Catalytic growth of single-and double-wall carbon nanotubes from metal particles

• US 7,201,887 B2
• Filed: 12/20/2002
• Issued: 04/10/2007
• Est. Priority Date: 09/18/1998
• Status: Expired due to Fees

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Colbert, Daniel T., Hafner, Jason H., Smith, Ken
• Primary Examiner(s): HENDRICKSON, STUART L
• Application Number:
  US10/327,405
• Publication Number:
  US 20030175200A1
• Time in Patent Office: 1,572 Days
• Field of Search: 423/447.3, 423/447.1, 423/447.2, 423/445.R, 423/445.B, 977/742, 977/750, 977/843
• US Class Current: 423/447.3
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/881 and iron
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/08 Aligned nanotubes
• CPC Class Codes: C01B 2202/36 Diameter
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: D01F 9/127 by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
• CPC Class Codes: Y10S 977/75 Single-walled
• CPC Class Codes: Y10S 977/843 Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/845 Purification or separation of fullerenes or nanotubes

Abstract

The present invention concerns a method for growing carbon nanotubes using a catalyst system that preferentially promotes the growth of single- and double-wall carbon nanotubes, rather than larger multi-walled carbon nanotubes. Ropes of the carbon nanotubes are formed that comprise single-wall and/or double-wall carbon nanotubes.

Claims

1. A method for producing carbon nanotubes comprising:

contacting metal catalyst particles in a reaction zone maintained at an elevated temperature with a carbon-containing compound to produce carbon nanotubes, wherein the metal catalyst particles are introduced with a support, wherein the metal catalyst particles comprise a Group VIB transition metal and a Group VIIIB transition metal, wherein the Group VIIIB transition metal is present in greater mass than the Group VIB transition metal, wherein the support and the Group VIB transition metal are present in a mass ratio of at least about 34;

1, and wherein the carbon nanotubes are predominately single-wall carbon nanotubes.

2. The method of claim 1, wherein the Group VIB transition metal is selected from the group consisting of chromium, molybdenum and tungsten.

3. The method of claim 1, wherein the Group VIIIB transition metal is selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.

4. The method of claim 1, wherein the Group VIIIB transition metal is iron.

5. The method of claim 4, wherein the Group VIB transition metal is molybdenum.

6. The method of claim 1, wherein the Group VIB transition metal is molybdenum.

7. The method of claim 1, wherein the carbon-containing compound is selected from the group consisting of carbon monoxide, aromatic hydrocarbons, non-aromatic hydrocarbons, oxygen-containing hydrocarbons, other hydrocarbons, and mixtures thereof.

8. The method of claim 7, wherein the aromatic hydrocarbon is selected from the group consisting of benzene, toluene, xylene, cumene, ethylbenzene, naphthalene, phenanthrene, anthracene, and mixtures thereof.

9. The method of claim 7, wherein the non-aromatic hydrocarbon is selected from the group consisting of methane, ethane, propane, ethylene, propylene, acetylene, and mixtures thereof.

10. The method of claim 7, wherein the oxygen-containing hydrocarbon is selected from the group consisting of formaldehyde, acetaldehyde, acetone, methanol, ethanol, and mixtures thereof.

11. The method of claim 1, wherein at least about 30% of the carbon nanotubes are single-wall carbon nanotubes.

12. The method of claim 1, wherein at least about 70% of the carbon nanotubes are single-wall carbon nanotubes.

13. The method of claim 1, wherein the carbon-containing compound is ethylene.

14. The method of claim 1, wherein the carbon-containing compound is carbon monoxide.

15. The method of claim 1, wherein the temperature in the reaction zone ranges between about 600°

C. and about 900°

C.

16. The method of claim 1, wherein the temperature in the reaction zone ranges between about 700°

C. and about 850°

C.

17. The method of claim 1, wherein the Group VIIIB transition metal and the Group VIB transition metal are present in a mass ratio of at least about 9:

1.

18. The method of claim 1, wherein the support is carbon.

19. The method of claim 1, wherein the support is an oxide compound.

20. The method of claim 19 wherein the oxide compound is selected from the group consisting of alumina, quartz, silicates, aluminum silicates, mullite, and mixtures thereof.

21. The method of claim 1, wherein the support is a metal oxide.

22. The method of claim 1, wherein the support is alumina.

23. The method of claim 1, wherein the support is present in greater mass than the combined mass of the Group VIIIB transition metal and the Group VIB transition metal.

24. The method of claim 1, wherein the support is present in greater mass than the metal catalyst particles.

25. The method of claim 1, wherein the support and the Group VIIIB transition metal are present in a mass ratio of at least about 34:

9.

26. The method of claim 1, wherein the support and the combined mass of the Group VIIIB transition metal and the Group VIB transition metal are present in a mass ratio of at least about 9:

1.

27. The method of claim 1, wherein the support and metal catalyst particles are present in a mass ratio of at least about 9:

1.