Alkyne-assisted nanostructure growth
The present invention relates to the formation and processing of nanostructures including nanotubes. Some embodiments provide processes for nanostructure growth using relatively mild conditions (e.g., low temperatures). In some cases, methods of the invention may improve the efficiency (e.g., catalyst efficiency) of nanostructure formation and may reduce the production of undesired byproducts during nanostructure formation, including volatile organic compounds and/or polycylic aromatic hydrocarbons. Such methods can both reduce the costs associated with nanostructure formation, as well as reduce the harmful effects of nanostructure fabrication on environmental and public health and safety.
1. A method for forming carbon nanostructures, comprising:
heating a reactant vapor comprising a nanostructure precursor material to a temperature between 700° C. and 1200° C.;
after the heating step, cooling the reactant vapor to a temperature of less than 400° C.;
after the cooling step, contacting the reactant vapor at the temperature of less than 400° C. with a catalyst material to cause formation of nanostructures,
wherein the nanostructure precursor material comprises an alkyne and an alkene.
2. A method as in claim 1 , wherein the alkyne is ethyne, propyne, but-1-en-3-yne, or 1,3-butadiyne.
3. A method as in claim 1 , wherein the reactant vapor comprises ethylene, hydrogen, and an alkyne.
4. A method as in claim 1 , wherein the reactant vapor comprises, by volume, 35% or less ethylene, 70% or less hydrogen, and 0.1% or less alkyne, such that the total amount of ethylene, hydrogen, and alkyne equals 100%.
5. A method as in claim 1 , wherein the reactant vapor comprises, by volume, 16% to 35% ethylene.
6. A method as in claim 1 , wherein the reactant vapor comprises, by volume, 16% to 70% hydrogen.
7. A method as in claim 1 , wherein the reactant vapor further comprises helium.
8. A method as in claim 1 , wherein the reactant vapor further comprises argon.
9. A method as in claim 1 , wherein the reactant vapor comprises, by volume, 20% ethylene, 51% hydrogen, and 29% helium.
10. A method as in claim 1 , wherein the reactant gas is substantially free of an oxygen-containing species, provided that the oxygen-containing species is not water.
11. A method as in claim 1 , wherein the act of contacting causes formation of a product vapor comprising at least one carbon-containing byproduct.
12. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 300° C. prior to contacting the catalyst material.
13. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 200° C. prior to contacting the catalyst material.
14. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 100° C. prior to contacting the catalyst material.
15. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 75° C. prior to contacting the catalyst material.
16. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 50° C. prior to contacting the catalyst material.
17. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 30° C. prior to contacting the catalyst material.
18. A method as in claim 1 , wherein the reactant vapor is maintained at a temperature of less than 25° C. prior to contacting the catalyst material.
19. A method as in claim 1 , further comprising:
pre-heating, prior to the act of introducing, the reactant vapor to a temperature of at least 700° C.; and
cooling the reactant vapor prior to contacting the catalyst material.
20. A method as in claim 1 , further comprising:
pre-heating, prior to the act of introducing, the reactant vapor to a temperature of at least 900° C.; and
cooling the reactant vapor prior to contacting the catalyst material.
21. A method as in claim 1 , further comprising:
pre-heating, prior to the act of introducing, the reactant vapor to a temperature of at least 1100° C.; and
cooling the reactant vapor prior to contacting the catalyst material.
22. A method as in claim 1 , wherein the nanostructures are formed on a surface of the catalyst material.
23. A method as in claim 1 , wherein the nanostructures are nanotubes.
24. A method as in claim 23 , wherein the nanostructures are single-walled carbon nanotubes or multi-walled carbon nanotubes.
25. A method as in claim 23 , wherein the nanostructures are vertically aligned multi-walled carbon nanotubes.
26. A method as in claim 1 , wherein the nanostructures are arranged on or in a surface of the catalyst material, such that the long axes of the nanostructures are substantially aligned and non-parallel to the surface.
27. A method as in claim 1 , wherein the nanostructures are arranged on or in a surface of the catalyst material, such that the long axes of the nanostructures are substantially parallel to the surface.
28. A method as in claim 1 , wherein the catalyst material comprises a metal or metal oxide.
29. A method as in claim 28 , wherein the catalyst material comprises iron.
30. A method as in claim 11 , wherein the at least one carbon-containing byproduct is a volatile organic compound (VOC) or a polycyclic aromatic hydrocarbon (PAH).
31. A method as in claim 30 , wherein the volatile organic compound is methane, ethane, propane, propene, 1,2-butadiene, 1,3-butadiene, 1,3-butadiyne, pentane, pentene, cyclopentadiene, hexene, or benzene.
32. A method as in claim 30 , wherein the volatile organic compound is methane, 1,3-butadiene, or benzene.
33. A method as in claim 30 , wherein the polycyclic aromatic hydrocarbon is naphthalene, acenaphthalene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, coronene, triphenylene, naphthacene, phenanthrelene, picene, fluorene, perylene, or benzopyrene.
34. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 10% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
35. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 5% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
36. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 3% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
37. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 2.6% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
38. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 2.0% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
39. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 1.5% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
40. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 1.0% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
41. A method as in claim 11 , wherein the product vapor comprises one or more volatile organic compounds in an amount less than 0.9% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, wherein the volatile organic compound is not ethylene.
42. A method as in claim 11 , wherein the product vapor comprises methane in an amount less than 0.4% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, and wherein methane is substantially not present in the reactant vapor.
43. A method as in claim 11 , wherein the product vapor comprises 1,3-butadiene in an amount less than 0.4% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, and wherein 1,3-butadiene is substantially not present in the reactant vapor.
44. A method as in claim 11 , wherein the product vapor comprises benzene in an amount less than 0.3% of the total volume of product vapor that exits the reaction chamber during formation of the nanostructure, and wherein benzene is substantially not present in the reactant vapor.
45. A method for forming carbon nanostructures, comprising:
contacting a reactant vapor comprising, by volume, 20% ethylene, 51% hydrogen, and 29% helium, with a catalyst material to cause formation of nanostructures,
wherein the reactant vapor is maintained at a temperature of less than about 400° C.