein the nicotinamide co-factor dependent membrane hydrogenase is a [Ni/Fe] hydrogenase from Allochromatium vinosum, Methanosarcina barkeri, Escherichia coli, and Rhodospirillum rubrum Desulfomicrobium baculatum and Ralstonia species.

39. The system according to claim 37, wherein the nicotinamide co-factor dependent membrane hydrogenase is a [Ni/Fe] hydrogenase from Pyrococcus Furiosus.