IP Library Granted Patent US 10,003,084
Granted Patent B2
US 10,003,084 · App. 14/413,395 · Granted Jun 19, 2018

Metal nanoparticle-graphene composites and methods for their preparation and use

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Quick Facts
Patent No.
US 10,003,084
App. No.
14/413,395
Granted
Jun 19, 2018
Kind
B2
Abstract

Methods of forming metal nanoparticle-graphene composites are provided. The methods can include mixing a metal precursor with graphite oxide in the presence of a liquid medium to form a metal precursor-graphite oxide mixture, and exfoliating the graphite oxide and reducing the metal precursor in the metal precursor-graphite oxide mixture to deposit metal nanoparticles on a first major surface of a graphene sheet formed by exfoliation of the graphite oxide.

Claims (31)

1. A method to form a metal nanoparticle-graphene composite, the method comprising:

mixing a metal precursor with graphite oxide in presence of a liquid medium to form a metal precursor-graphite oxide mixture;

exfoliating the graphite oxide of the metal precursor-graphite oxide mixture with hydrogen to chemically modify the graphite oxide to form a hydrogen-exfoliated graphene sheet; and

while exfoliating the graphite oxide, simultaneously reducing the metal precursor in the metal precursor-graphite oxide mixture to adsorb metal nanoparticles on a first major surface of the hydrogen-exfoliated graphene sheet.

2. The method of claim 1 , wherein the metal nanoparticles comprise platinum (Pt), palladium (Pd), silver (Ag), gold (Au), nickel (Ni), titanium (Ti), tin (Sn), ruthenium (Ru), or combinations thereof.

3. The method of claim 1 , wherein the metal precursor comprises platinum (Pt), palladium (Pd), silver (Ag), gold (Au), nickel (Ni), titanium (Ti), tin (Sn), ruthenium (Ru), or combinations thereof.

4. The method of claim 1 , wherein the metal precursor comprises hexachloroplatinic acid (H 2 PtCl 6 .6H 2 O).

5. The method of claim 1 , wherein the liquid medium is water, acetone, ethanol, toluene, or combinations thereof.

6. The method of claim 1 , further comprising drying the metal precursor-graphite oxide mixture before exfoliating the graphite oxide of the metal precursor-graphite oxide mixture.

7. The method of claim 1 , wherein exfoliating the graphite oxide and reducing the metal precursor comprises:

contacting hydrogen gas (H 2 ) with oxygen-based functional groups of the graphite oxide within a reaction chamber to form the hydrogen-exfoliated graphene sheet; and

reducing the metal precursor using a hydrogen gas to attach the metal nanoparticles to the hydrogen-exfoliated graphene sheet.

8. The method of claim 7 , wherein a temperature within the reaction chamber is about 200° C. to about 600° C.

9. The method of claim 7 , wherein a flow rate of the hydrogen gas within the reaction chamber is about 50 sccm to about 200 sccm.

10. The method of claim 7 , wherein substantially 100% of the metal precursor is reduced to the metal nanoparticles attached to the hydrogen-exfoliated graphene sheet.

11. The method of claim 7 , wherein the metal precursor is reduced to the metal nanoparticles within about 10 seconds to about 15 seconds.

12. The method of claim 1 , wherein the metal precursor comprises hexachloroplatinic acid (H 2 PtCl 6 .6H 2 O) and the metal nanoparticles comprise platinum nanoparticles.

13. The method of claim 1 , wherein a density of graphene in the metal nanoparticle-graphene composite is about 0.5 g/cm 3 to about 0.8 g/cm 3 .

14. A mixture comprising:

a metal precursor;

graphite oxide;

hydrogen gas;

a liquid medium;

a hydrogen-exfoliated graphene sheet; and

a plurality of platinum nanoparticles dispersed on a first major surface of the hydrogen-exfoliated graphene sheet.

15. The mixture of claim 14 , wherein the metal precursor comprises platinum (Pt), palladium (Pd), silver (Ag), gold (Au), nickel (Ni), titanium (Ti), tin (Sn), ruthenium (Ru), or combinations thereof.

16. The mixture of claim 14 , wherein the metal precursor comprises hexachloroplatinic acid (H 2 PtCl 6 .6H 2 O).

17. The mixture of claim 14 , wherein the liquid medium is water, acetone, ethanol, toluene, or combinations thereof.

18. The mixture of claim 14 , wherein the hydrogen-exfoliated graphene sheet and the plurality of platinum nanoparticles dispersed on the first major surface of the hydrogen-exfoliated graphene sheet to form an electrocatalyst, an average size of the platinum nanoparticles of the platinum nanoparticles is about 3 nanometers to about 5 nanometers, and a current density of the electrocatalyst is at least about 1239 mA cm −2 .

19. The mixture of claim 18 , wherein the current density is measured at a voltage of 0.5 V.

20. The mixture of claim 14 , wherein an average particle size of the plurality of platinum nanoparticles is about 3.3 nanometers.

Assignments (4)
RELEASE OF SECURITY INTEREST IN PATENTS, RECORDED ON JANUARY 29, 2019 AT REEL 048373 FRAME 0217 Recorded Sep 22, 2025
From: CRESTLINE DIRECT FINANCE, L.P., AS COLLATERAL AGENT
To: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Reel/Frame 072936/0464 →
RELEASE OF SECURITY INTEREST Recorded Jul 31, 2019
From: CRESTLINE DIRECT FINANCE, L.P.
To: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Reel/Frame 049924/0794 →
SECURITY INTEREST Recorded Jan 29, 2019
From: EMPIRE TECHNOLOGY DEVELOPMENT LLC
To: CRESTLINE DIRECT FINANCE, L.P.
Reel/Frame 048373/0217 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 7, 2015
From: SUNDARA, RAMAPRABHU; PARAMBATH, VINAYAN BHAGHAVATHI; NAGAR, RUPALI
To: INDIAN INSTITUTE OF TECHNOLOGY MADRAS
Reel/Frame 034657/0241 →