Method of producing graphene from a hydrocarbon gas and liquid metal catalysts

Patent metadata

Field	Value
Publication number	US-10059591-B2
Application number	US-201415117332-A
Country	US
Kind code	B2
Filing date	Feb 7, 2014
Priority date	Feb 7, 2014
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

Methods of producing graphene, reaction chambers for forming graphene, and graphene sheets formed from the methods are described herein. A method may include adding at least one metal catalyst in a reaction chamber, adding at least one hydrocarbon gas in the reaction chamber, allowing the at least one metal catalyst and the at least one hydrocarbon gas to contact one another to produce a product, and dehydrogenating the product to produce the graphene.

First claim

What is claimed is:

1. A method of producing graphene, the method comprising:
adding at least one liquid metal catalyst in a reaction chamber;
adding at least one hydrocarbon gas in the reaction chamber;
allowing the at least one liquid metal catalyst and the at least one hydrocarbon gas to contact one another to produce a product;
dehydrogenating the product to produce graphene; and
removing the at least one liquid metal catalyst from the reaction chamber by straining the at least one liquid metal catalyst through a porous substrate, wherein the graphene dispersed in the liquid metal catalyst is captured by the porous substrate.

2. The method of claim 1 , further comprising combining the at least one liquid metal catalyst with at least one additive prior to contacting with the at least one hydrocarbon gas.

3. The method of claim 2 , wherein combining comprises combining with sodium carbonate, potassium nitrate, lithium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, lithium nitrate, sodium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, zinc nitrate, lead nitrate, copper nitrate, iron nitrate, chromium nitrate, cobalt nitrate, nickel nitrate, titanium nitrate, lithium nitrite, sodium nitrite, rubidium nitrite, cesium nitrite, magnesium nitrite, calcium nitrite, strontium nitrite, barium nitrite, zinc nitrite, lead nitrite, copper nitrite, iron nitrite, chromium nitrite, cobalt nitrite, nickel nitrite, titanium nitrite, lithium chlorite, sodium chlorite, rubidium chlorite, cesium chlorite, magnesium chlorite, calcium chlorite, strontium chlorite, barium chlorite, zinc chlorite, lead chlorite, copper chlorite, iron chlorite, chromium chlorite, cobalt chlorite, nickel chlorite, titanium chlorite, lithium hypochlorite, sodium hypochlorite, rubidium hypochlorite, cesium hypochlorite and magnesium hypochlorite, calcium chlorite, strontium chlorite, barium chlorite, zinc chlorite, lead chlorite, copper chlorite, iron chlorite, chromium chlorite, cobalt chlorite, nickel chlorite, titanium chlorite, lithium hypochlorite, sodium hypochlorite, rubidium hypochlorite, cesium hypochlorite, magnesium hypochlorite, calcium hypochlorite, strontium hypochlorite, barium hypochlorite, zinc hypochlorite, or a combination thereof.

4. The method of claim 1 , further comprising placing a reducing agent in the reaction chamber after adding the at least one hydrocarbon gas in the reaction chamber.

5. The method of claim 4 , wherein the placing comprises placing methane, ethane, propane, butane, pentane, hexane, hydrogen, lithium, sodium, potassium, rubidium, cesium, magnesium, or a combination thereof.

6. The method of claim 1 , further comprising dissolving the hydrocarbon gas in a solvent prior to placing the at least one hydrocarbon gas in the reaction chamber.

7. The method of claim 6 , wherein the dissolving comprises dissolving in ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, sorbitol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, galactitol, fucitol, iditol, inositol, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, or a combination thereof.

8. The method of claim 1 , wherein allowing the at least one metal catalyst and the at least one hydrocarbon gas to contact one another comprises allowing the at least one metal catalyst and the at least one hydrocarbon gas to contact one another at a temperature of about 300° C. to about 400° C.

9. The method of claim 1 , wherein adding the hydrocarbon gas comprises adding methane, ethane, ethyne, ethene, carbon monoxide, ethanol, propane, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene, toluene, carbon dioxide, chloromethane, dichloromethane, chloroform, bromomethane, dibromomethane, bromoform, iodomethane, diodomethane, iodoform, carbon tetrachloride, carbon tetrabromide, or a combination thereof.

10. The method of claim 1 , wherein the at least one liquid metal catalyst is a molten metal catalyst.

11. The method of claim 1 , wherein adding the at least one liquid metal catalyst comprises adding at least one liquid metal catalyst comprising mercury, bismuth, cesium, gallium, nickel, silver, an alloy thereof, or a combination thereof.

12. The method of claim 1 , wherein adding the at least one liquid metal catalyst comprises adding an alloy including a Wood's metal, a Rose's metal, a Field's metal, cerrosafe, cerrolow, or a combination thereof.

13. The method of claim 1 , wherein adding the at least one liquid metal catalyst comprises adding an amalgam comprising mercury and at least one of bismuth, potassium, lithium, sodium, rubidium, cesium, magnesium, calcium, strontium, barium, copper, silver, gold, platinum, nickel, palladium, cobalt, rhodium, iridium, iron, ruthenium, rhenium, and wolfram.

14. The method of claim 1 , wherein adding the at least one liquid metal catalyst comprises adding an alloy having a melting point equal to or less than about 150° C.

15. The method of claim 1 , wherein allowing the at least one liquid metal catalyst and the at least one hydrocarbon gas to contact one another comprises contacting at an interface between the at least one liquid metal catalyst and the at least one hydrocarbon gas, wherein the interface is a substantially horizontal surface with respect to a bottom surface of the reaction chamber.

16. The method of claim 1 , wherein allowing the at least one liquid metal catalyst and the at least one hydrocarbon gas to contact one another comprises producing the product by a (2+2+2) cycloaddition reaction.

17. The method of claim 1 , wherein dehydrogenating the product comprises producing the graphene containing substantially no defects.

18. A method of producing graphene, the method comprising:
combining at least one metal catalyst with an additive;
adding the at least one metal catalyst and the additive into a reaction chamber;
evacuating any gas in the reaction chamber;
adding at least one hydrocarbon gas into the reaction chamber;
adding a solvent into the reaction chamber;
heating the reaction chamber;
allowing the at least one metal catalyst and the at least one hydrocarbon gas to contact one another to produce a product;
dehydrogenating the product to produce the graphene;
removing the at least one metal catalyst from the reaction chamber;
removing the solvent from the reaction chamber; and
collecting the graphene on a porous substrate in the reaction chamber.

19. The method of claim 18 , further comprising melting the at least one metal catalyst prior to adding the at least one hydrocarbon gas into the reaction chamber.

20. The method of claim 18 , wherein combining comprises combining with sodium carbonate, potassium nitrate, lithium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, lithium nitrate, sodium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, zinc nitrate, lead nitrate, copper nitrate, iron nitrate, chromium nitrate, cobalt nitrate, nickel nitrate, titanium nitrate, lithium nitrite, sodium nitrite, rubidium nitrite, cesium nitrite, magnesium nitrite, calcium nitrite, strontium nitrite, barium nitrite, zinc nitrite, lead nitrite, copper nitrite, iron nitrite, chromium nitrite, cobalt nitrite, nickel nitrite, titanium nitrite, lithium chlorite, sodium chlorite, rubidium chlorite, cesium chlorite, magn

Assignees

• Empire Technology Dev Llc

Inventors

• Carlson William Brenden
• Casasanta Iii Vincent
• Wan Feng
• Roberts Bradley Kirk
• Londergan Timothy Martin

Classifications

• B01J23/08

  of gallium, indium or thallium · CPC title

• B01J23/04

  Alkali metals · CPC title

• B01J27/232

  Carbonates · CPC title

• B01J23/66

  Silver or gold · CPC title

• B01J23/06

  of zinc, cadmium or mercury · CPC title