IP Library › Granted Patent US 7,670,510
Granted Patent B2
US 7,670,510 · App. 11/484,960 · Granted Mar 2, 2010

Carbon nanotube adducts and methods of making the same

Assignee: The Research Foundation of State University of New York
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Quick Facts
Patent No.
US 7,670,510
App. No.
11/484,960
Granted
Mar 2, 2010
Kind
B2
Abstract

The invention provides an adduct comprising a carbon nanotube and a transitional metal coordination complex, wherein the metal of the complex is attached by a covalent linkage to at least one oxygen moiety on the nanotube.

Claims (40)

1. An adduct comprising a carbon nanotube and a transitional metal coordination complex, wherein the metal of the complex is attached by a covalent linkage to at least one oxygen moiety on the nanotube, and wherein the transitional metal coordination complex is selected from the group consisting of Wilkinson's complex, [Ag(NH 3 ) 2 ] + , [Cu(NH 3 ) 4 ] 2+ , [Fe(CN) 6 ] 4− , [Fe(CN) 6 ] 3− , [Co(NH 3 ) 6 ] 3+ , [Pt(NH 3 ) 2 Cl 2 ], [Cr(ethylenediamine) 3 ] 3+ , [Pt(NH 3 ) 4 ] 2+ , Fe(C 5 H 5 ) 2 , Ni(C 5 H 5 ) 2 , [PdCl 4 ] 2− , Cr(CO) 6 , [Ni(NH 3 ) 6 ] 2+ , [CoF 6 ] 3− , [Pt(ethylenediamine) 2 Cl 2 ]Br 2 , [Co(NH 3 ) 4 (SCN)Br]Cl, [Fe(H 2 O) 6 ] 3+ , [CeCl 6 ] 2− , [La(acetylacetone) 3 (H 2 O) 2 ], [Nd(H 2 O) 9 ] 3+ , [Er(NCS) 6 ], [Lu(2,6-dimethylphenyl) 4 ] − and [Ho(tropolonate) 4 ] − .

2. An adduct as in claim 1 wherein said covalent linkage is a coordinative linkage.

3. An adduct as in claim 1 wherein said at least one oxygen moiety is selected from the group consisting of a carboxyl group, a hydroxyl group, an aldehyde group and a ketone group.

4. An adduct as in claim 1 wherein said transitional metal is in the form of a nitrate, a halide, or a salt.

5. An adduct as in claim 1 wherein said adduct comprises different types of transitional metal coordination complexes.

6. An adduct as in claim 1 wherein said adduct has high degree of solubility in organic or aqueous solvents.

7. An adduct as in claim 6 wherein said organic solvent is selected from the group consisting of dimethylsulfoxide (DMSO), tetrahydrofuran (THF) or dimethylformamide (DMF), methanol, ethanol, 2-propanol, acetone, o-dichlorobenzene (ODCB), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate, benzene and dimethylformamide (DMF).

8. An adduct as in claim 1 wherein the transitional metal coordination complex is a Wilkinson's complex.

9. An adduct as in claim 8 wherein said adduct is a hexacoordinate structure.

10. An adduct as in claim 8 wherein the rhodium of said Wilkinson's complex has an oxidation state of three.

11. An adduct as in claim 8 wherein said adduct has a solubility of greater than 250 mg/L in DMSO.

12. An adduct as in claim 8 wherein said adduct has a solubility of greater than 75 mg/L in THF or DMF.

13. An adduct as in claim 1 wherein said carbon nanotube is a semi-conductor.

14. An adduct as in claim 1 wherein said carbon nanotube is a metal.

15. An adduct as in claim 1 wherein said carbon nanotube is single-walled.

16. An adduct as in claim 15 wherein the diameter of said single-walled carbon nanotube is about 0.7 to about 1.5 nm.

17. An adduct as in claim 1 wherein said carbon nanotube is multi-walled.

18. An adduct as in claim 17 wherein the diameter of said multi-walled carbon nanotube is about 3 to about 30 nm.

19. An adduct as in claim 1 wherein at least one end of the carbon nanotube is open.

20. A method of producing a plurality of carbon nanotubes with increased solubility, the method comprising:

adding a solution comprising a transitional metal coordination complex to a carbon nanotube dispersion to form a resultant dispersion comprising carbon nanotube-metal adducts, wherein a plurality of carbon nanotubes with increased solubility is formed, wherein said transitional metal coordination complex is selected from the group consisting of Wilkinson's complex, [Ag(NH 3 ) 2 ] + , [Cu(NH 3 ) 4 ] 2+ , [Fe(CN) 6 ] 4− , [Fe(CN) 6 ] 3− , [Co(NH 3 ) 6 ] 3+ , [Pt(NH 3 ) 2 Cl 2 ], [Cr(ethylenediamine) 3 ] 3+ , [Pt(NH 3 ) 4 ] 2+ , Fe(C 5 H 5 ) 2 , Ni(C 5 H 5 ) 2 , [PdCI 4 ] 2− , Cr(CO) 6 , [Ni(NH 3 ) 6 ] 2+ , [CoF 6 ] 3− , [Pt(ethylenediamine) 2 Cl 2 ]Br 2 , [Co(NH 3 ) 4 (SCN)Br]Cl, [Fe(H 2 O) 6 ] 3+ , [CeCl 6 ] 2− , [La(acetylacetone) 3 (H 2 O) 2 ], [Nd(H 2 O) 9 ] 3+ , [Er(NCS) 6 ], [Lu(2,6-dimethylphenyl) 4 ] − , and [Ho(tropolonate) 4 ] + .

21. A method as in claim 20 wherein 50-99 wt % of said carbon nanotube-metal adduct dispersion comprises nanotubes.

22. A method as in claim 20 wherein a transitional metal is in the form of a nitrate, a halide, or a salt.

23. A method as in claim 20 wherein the solution comprises a mixture of different transitional metal coordination complexes.

24. A method as in claim 20 wherein the nanotube dispersion comprises nanotubes in DMSO, THF or DMF.

25. A method as in claim 20 further comprising precipitating the adduct from the solution.

26. A method of exfoliating a plurality of carbon nanotube bundles, comprising:

contacting a carbon nanotube dispersion comprising a plurality of nanotube bundles wherein the bundles have an average first diameter with a solution comprising transitional metal coordination complexes, thereby exfoliating the bundles, wherein the exfoliated bundles have an average second diameter, wherein said transitional metal coordination complex is selected from the group consisting of Wilkinson's complex, [Ag(NH 3 ) 2 ] + , [Cu(NH 3 ) 4 ] 2+ , [Fe(CN) 6 ] 4− , [Fe(CN) 6 ] 3− , [Co(NH 3 ) 6 ] 3+ , [Pt(NH 3 ) 2 Cl 2 ], [Cr(ethylenediamine) 3 ] 3+ , [Pt(NH 3 ) 4 ] 2+ , Fe(C 5 H 5 ) 2 , Ni(C 5 H 5 ) 2 , [PdCI 4 ] 2− , Cr(CO) 6 , [Ni(NH 3 ) 6 ] 2+ , [CoF 6 ] 3− , [Pt(ethylenediamine) 2 Cl 2 ]Br 2 , [Co(NH 3 ) 4 (SCN)Br]Cl, [Fe(H 2 O) 6 ] 3+ , [CeCl 6 ] 2− , [La(acetylacetone) 3 (H 2 O) 2 ], [Nd(H 2 O) 9 ] 3+ , [Er(NCS) 6 ], [Lu(2,6-dimethylphenyl) 4 ] − , and [Ho(tropolonate) 4 ] + .

27. A method as in claim 26 wherein said average second diameter is about 10-80% of said average first diameter.

28. A method as in claim 26 wherein said exfoliated bundles are about 15-20 nm in diameter.

29. method as in claim 26 wherein said bundles are exfoliated to a single nanotube.

30. A method of providing single carbon nanotubes and carbon nanotube bundles with a selected diameter, comprising:

contacting a carbon nanotube dispersion with a solution comprising a transitional metal coordination complex, wherein adducts are formed between single nanotubes and said transitional metal complex, and between carbon nanotube bundles of a selected diameter and said transitional metal complex, wherein the selected diameter is less than about 10 nanometers; and

precipitating the adducts from the solution, wherein carbon nanotubes with a selected diameter are provided, wherein said transitional metal coordination complex is selected from the group consisting of Wilkinson's complex, [Ag(NH 3 ) 2 ] + , [Cu(NH 3 ) 4 ] 2+ , [Fe(CN) 6 ] 4− , [Fe(CN) 6 ] 3− , [Co(NH 3 ) 6 ] 3+ , [Pt(NH 3 ) 2 Cl 2 ], [Cr(ethylenediamine) 3 ] 3+ , [Pt(NH 3 ) 4 ] 2+ , Fe(C 5 H 5 ) 2 , Ni(C 5 H 5 ) 2 , [PdCI 4 ] 2− , Cr(CO) 6 , [Ni(NH 3 ) 6 ] 2+ , [CoF 6 ] 3− , [Pt(ethylenediamine) 2 Cl 2 ]Br 2 , [Co(NH 3 ) 4 (SCN)Br]Cl, [Fe(H 2 O) 6 ] 3+ , [CeCl 6 ] 2− , [La(acetylacetone) 3 (H 2 O) 2 ], [Nd(H 2 O) 9 ] 3+ , [Er(NCS) 6 ], [Lu(2,6-dimethylphenyl) 4 ] − , and [Ho(tropolonate) 4 ] + .

31. A method of modifying a physical property of a nanotube wherein the method comprises:

contacting a carbon nanotube with a solution of a transitional metal coordination complex to form a carbon nanotube-transitional metal coordination complex adduct, wherein a physical property of the carbon nanotube is modified, wherein said transitional metal coordination complex is selected from the group consisting of Wilkinson's complex, [Ag(NH 3 ) 2 ] + , [Cu(NH 3 ) 4 ] 2+ , [Fe(CN) 6 ] 4− , [Fe(CN) 6 ] 3− , [Co(NH 3 ) 6 ] 3+ , [Pt(NH 3 ) 2 Cl 2 ], [Cr(ethylenediamine) 3 ] 3+ , [Pt(NH 3 ) 4 ] 2+ , Fe(C 5 H 5 ) 2 , Ni(C 5 H 5 ) 2 , [PdCI 4 ] 2− , Cr(CO) 6 , [Ni(NH 3 ) 6 ] 2+ , [CoF 6 ] 3− , [Pt(ethylenediamine) 2 Cl 2 ]Br 2 , [Co(NH 3 ) 4 (SCN)Br]Cl, [Fe(H 2 O) 6 ] 3+ , [CeCl 6 ] 2− , [La(acetylacetone) 3 (H 2 O) 2 ], [Nd(H 2 O) 9 ] 3+ , [Er(NCS) 6 ], [Lu(2,6-dimethylphenyl) 4 ] − , and [Ho(tropolonate) 4 ] + .

32. A method according to claim 31 wherein the physical property is selected from the group consisting of an electronic property, an electrical property, an electromechanical property, an optical property, a chemical property, a mechanical property, a structural property, a thermal property and a thermoelectric property.

33. A method according to claim 32 wherein the electrical property is selected from the group consisting of conductance, resistivity, carrier mobility, a transport property, permittivity, and a charge transfer property.

34. A method according to claim 33 wherein the modification of conductance is a tunability in conductance.

35. A method according to claim 32 wherein the structural property is selected from the group consisting of elasticity and ease of composite formation.

Continuity (2)
Division 1061549200 · Jul 7, 2003
Related Publication 20100004468A1 · Jan 7, 2010