Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof

• US 7,090,819 B2
• Filed: 02/08/2002
• Issued: 08/15/2006
• Est. Priority Date: 02/12/2001
• Status: Active Grant

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Chiang, Wan-Ting, Kittrell, Wilber Carter, Smalley, Richard E., Smith, Kenneth A., Gu, Zhenning, Yang, Yuemei, Hauge, Robert H.
• Primary Examiner(s): HENDRICKSON, STUART L
• Application Number:
  US10/071,166
• Publication Number:
  US 20020159944A1
• Time in Patent Office: 1,649 Days
• Field of Search: 423/447.6, 423/447.7, 423/460, 423/447.1, 423/461
• US Class Current: 423/447.6
• 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 32/17 Purification
• CPC Class Codes: D01F 11/121 Halogen, halogenic acids or their salts
• CPC Class Codes: D01F 9/1278 Carbon monoxide

Abstract

The present invention relates to an all gas-phase process for the purification of single-wall carbon nanotubes and the purified single-wall carbon nanotube material. Known methods of single-wall carbon nanotube production result in a single-wall carbon nanotube product that contains single-wall carbon nanotubes in addition to impurities including residual metal catalyst particles and amounts of small amorphous carbon sheets that surround the catalyst particles and appear on the sides of the single-wall carbon nanotubes and “ropes” of single-wall carbon nanotubes. The purification process removes the extraneous carbon as well as metal-containing residual catalyst particles. The process comprises oxidation of the single-wall carbon nanotube material, reduction and reaction of a halogen-containing gas with the metal-containing species. The oxidation step may be done dry or in the presence of water vapor. The present invention provides a scalable means for producing high-purity single-wall carbon nanotube material.

Claims

1. A method for purifying single-wall carbon nanotubes comprising the steps of:

(a) oxidizing a single-wall carbon nanotube material in an oxidizing gaseous atmosphere at a temperature between about 200°

C. and about 500°

C. and at a pressure between about 0.01 and about 100 atmospheres, wherein the oxidizing gaseous atmosphere comprises a gas selected from the group consisting of oxygen, carbon dioxide, and mixtures thereof; and

(b) treating the single-wall carbon nanotube material with a halogen-containing gas subsequent to the step of oxidizing.

2. The method of claim 1, wherein the oxidizing gaseous atmosphere comprises water vapor.

3. The method of claim 1, wherein the oxidizing gaseous atmosphere comprises oxygen and water vapor.

4. The method of claim 1, wherein the oxidizing gaseous atmosphere comprises carbon dioxide.

5. The method of claim 1, wherein the halogen-containing gas comprises a halogen-containing compound selected from the group consisting of chlorine, bromine, fluorine, iodine, HCl, HBr, HF, HI, and combinations thereof.

6. The method of claim 1, wherein the halogen-containing gas comprises HCl.

7. The method of claim 1, wherein the halogen-containing gas comprises a halogen-containing compound at a concentration between about 1 vol % and about 100 vol % of the halogen-containing gas.

8. The method of claim 1, wherein the treating step is preformed at a pressure of at least about 1 Torr.

9. The method of claim 1, wherein the treating step is performed at a temperature between about 400°

C. and about 850°

C.

10. The method of claim 1 further comprising reducing the single-wall carbon nanotube material with a gas comprising hydrogen gas.

11. The method of claim 10, wherein the reducing step is performed at a temperature between about 250°

C. and about 500°

C.

12. The method of claim 1 further comprising annealing the single-wall carbon nanotube material.

13. The method of claim 12, wherein the annealing step is performed at a temperature between about 600°

C. and about 1000°

C.

15. The method of claim 12 wherein the annealing step is performed with an annealing gas comprising a gas selected from the group consisting of carbon dioxide, inert gases, nitrogen, and combinations thereof.

18. The method of claim 1 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material, wherein

(a) the single-wall carbon nanotube material comprises single-wall carbon nanotubes, amorphous carbon, and a metallic impurity, and

(b) the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.

19. The method of claim 18, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.

20. The method of claim 18, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.

21. The method of claim 1 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material, wherein

(a) the single-wall carbon nanotube material comprises single-wall carbon nanotubes, amorphous carbon, and a metallic impurity,

(b) the metallic impurity comprises metal;

and

(c) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.

22. The method of claim 21, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.

23. The method of claim 21, wherein the metal is present in an amount at most about 0.1 wt % of the purified single-wall carbon nanotube material.

14. A method for purifying single-wall carbon nanotubes comprising:

(a) oxidizing a single-wall carbon nanotube material in an oxidizing gaseous atmosphere;

(b) treating the single-wall carbon nanotube material with a halogen-containing gas; and

(c) annealing the single-wall carbon nanotube material, wherein the annealing step is performed in a vacuum.

16. A method for purifying single-wall carbon nanotubes comprising:

(a) oxidizing a single-wall carbon nanotube material in an oxidizing gaseous atmosphere;

(b) treating the single-wall carbon nanotube material with a halogen-containing gas; and

(c) annealing the single-wall carbon nanotube material, wherein the annealing step is performed with an annealing gas comprising a gas selected from the group consisting of carbon dioxide, inert gases, nitrogen, and combinations thereof and wherein the annealing gas further comprises water vapor.

17. The method of claim 16, wherein the water vapor is at a concentration of at least about 0.5 vol % of the annealing gas.

24. A method for purifying single-wall carbon nanotubes comprising the steps of:

(a) oxidizing a single-wall carbon nanotube material comprising single-wall carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere, wherein the oxidizing gaseous atmosphere comprises a gas selected from the group consisting of oxygen, carbon dioxide and mixtures thereof;

(b) reducing the single-wall carbon nanotube material with a reducing gas comprising hydrogen subsequent to the step of oxidizing; and

(c) treating the single-wall carbon nanotube material with a halogen-containing gas subsequent to the step of reducing.

25. The method of claim 24, wherein the gas is oxygen and the oxygen is at a concentration of at least about 1 vol % of the oxidizing gaseous atmosphere.

26. The method of claim 24, wherein the oxidizing gaseous atmosphere comprises air.

27. The method of claim 24, wherein the oxidizing gaseous atmosphere comprises water vapor.

28. The method of claim 27 wherein the water vapor is at a concentration of at least about 0.5 vol % of the oxidizing gaseous atmosphere.

29. The method of claim 24, wherein the oxidizing gaseous atmosphere comprises oxygen and water vapor.

30. The method of claim 24, wherein the gas is oxygen and the oxygen is at a concentration between about 10 vol % and about 100 vol % of the oxidizing gaseous atmosphere.

31. The method of claim 24, wherein the oxidizing gaseous atmosphere comprises carbon dioxide.

32. The method of claim 31, wherein the carbon dioxide is at a concentration of at least about 1 vol % of the oxidizing gaseous atmosphere.

33. The method of claim 24, wherein the oxidizing gaseous atmosphere comprises a second gas selected from the group consisting of inert gases, nitrogen, and combinations thereof.

34. The method of claim 24, wherein the oxidizing step is performed at a temperature at least about 200°

C.

35. The method of claim 24, wherein the halogen-containing gas comprises a gas selected from the group consisting of chlorine, bromine, fluorine, iodine, HCl, HBr, HF, HI, and combinations thereof.

36. The method of claim 24, wherein the halogen-containing gas comprises HCl.

37. The method of claim 24, wherein the halogen-containing gas comprises a halogen-containing compound at a concentration between about 1 vol % and about 100 vol % of the halogen-containing gas.

38. The method of claim 24, wherein the treating step is performed at a pressure between about 1 Torr and about 760 Torr.

39. The method of claim 24, wherein the treating step is preformed at a temperature between about 400°

C. and about 850°

C.

40. The method of claim 24, wherein the reducing step is performed at a temperature between about 250°

C. and about 500°

C.

41. The method of claim 24, wherein the reducing step is performed at a pressure between about 1 Torr and about 760 Torr.

42. The method of claim 24 further comprising annealing the single-wall carbon nanotube material.

43. The method of claim 42, wherein the annealing step is performed at a temperature between about 600°

C. and about 1000°

C.

44. The method of claim 42, wherein the annealing, step is performed in a vacuum.

45. The method of claim 42 wherein the annealing step is performed with an annealing gas comprising a gas selected from the group consisting of carbon dioxide, inert gases, nitrogen, and combinations thereof.

46. The method of claim 45, wherein the annealing gas comprises water vapor.

47. The method of claim 46, wherein the water vapor is at a concentration of at least about 0.5 vol % of the annealing gas.

48. The method of claim 24 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material, wherein the amorphous carbon is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.

49. The method of claim 48, wherein the amorphous carbon is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.

50. The method of claim 48, wherein the amorphous carbon is present in an amount at most about 0.2 wt % of the purified single-wall carbon nanotube material.

51. The method of claim 24 further comprising recovering the single-wall carbon nanotube material to obtain purified single-wall carbon nanotube material, wherein

(a) the metallic impurity comprises metal, and

(b) the metal is present in an amount at most about 5 wt % of the purified single-wall carbon nanotube material.

52. The method of claim 51, wherein the metal is present in an amount at most about 1 wt % of the purified single-wall carbon nanotube material.

53. The method of claim 51, wherein the metal is present in an amount at most about 0.1 wt % of the purified single-wall carbon nanotube material.

54. A method for purifying carbon nanotubes comprising the steps of:

(a) oxidizing a carbon nanotube material in an oxidizing gaseous at a temperature between about 200°

C. and about 500°

C. and at a pressure between about 0.01 and about 100 atmospheres, wherein the oxidizing gaseous atmosphere comprises a gas selected from the group consisting of oxygen, carbon dioxide and mixtures thereof; and

(b) treating the carbon nanotube material with a halogen-containing gas subsequent to the step of oxidizing.

55. A method for purifying carbon nanotubes comprising the steps of:

(a) oxidizing a carbon nanotube material comprising carbon nanotubes, amorphous carbon, and a metallic impurity in an oxidizing gaseous atmosphere, wherein the oxidizing gaseous atmosphere comprises a gas selected from the group consisting of oxygen, carbon dioxide and mixtures thereof;

(b) reducing the carbon nanotube material with a reducing gas comprising hydrogen subsequent to the step of oxidizing; and

(c) treating the carbon nanotube material with a halogen-containing gas subsequent to the step of reducing.