Methods of chemically derivatizing single-wall carbon nanotubes

• US 6,841,139 B2
• Filed: 03/16/2001
• Issued: 01/11/2005
• Est. Priority Date: 09/18/1998
• Status: Expired due to Term

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Smalley, Richard E., Liu, Jie, Colbert, Daniel T., Smith, Ken, Margrave, John L., Hauge, Robert, Boul, Peter, Mickelson, Edward T., Huffman, Chad
• Primary Examiner(s): Hendrickson, Stuart L.
• Application Number:
  US09/810,390
• Publication Number:
  US 20020004028A1
• Time in Patent Office: 1,397 Days
• Field of Search: 423/447.1, 423/460
• US Class Current: 423/447.1
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 35/58 Fabrics or filaments
• 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 2202/06 Multi-walled nanotubes
• CPC Class Codes: C01B 2202/08 Aligned nanotubes
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: C01B 32/174 Derivatisation; Solubilisation; Dispersion in solvents
• CPC Class Codes: D01F 11/121 Halogen, halogenic acids or their salts
• CPC Class Codes: Y10S 977/745 having a modified surface
• CPC Class Codes: Y10S 977/75 Single-walled
• CPC Class Codes: Y10S 977/835 Chemical or nuclear reactivity/stability of composition or compound forming nanomaterial
• CPC Class Codes: Y10S 977/843 Gas phase catalytic growth, i.e. chemical vapor deposition
• CPC Class Codes: Y10S 977/848 Tube end modifications, e.g. capping, joining, splicing
• CPC Class Codes: Y10T 428/139 Open-ended, self-supporting conduit, cylinder, or tube-type article
• CPC Class Codes: Y10T 428/2918 including free carbon or carbide or therewith [not as steel]

Abstract

This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.

Claims

1. A method for derivatizing a single wall carbon nanotube comprising the step of covalently bonding substituents to carbon atoms on a sidewall of the single wall carbon nanotube.

2. The method of claim 1, wherein the substituents are selected from the group consisting of alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, hydroxy, and OR′

, wherein R′

is selected from the group consisting of hydrogen, alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain, and a cyclic carbon chain.

3. The method of claim 2, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with at least one heteroatom.

4. The method of claim 2, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with one or more of the group consisting of ═

O, ═

S, hydroxy, an aminoalkyl, an amino acid, and a peptide of 2-8 amino acids.

5. The method of claim 1, wherein the substituents are selected from the group consisting of alkyls and phenyls.

6. The method of claim 1, further comprising the step of complexing a metal to at least one of the substituents.

7. The method of claim 6, wherein the metal is selected from the group consisting of Group VI B metals and Group VIII B metals.

8. The method of claim 1, wherein the amount of substituent bonded to carbon atoms of the single wall carbon nanotube is at a substituent to carbon ratio of from (a) one substituent to about 26 carbon atoms to (b) one substituent to about two carbon atoms.

9. The method of claim 8, wherein the amount of substituent bonded to the carbon atoms of the single wall carbon nanotube is at the substituent to carbon ratio of from (a) one substituent to about ten carbon atoms to (b) one substituent to about two carbon atoms.

10. The method of claim 9, wherein the amount of substituent bonded to the carbon atoms of the single wall carbon nanotube is at a substituent to carbon ratio of from (a) one substituent to about three carbon atoms to (b) one substituent to about two carbon atoms.

11. A method for derivatizing a sidewall of a single wall carbon nanotube comprising:

(i) fluorinating a single wall carbon nanotube; and

(ii) reacting the fluorinated single wall carbon nanotube with a compound containing a substituent to covalently bond the substituents to the single wall carbon nanotube.

12. The method of claim 11, wherein the substituents are selected from the group consisting of alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, hydroxy, and OR′

, wherein R′

is selected from the group consisting of hydrogen, alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain, and a cyclic carbon chain.

13. The method of claim 12, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with at least one heteroatom.

14. The method of claim 12, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with one or more of the group consisting of ═

O, ═

S, hydroxy, an aminoalkyl, an amino acid, and a peptide of 2-8 amino acids.

15. The method of claim 11, wherein the substituents selected from the group consisting of alkyls and phenyls.

16. The method of claim 11, further comprising the step of complexing a metal to at least one of the substituents.

17. The method of claim 16, wherein the metal is selected from the group consisting of Group VI B metals and Group VIII B metals.

18. The method of claim 11, wherein the amount of substituent bonded to carbon atoms of the single wall carbon nanotube is at a substituent to carbon ratio of from (a) one substituent to about 26 carbon atoms to (b) one substituent to about two carbon atoms.

19. The method of claim 18, wherein the amount of substituent bonded to the carbon atoms of the single wall carbon nanotube is at the substituent to carbon ratio of from (a) one substituent to about ten carbon atoms to (b) one substituent to about two carbon atoms.

20. The method of claim 19, wherein the amount of substituent bonded to the carbon atoms of the single wall carbon nanotube is at the substituent to carbon ratio of from (a) one substituent to about three carbon atoms to (b) one substituent to about two carbon atoms.

21. A method for preparing single wall carbon nanotubes having substituents attached to the sidewall of the nanotube comprising:

(i) reacting the single wall carbon nanotubes with a fluorinating agent;

(ii) reacting the fluorine derivatized single wall carbon nanotubes with a compound containing a substituent; and

(iii) recovering the single wall carbon nanotubes with substituents covalently bonded to carbon atoms of the sidewall of the single wall carbon nanotubes.

22. The method of claim 21, wherein the substituents are selected from the group consisting of alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, hydroxy, and OR′

, wherein R′

is selected from the group consisting of hydrogen, alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain, and a cyclic carbon chain.

23. The method of claim 22, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with at least one heteroatom.

25. The method of claim 21, wherein the fluorinating agent is selected from the group consisting of fluorine, XeF₂, XeF₄, CIF₃, BrF₃, TF₅, AgF₂, and MnF₃.

26. The method of claim 21, wherein the substituents are part of an organometallic compound before being covalently bonded to the sidewall of the single wall carbon nanotube.

27. The method of claim 21, wherein said organometallic compound is a compound of an alkali metal, said compound having from 1 to 20 carbon atoms and said compound being selected from the group consisting of a substituted alkyl compound of the alkali metal, an unsubstituted alkyl of the alkali metal, a substituted aryl compound of the alkali metal, and an unsubstituted aryl compound of the alkali metal.

28. The method of claim 27, wherein the alkali metal is sodium or lithium.

29. The method of claim 28, further comprising removing residual fluorine from the single wall carbon nanotube subsequent to bonding the substituent to the single wall carbon nanotube.

24. The method of 22, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with one or more of the group consisting of ═

O, ═

S, hydroxy, an aminoalkyl, an amino acid, and a peptide of 2-8 amino acids.

30. A method for preparing carbon nanotubes having substituents attached to the sidewall of the nanotube comprising:

i) reacting the carbon nanotubes with a fluorinating agent;

ii) recovering the fluorine derivatized carbon nanotubes;

iii) reacting the fluorine derivatized carbon nanotubes with a compound containing a substituent; and

iv) recovering the carbon nanotubes with substituents covalently bonded to carbon atoms of the sidewall of the carbon nanotubes.

31. The method of claim 30, wherein the substituents are selected from the group consisting of alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, hydroxy, and OR′

, wherein R′

is selected from the group consisting of hydrogen, alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain, and a cyclic carbon chain.

32. The method of claim 31, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with at least one heteroatom.

33. The method of claim 31, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with one or more of the group consisting of ═

O, ═

S, hydroxy, an aminoalkyl, an amino acid, and a peptide of 2-8 amino acids.

34. The method of claim 30, wherein the fluorinating agent is selected from the group consisting of fluorine, XeF₂, XeF₄, CIF₃, BrF₃, IF₅, AgF₂, and MnF₃.

35. The method of claim 30, wherein the substituents are part of an organometallic compound before being covalently bonded to the sidewall of the carbon nanotube.

36. The method of claim 30, wherein said organometallic compound is a compound of an alkali metal, said compound having from 1 to 20 carbon atoms and said compound being selected from the group consisting of a substituted alkyl compound of the alkali metal, an unsubstituted alkyl of the alkali metal, a substituted aryl compound of the alkali metal, and an unsubstituted aryl compound of the alkali metal.

37. The method of claim 36, wherein the alkali metal is sodium or lithium.

38. The method of claim 30, further comprising removing residual fluorine from the carbon nanotube subsequent to bonding the substituent to the carbon nanotube.

39. A method for derivatizing sidewalls of single wall carbon nanotubes comprising the steps of:

(i) reacting the single wall carbon nanotubes with a fluorinating agent;

(ii) solvating the single wall carbon nanotubes; and

(iii) reacting the single wall carbon nanotubes with a compound containing a substituent to covalently bond the substituents to the single wall carbon.

40. The method of claim 39, wherein the substituents are selected from the group consisting of alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, hydroxy, and OR′

, wherein R′

is selected from the group consisting of hydrogen, alkyl, acyl, aryl, aralkyl, halogen, substituted thiol, unsubstituted thiol, substituted amino, unsubstituted amino, a linear carbon chain, and a cyclic carbon chain.

41. The method of claim 40, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with at least one heteroatom.

42. The method of claim 40, wherein the linear carbon chain or the cyclic carbon chain or both is substituted with one or more of the group consisting of ═

O, ═

S, hydroxy, an aminoalkyl, an amino acid, and a peptide of 2-8 amino acids.

43. The method of claim 39, wherein the fluorinating agent is selected from the group consisting of fluorine, CIF₃, BrF₃, IF₅, XeF₂, XeF₄, AgF₂, and MnE₃.

44. The method of claim 39, wherein the solvation step comprises sonication.

45. The method of claim 39, wherein the solvation step comprises using a solvent selected from the group consisting of an alcohol, CHC1₃, and dimethylformamide.

46. The method of claim 45, wherein the alcohol is selected from the group consisting of methanol, ethanol, 2,2,2-trifluoroethanol, 2-propanol, 2-butanol, n-pentanol, n-hexanol, cyclohexanol and n-heptanol.

47. The method of claim 39, wherein the amount of substituent bonded to carbon atoms of the single wall carbon nanotubes is at a substituent to carbon ratio of from (a) one substituent to about 26 carbon atoms to (b) one substituent to about two carbon atoms.

48. The method of claim 47, wherein the amount of substituent bonded to the carbon atoms of the single wall carbon nanotubes is at the substituent to carbon ratio of from (a) one substituent to about ten carbon atoms to (b) one substituent to about two carbon atoms.

49. The method of claim 48, wherein the amount of substituent bonded to the carbon atoms of the single wall carbon nanotubes is at a substituent to carbon ratio of from (a) one substituent to about three carbon atoms to (b) one substituent to about two carbon atoms.