Methods of synthesizing three-dimensional heteroatom-doped carbon nanotube macro materials and compositions thereof
Methods for synthesizing macroscale 3D heteroatom-doped carbon nanotube materials (such as boron doped carbon nanotube materials) and compositions thereof. Macroscopic quantities of three-dimensionally networked heteroatom-doped carbon nanotube materials are directly grown using an aerosol-assisted chemical vapor deposition method. The porous heteroatom-doped carbon nanotube material is created by doping of heteroatoms (such as boron) in the nanotube lattice during growth, which influences the creation of elbow joints and branching of nanotubes leading to the three dimensional super-structure. The super-hydrophobic heteroatom-doped carbon nanotube sponge is strongly oleophilic and an soak up large quantities of organic solvents and oil. The trapped oil can be burnt off and the heteroatom-doped carbon nanotube material can be used repeatedly as an oil removal scaffold. Optionally, the heteroatom-doped carbon nanotubes in the heteroatom-doped carbon nanotube materials can be welded to form one or more macroscale 3D carbon nanotubes.
1. A method for making solid three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes directly during chemical vapor deposition synthesis of carbon nanotubes, comprising reacting a hydrocarbon, a boron source, and a metal catalyst source into a chemical vapor deposition reactor, wherein the ratio of the metal atoms to the boron atoms is between 2 and 20,
wherein the solid three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes form a macroscale three-dimensional material of entangled carbon nanotube networks.
2. The method of claim 1 , wherein the ratio of the metal atoms to the boron atoms present is between 4 and 6.
3. The method of claim 1 , wherein the carbon source comprises toluene or hexane.
4. The method of claim 1 , wherein the metal catalyst source comprises ferrocene.
5. The method of claim 1 , wherein the boron source comprises triethylborane.
6. The method of claim 1 , wherein the hydrocarbon, the boron source, and the metal catalyst source are combined to form a chemical precursor within the reactor.
7. The method of claim 6 , wherein the hydrocarbon is between about 87 wt % and about 97 wt % of the hydrocarbon, the metal catalyst source, and the boron source.
8. The method of claim 6 , wherein the metal catalyst source is between about 2.5 wt % and about 12 wt % of the hydrocarbon, the metal catalyst source, and the boron source.
9. The method of claim 6 , wherein the boron source is between about 0.1 wt % and about 2 wt % of the hydrocarbon, the metal catalyst source, and the boron source.
10. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes form a macroscale three-dimensional structure of nanotubes wherein the macrostructure is at least 1 cm in two perpendicular directions.
11. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes form a macroscale three-dimensional structure of nanotubes wherein the macrostructure is at least 1 cm in three orthogonal directions.
12. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes are porous materials having a bulk density less than 10 mg/cm 3 .
13. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes are porous materials having a bulk density between 10 mg/cm 3 and 29 mg/cm 3 .
14. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes are comprised of an isotropic ensemble of entangled individual carbon nanotubes comprising elbow defects or covalent junction sites.
15. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes are comprised of an isotropic ensemble of entangled individual carbon nanotubes which does not comprise elbow defects or covalent junction sites.
16. The method of claim 1 , wherein the boron source is selected from the group consisting of organoboranes, organoborates, and combinations thereof.
17. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes exhibit elastic mechanical behavior.
18. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes exhibit magnetic properties with a high coercive field of about 400 Oersted.
19. The method of claim 1 , wherein the three-dimensional carbon nanotube structures comprising boron-containing carbon nanotubes are porous solids.
20. The method of claim 1 , further comprising welding the boron-containing carbon nanotubes of the three-dimensional macroscale carbon nanotube structures.
21. The method of claim 1 , wherein the boron source is the boron containing gas source, boron trichloride.