IP Library Granted Patent US 10,471,409
Granted Patent B2
US 10,471,409 · App. 14/439,304 · Granted Nov 12, 2019

Methods for producing hydrogen using nanoparticle-catalyst mixtures

Inventors: Todd D. Krauss (Pittsford, NY); Richard Eisenberg (Rochester, NY); Patrick Holland (New Haven, CT); Fen Qiu (Rochester, NY); Zhiji Han (Rochester, NY)
Assignee: University of Rochester
B01J19/122B01J23/755C01B3/06Y02E60/36
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Quick Facts
Patent No.
US 10,471,409
App. No.
14/439,304
Granted
Nov 12, 2019
Kind
B2
Abstract

Provided are compositions for and methods of producing hydrogen. For example, the compositions comprise nanocrystals, a catalyst, a source of electrons, and an aqueous medium. The nanocrystals, catalyst, aqueous medium, and, optionally, the source of electrons are present as a mixture. The methods produce hydrogen by exposing the compositions to electromagnetic radiation (e.g., solar flux).

Claims (38)

1. A method for producing hydrogen comprising the steps of:

a) contacting a nanoparticle, wherein the nanoparticle is selected from CdSe, CdS, CdTe, PbS, PbTe, PbSe, GaAs, InP, InAs, Si, and Ge nanoparticles and the nanoparticles are core-shell nanocrystals, nanorods, or dot-in rods, and a group 6 to group 11 transition metal salt catalyst in an aqueous medium to form a mixture in the presence of a source of electrons; and

b) exposing the mixture from a) to electromagnetic radiation having at least a wavelength in the absorption profile of the nanoparticle,

wherein the nanoparticle, the group 6 to group 11 transition metal salt complex catalyst, and aqueous medium are present as a mixture and,

wherein upon exposure to the electromagnetic radiation the nanoparticle is capable of generating an electron that can reduce, in the presence of the group 6 to group 11 transition metal salt complex catalyst, a proton in the aqueous medium, and

wherein the source of electrons is capable of reducing the nanoparticle after reduction of the proton,

such that hydrogen is produced.

2. The method of claim 1 , wherein the group 6 to group 11 transition metal salt is generated in situ.

3. The method of claim 1 , wherein the source of electrons is a sacrificial electron donor and is present in the mixture.

4. The method of claim 1 , wherein the source of electrons is an external source of electrons.

5. The method of claim 4 , wherein the external source of electrons is a solar cell or an electrochemical bias.

6. The method of claim 1 , wherein the aqueous medium is water.

7. A composition for producing hydrogen comprising:

a) a nanoparticle, wherein the nanoparticle is selected from CdSe, CdS, CdTe, PbS, PbTe, PbSe, GaAs, InP, InAs, Si, and Ge nanoparticles, wherein the nanoparticles are core-shell nanocrystals, nanorods, or dot-in rods;

b) a group 6 to group 11 transition metal salt catalyst;

c) a source of electrons; and

d) an aqueous medium;

wherein the nanoparticle, the group 6 to group 11 transition metal salt complex catalyst, and aqueous medium are present as a mixture and,

wherein upon exposure to electromagnetic radiation having a wavelength in the absorption profile of the nanoparticle the nanoparticle is capable of generating an electron that can reduce, in the presence of the group 6 to group 11 transition metal salt complex catalyst, a proton in the aqueous medium and the source of electrons is capable of reducing the nanoparticle after reduction of the proton.

8. The composition of claim 7 , wherein the source of electrons is also present in the mixture.

9. The composition of claim 7 , wherein the nanoparticles are nanocrystals.

10. The composition of claim 7 , wherein the group 6 to group 11 transition metal salt is a Ni 2+ salt.

11. The composition of claim 7 , wherein the source of electrons is a sacrificial electron donor.

12. The composition of claim 7 , wherein the source of electrons is an external source of electrons.

13. The composition of claim 12 , wherein the external source of electrons is a solar cell or an electrochemical bias.

14. The composition of claim 7 , wherein the aqueous medium is water.

15. The composition of claim 7 , wherein the group 6 to group 11 transition metal salt catalyst is in solution in the aqueous medium.

16. A composition for producing hydrogen comprising:

a) a nanoparticle, wherein the nanoparticle is selected from CdSe, CdS, CdTe, PbS, PbTe, PbSe, GaAs, InP, InAs, Si, and Ge nanoparticles;

b) a group 6 to group 11 transition metal salt catalyst;

c) a source of electrons; and

d) an aqueous medium comprising water and a protic organic solvent;

wherein the nanoparticle, the group 6 to group 11 transition metal salt complex catalyst, and aqueous medium are present as a mixture and,

wherein upon exposure to electromagnetic radiation having a wavelength in the absorption profile of the nanoparticle the nanoparticle is capable of generating an electron that can reduce, in the presence of a metal complex catalyst, a proton in the aqueous medium and the source of electrons is capable of reducing the nanoparticle after reduction of the proton.

17. The composition of claim 16 , wherein the source of electrons is also present in the mixture.

18. The composition of claim 16 , wherein the source of electrons is a sacrificial electron donor.

19. The composition of claim 16 , wherein the source of electrons is an external source of electrons.

20. The composition of claim 16 , wherein the aqueous medium is water.

Assignments (2)
CONFIRMATORY LICENSE Recorded Aug 4, 2016
From: ROCHESTER UNIVERSITY OF
To: ENERGY, UNITED STATES DEPARTMENT OF
Reel/Frame 039627/0548 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 29, 2015
From: KRAUSS, TODD D.; EISENBERG, RICHARD; HOLLAND, PATRICK; QIU, FEN; HAN, ZHIJI
To: UNIVERSITY OF ROCHESTER
Reel/Frame 035523/0968 →
Continuity (2)
Provisional Application 61722374 · Nov 5, 2012
Related Publication 20150290615A1 · Oct 15, 2015