Ionic peapods from carbon nanotubes and phosphotungstic acid

Using a mild wet-chemical route, cage-like phosphotungstic acid (HPW) molecules of 1.2 nm diameter were successfully filled into opened carbon nanotubes (CNTs) with cavity diameter of 2 nm. High resolution transmission electron microscope revealed that HPW molecules arrayed in a chain in the tube cavity, forming a new kind of peapod structure. In aqueous solution these unusual peapods showed higher ionic property than the opened nanotubes, with a ζ-potential of −47.5 ± 1.3 mV, and dissolved finely as a stable solution. Raman spectra confirmed the strong interaction between HPW molecules and CNT graphite wall. It could substantially tune the electronic properties of CNTs and thus promote their applications in novel electronic devices.     

Solvothermal preparation of amorphous carbon nanotubes and Fe/C coaxial nanocables from sulfur, ferrocene, and benzene

Amorphous carbon nanotubes and Fe/C coaxial nanocables were synthesized by a solvothermal treatment of ferrocene and sulfur. In this process, the amount of sulfur played an important role in the formation of products. When the molar ratio of ferrocene to sulfur was 1:1, the products were amorphous carbon nanotubes and Fe/C coaxial nanocables. And as the ratio was decreased to 1:2, amorphous carbon nanotubes were the main products.     

Easy synthesis of carbon nanotubes with polypyrrole nanotubes as the carbon precursor

An easy synthesis route for carbon nanotubes with polypyrrole nanotubes as a carbon precursor has been developed. Polypyrrole nanotubes were fabricated via a reactive self-degraded template method. Carbon nanotubes were further obtained by pyrolysis of the polypyrrole nanotube at 900 °C under a nitrogen atmosphere. The resultant carbon nanotube structure was found to be amorphous carbon on the basis of XRD, Raman spectra and high-resolution transmission electron microscopy (HRTEM) studies.     

Etching effects of ethanol on multi-walled carbon nanotubes

The morphology and microstructure of multi-walled carbon nanotubes (MWCNTs) were modified using ethanol as a mild gas reactant. The etching by OH radicals and deposition of C radicals on the carbon nanotubes were considered to be responsible for the modification of the MWCNT structures and the formation of new carbon nanostructures. The effects of etching and deposition on the MWCNTs were confirmed by using methanol as another gas reactant; this molecule has a higher ratio of hydroxyl radicals to carbon atoms than ethanol. In addition, water vapor, containing no carbon atoms in the molecule, was also applied to etch the MWCNTs as a weak oxidant which resulted in stronger etching effects on the MWCNTs than methanol and ethanol.     

Carbon nanotubes with 2D and 3D multiple junctions

Multiple junction CNTs and 3D junction CNTs were obtained using a thermal chemical vapor deposition method without using a template substrate. The silicon substrates used were simply scratched using various types of abrasives prior to the growth of carbon nanotube. The hydrocarbon gas used was methane, which was balanced by hydrogen. A total of four catalyst precursors, Fe powders, Ni powders, FeS powders, and ferrocene, were used. It was found that only the use of ferrocene gave the formation of multiple junction CNTs. These multiple junction CNTs are found and suspended exclusively in the scratched striations. The mechanism of (multiple) junction CNT formation is discussed by addressing the role of the substrate and the catalyst.     

Structure modification of single-wall carbon nanotubes

Various purification processes were applied to single-wall carbon nanotubes synthesized by metal catalyzed laser ablation. Structure modifications introduced by these processes were investigated by high-resolution transmission electron microscopy and Raman spectroscopy. An apparent structure modification after purification was the increase of bundle size although breaking of nanotubes and a change of nanotube diameter distribution were also observed. More vigorous attacking of single-wall carbon nanotube structure was identified by a strong mixed-acid treatment.     

Diameter control of multiwalled carbon nanotubes using experimental strategies

Multiwalled carbon nanotubes (MWNTs) were synthesized using a chemical vapor deposition floating feed method in a vertical reactor. Effects of the preparation variables on the average diameter of carbon nanotubes were systematically examined using the fractional factorial design (FFD), path of the steepest ascent, and central composite design (CCD) coupled with the response surface methodology. From the FFD study, the main and interactive effects of reaction temperature, methane flow rate, and chamber pressure were concluded to be the key factors influencing the diameter of MWNTs. Two empirical models, representing the dependence of the diameter of carbon nanotubes at the vicinities around maximum (420 nm) and minimum (15 nm) on the reaction temperature and methane flow rate, were constructed in two independent CCD studies. These models, shown as contour diagrams, indicated that the diameter of carbon nanotubes generally increased with increasing reaction temperature and methane flow rate. Based on both models, the diameter of MWNTs from 15 to 420 nm can be controlled precisely by using a continuous CVD fabrication method.     

In-situ studies of electron field emission of single carbon nanotubes inside the TEM

Electron field emission characteristics of individual multi-walled carbon nanotubes (MWCNTs) were investigated in situ inside the transmission electron microscope (TEM). For a single MWCNT it was found that while field-emission can hardly occur from the side of the nanotube, a curved nanotube may result in finite side emission and the best emission geometry is the top emission geometry. Current-voltage (I-V) measurements made at different vacuum conditions and voltage sweeps emphasize the importance of the adsorbates on the electron field emission of MWCNTs. For a contaminated MWCNT, although the field emission current was reduced, the stability of its emission was improved. A current of up to several tens of μA was observed for a single MWCNT, but it was found that long time emission usually results in drastic structure damage that may lead to sudden emission failure.     

Liquid crystal engineering of carbon nanofibers and nanotubes

Four high-aspect-ratio carbon nanomaterials were fabricated by template-directed liquid crystal assembly and covalent capture. By selecting from two different liquid crystal precursors (thermotropic AR mesophase, and lyotropic indanthrone disulfonate) and two different nanochannel template wall materials (alumina and pyrolytic carbon) both the shape of the nanocarbon and the graphene layer arrangement can be systematically engineered. The combination of AR mesophase and alumina channel walls gives platelet-symmetry nanofibers, whose basic crystal symmetry is maintained and perfected upon heat treatment at 2500 °C. In contrast, AR infiltration into carbon-lined nanochannels produces unique C/C-composite nanofibers whose graphene planes lie parallel to the fiber axis. The transverse section of these composite nanofibers shows a planar polar structure with line defects, whose existence had been previously predicted from liquid crystal theory. Use of solvated AR fractions or indanthrone disulfonate produces platelet-symmetry tubes, which are either cellular or fully hollow depending on solution concentration. The use of barium salt solutions to force precipitation of indanthrone disulfonate within the nanochannels yields continuous nanoribbons rather than tubes. Overall the results demonstrate that liquid crystal synthesis routes provide molecular control over graphene layer alignment in nanocarbons with a power and flexibility that rivals the much better known catalytic routes.     

A novel hybrid of carbon nanotubes/iron nanoparticles: iron-filled nodule-containing carbon nanotubes

A straightforward, one-step method for the preparation of novel carbon nanotube/iron nanoparticle hybrids with some degree of shape control is reported herein. These carbon nanostructures differ from those reported previously: the nanoparticles were not attached to or coated onto the surface of carbon nanotubes but embedded inside the carbon wall. They were synthesized in good yield by thermolysis of ferrocene and thiophene mixtures in a closed steel vessel. The shapes and compositions of these nanostructures can be simply controlled by adjusting the reaction temperature and relative amounts of the precursors. Iron-filled T-junction carbon nanotubes were also obtained easily by this procedure. These iron-filled nodule-containing carbon nanotubes (INCNTs) are either empty or filled with iron or iron carbide (Fe(C)) nanowires. The outer diameters of these nanotubes range from 70 to 150 nm and the lengths reach up to several micrometers. The average size of the Fe(C) nanoparticles (or empty cores) inside the nodules is about 50 nm in diameter. The carbon in the INCNTs is amorphous. Sulfur was found being responsible for the disordered structure and playing a unique role in promoting the growth of INCNTs as well as the formation of T- or Y-junctions.     

Luminescent short thiol-functionalized multi-wall carbon nanotubes

Luminescent short thiol-functionalized multi-wall carbon nanotubes (mean length 100-200 nm) were produced by the reaction between 2-aminoethanethiol molecules and oxidized carbon nanotubes with the aid of a coupling agent in ethanol. After the reactions stop the carbon nanotubes suspension was purified and filtered to separate the shorter carbon nanotubes. The short length carbon nanotubes fraction exhibits an intense luminescence visible to the naked eye. The maximum of the luminescence band and its intensity strongly depends on the excitation wavelength. The sample chemistry and morphology were characterized by means of X-ray photoelectron spectroscopy and scanning electron microscopy.     

Highly dispersed multi-walled carbon nanotubes in ethanol using potassium doping

We demonstrated the production of an effective dispersion of multi-walled carbon nanotubes (MWCNTs) in ethanol using potassium doping (π-stacking interaction). The homogeneous dispersion of individual MWCNTs was achieved without any contamination or severe disruption at the end caps or periphery of the tubes. Potassium as a doping material, phenanthrene as a nonpolar molecule, and 1,2-dimethoxyethane as a dipole solvent were used for our experiment. From UV-visible spectroscopy and visual observation, it was found that the dispersibility of the MWCNTs in ethanol was about 14 mg/dm³. High resolution transmission electron microscopy and Raman spectroscopy showed that disruption of the end caps of the tubes and severance along the tube axis were rarely found. The scanning electron microscopy and corresponding EDX results indicated that the key to the dispersion mechanism was the potassium doping, which is driven by π-stacking complex formation. We suggest that the dispersion of the MWCNTs was influenced by the potassium doping, which caused the enlargement and separation of the entangled-MWCNT networks, and was not affected by defects or modification of the surface morphology.     

Mechanical and morphological characterization of polymer-carbon nanocomposites from functionalized carbon nanotubes

Carbon nanotubes were functionalized with poly(vinyl alcohol) (PVA). The water-soluble PVA-functionalized carbon nanotubes were then embedded into PVA matrix via a wet-casting method, resulting in polymer-carbon nanocomposite films with homogeneous nanotube dispersion. Composites with pristine and functionalized nanotubes were tested in tension. It was found that the mechanical properties of these nanocomposite films were significantly improved compared to the neat polymer film. Functionalization allowed good distribution of the nanotubes in the matrix, leading to higher film strength. Scanning electron microscopy shows an apparent good wetting of the nanotubes by the PVA matrix. These results are supportive of good interfacial bonding between the functionalized carbon nanotubes and the hosting polymer matrix.     

Encapsulating C59N azafullerene derivatives inside single-wall carbon nanotubes

Filling of single-wall carbon nanotubes with C₅₉N azafullerene derivatives is reported from toluene solvent at ambient temperature. The filling is characterized by high-resolution transmission electron microscopy and Raman spectroscopy. The filling efficiency is the same as for C₆₀ fullerenes and the tube-azafullerene interaction is similar to the tube-C₆₀ interaction. Vacuum annealing of the encapsulated azafullerene results in the growth of inner tubes, however no spectroscopic signature of nitrogen built in the inner walls is detected.     

Pore structures of multi-walled carbon nanotubes activated by air, CO2 and KOH

Multi-walled carbon nanotubes (MWNTs) synthesized by the catalytic decomposition of benzene were activated by KOH, CO₂ or air. The adsorption isotherms of the activated MWNTs were analyzed and their pore size distributions were obtained. The results showed that the specific surface areas of the MWNTs activated by KOH, CO₂ and air were increased to 785 m²/g, 429 m²/g and 270 m²/g, respectively. The MWNTs activated by KOH were rich in micropores and mesopores, especially high mesopores having volumes up to 1.04 cm³/g. The CO₂-activated MWNTs also had many micropores while the air-activated MWNTs had a much smaller micropore volume. The morphologies of the activated MWNTs were examined by transmission electron microscopy and high resolution transmission electron microscopy, and the activation mechanisms were discussed.