Method of purifying nanotubes and nanofibers using electromagnetic radiation

• US 7,014,737 B2
• Filed: 06/17/2002
• Issued: 03/21/2006
• Est. Priority Date: 06/15/2001
• Status: Expired due to Fees

• Current Assignee: Penn State Research Foundation
• Original Assignee: Penn State Research Foundation
• Inventors: Harutyunyan, Avetik, Eklund, Peter C., Pradhan, Bhabendra K.
• Primary Examiner(s): Silverman, Stanley S.
• Assistant Examiner(s): LISH, PETER J
• Application Number:
  US10/174,477
• Publication Number:
  US 20030042128A1
• Time in Patent Office: 1,373 Days
• Field of Search: 204/158.2, 502/27, 502/56, 423/447.1, 423/447.2, 423/447.3, 423/445.R, 423/445.B, 423/461
• US Class Current: 204/158.2
• 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: Y10S 977/845 Purification or separation of fullerenes or nanotubes

Abstract

Disclosed are methods of purifying mixtures comprising nanofibers and/or nanotubes and residual catalyst particles that are covered by outer layers of the nanotube or nanofiber material. The mixtures are exposed to electromagnetic radiation, which induces localized heating in the residual catalyst particles. The localized heating creates breaches in the outer layers. Thereafter, the residual catalyst particles may be removed under relatively mild conditions that do not significantly affect the structural integrity of the nanotubes or nanofibers. The methods of the invention have been used to particular advantage in the purification of single wall carbon nanotubes (SWNTs) synthesized using metal catalysts. For these SWNTs, microwave radiation is preferably used to induce the localized heating, the outer layers are preferably removed at least in part by carrying out the localized heating under air, and the residual catalyst may be removed by exposure to relatively dilute aqueous acid.

Claims

1. A process for purifying a nanostructure mixture, said mixture comprising

a nanotube or a nanofiber, and a particle of a catalyst residue, said process comprising the steps of:

inducing localized heating of said particle by exposing the mixture to electromagnetic radiation or an electromagnetic field; and

removing the particle from the mixture.

2. The process of claim 1, wherein the localized heating is effected at least in part by exposure to a magnetic induction field.

3. The process of claim 1, wherein the localized heating is effected at least in part by exposure to microwave radiation.

4. The process of claim 1, wherein the localized heating is effected at least in part by cooling said nanofiber.

5. The process of claim 4, wherein the nanofiber is cooled at least in part by flowing a fluid over the mixture, wherein the fluid is selected from the group consisting of nitrogen, oxygen, argon, helium, hydrogen acid, nitric acid, and mixtures thereof.

6. The process of claim 1, wherein the particle comprises a metal, an oxide, a carbide, a silicide, a germanide, or an arsenide.

7. The process of claim 1, wherein the particle comprises a metal, a carbide, or a silicide.

8. The process of claim 1, wherein said nanotube or nanofiber comprises a material selected from the group consisting of carbon, silicon, germanium, gallium arsenide, gallium phosphide, indium arsenide, indiumphosphide, metal silicides, zinc sulfide, zinc selenide, cadmium sulfide, cadmium selenide, and mixtures thereof.

9. The process of claim 1, wherein said nanotube or nanofiber comprises carbon or silicon.

10. The process of claim 1, wherein the particle is at least partially surrounded by an outer layer comprising carbon, silicon, germanium, or gallium arsenide.

11. The process of claim 10, wherein the outer layer is at least partially removed.

12. The process of claim 10, wherein the localized heating and the removal of the outer layer are simultaneous.

13. The process of claim 10, wherein the outer layer is removed by gasification.

14. The process of claim 10, wherein the outer layer is removes by oxidation.

15. The process of claim 10, wherein the outer layer is removed by reaction with oxygen or hydrogen.

16. The process of claim 1, wherein the particle is removed by oxidation, dissolution, or both oxidation and dissolution.

17. The process of claim 16, wherein the particle is removed by reaction with a dilite acid.

18. The process of claim 16, wherein the particle is removed by vapor transport.

19. The process of claim 10, wherein the particle is removed by oxidation, dissolution, or both oxidation and dissolution.

20. The process of claim 19, wherein the local heating is effected by microwave radiation and by cooling the nanofiber by flowing a gas over the mixture, the particle comprises a metal, the removal of the outer layer is effected by heating in oxygen or a mixture comprising oxygen and an inert gas, and the removal of the particle is effected by dissolution in acid.

21. The process of claim 20 wherein the nanofiber is a carbon nanotube.

22. A process for purifying a nanostructure, comprising the steps of:

synthesizing a nanofiber by a synthesis process, said synthesis process yielding the nanofiber and particles of a residue of a material promoting formation of said nanofiber, each of said particles being surrounded completely or incompletely by an outer layer of a composition similar to the composition of the nanofiber;

locally heating the outer layers; and

removing the particles.

23. A process for purifying carbon nanotubes, comprising the steps of:

providing a mixture comprising the carbon nanotubes and particles of a catalyst residue, each of said particles being at least partially surrounded by an outer layer, said outer layer comprising graphene carbon;

exposing the particles to electromagnetic radiation or an electromagnetic field; and

removing the particles.

24. The process of claim 23 wherein the carbon nanotubes are single wall nanotubes.

25. The process of claim 23 wherein the catalyst is selected from the group consisting of iron, cobalt, nickel, or a combination thereof.

26. The process of claim 23 comprising exposing the particles to a magnetic induction field.

27. The process of claim 23 comprising exposing the particles to microwave radiation.

28. The process of claim 23 wherein the microwave radiation has a frequency of about 2.45 GHz and a power of about 150 W.

29. The process of claim 23 wherein the outer layers are at least partially removed.

30. The process of claim 29 wherein the removal is effected by contacting the mixture with a flowing gas during the exposure to the electromagnetic radiation or the magnetic induction field.

31. The process of claim 30 wherein the gas is selected from the group consisting of oxygen, air, hydrogen peroxide and hydrogen.

32. The process of claim 23 wherein the particles are removed by oxidation or dissolution or both oxidation and dissolution.

33. The process of claim 32, wherein the particles are removed by exposure to acid.

34. The process of claim 23 wherein the particles are exposed to microwave radiation;

the outer layers are at least partially removed by flowing dry air over the mixture simultaneously with the exposure to microwave radiation; and

the particles are removed by heating the mixture at reflux in dilute aqueous acid.

35. The process of claim 34 wherein the microwave radiation has a frequency of 2.45 GHz and a power of 150 W;

wherein the radiation exposure generates a temperature of about 500°

C. within the particles, which temperature is maintained for about 20 minutes;

wherein the dry air is flowed at a rate of approximately 100 standard cubic centimeters per minute;

wherein the dilute aqueous acid is hydrogen chloride at a concentration of approximately 4M; and

wherein the mixture is heated at reflux in the dilute aqueous acid for approximately 6 hours.