Magnetic separation of Fe catalyst from single-walled carbon nanotubes in an aqueous surfactant solution

We report an efficient technique to separate ferromagnetic catalyst particles from an aqueous surfactant solution of single-walled carbon nanotubes (SWNTs) by the use of a 1.3 T permanent magnet. High resolution transmission electron microscopy (HRTEM) demonstrates that SWNTs are coated with a surfactant layer that stabilises the aqueous dispersions of SWNTs. The residual quantities of Fe catalyst (∼3%) can be effectively removed from a colloid solution of SWNTs in a magnetic field while absorbance spectra of the initial and purified solutions show that the nanotube diameter distribution remains unchanged.     

Nitrogen-doped carbon nanotubes synthesized with carbon nanotubes as catalyst

Nitrogen-doped carbon (CN_x) nanotubes were synthesized with carbon nanotubes (CNTs) as catalyst by detonation-assisted chemical vapor deposition. CN_x nanotubes exhibited compartmentalized bamboo-like structure. Electron energy loss spectroscopy and elemental mapping studies indicated that the synthesized tubes contained high concentration of nitrogen (ca. 17.3 at.%), inhomogeneously distributed with an enrichment of nitrogen within the compartments. X-ray photoelectron spectroscopy analysis revealed the presence of pyridine-like N and graphitic N incorporated into the graphitic network. The catalytic activity of CNTs for CN_x nanotube growth was ascribed to the nanocurvature and opening edges of CNT tips, which adsorbed C_n/CN species and assembled them into CN_x nanotubes.     

CVD synthesis of coal-gas-derived carbon nanotubes and nanocapsules containing magnetic iron carbide and oxide

Iron carbide-oxide filled carbon nanotubes and nanocapsules (CNCs) are separately synthesized by catalytic chemical vapor deposition of coal gas at 950 °C with ferrocene as catalyst. The products are examined using transmission electron microscopy and XRD techniques, showing that nanosized iron carbide-oxide particles are encapsulated by well ordered carbon layers. Magnetic moment measurement reveals that these carbon encapsulated iron carbide-oxides exhibit large magnetic coercivity at room temperature. It has been found that the filled CNCs are corrosion-proof and stable in hydrochloric acid. The effect and interaction between different gaseous components in the coal-gas during the formation of magnetic iron carbide-oxide filled carbon nanostructures are discussed.     

Persistent currents in finite zigzag carbon nanotubes

Magnetic properties of finite zigzag carbon nanotubes are studied within the tight-binding model. The spin-B interaction (Zeeman splitting) causes the metal-semiconductor transition and thus produces a large persistent current (J) with special jump structures. This effect makes all zigzag carbon nanotubes exhibit a gigantic paramagnetism. It also destroys the periodicity of magnetic properties. The dependence on the magnetic flux, the length (w), the radius (r), the temperature (T), and the chirality (zigzag or armchair) is strong. The amplitude of J quickly decreases with increasing of (w, r, T). Zigzag carbon nanotubes differ significantly from armchair carbon nanotubes (or infinite zigzag carbon nanotubes) in features such as magnetic susceptibility and in special structures in J.     

Facile and efficient synthesis of magnetic fluorescent nanocomposites based on carbon nanotubes

Multifunctional nanomaterials composed of magnetic and fluorescent nanoparticles have been one of the most extensive pursuits because of the potential application in bio-research. In this paper, we demonstrated an efficient method by coupling CdSe/CdS/ZnS quantum dots (QDs) with Fe₃O₄ magnetic nanoparticles(MNPs) while functionalized multiwall carbon nanotubes (f-MWCNTs) were used as matrix to synthesize a kind of magnetic fluorescent nanocomposite. Compared with other matrix materials, carbon nanotubes have the advantages of high surface areas and good biocompatibility. The incorporation of f-MWCNTs supplies plenty of nucleation sites for the preferential growth of Fe₃O₄ nanoparticles, avoiding the agglomeration phenomenon of Fe₃O₄ MNPs in traditional co-precipitation method. Moreover, the un-reacted functional groups of f-MCNTs can further adsorb biological species and drugs, averting the decline of fluorescent intensity caused by the modification of biological species and drugs. The synthetic product maintains the unique properties of rapid magnetic response and efficient fluorescence, which shows a broad application prospect in fluorescent labeling, biological imaging, cell tracking and drug delivery.     

Iron filled carbon nanotubes grown on substrates with thin metal layers and their magnetic properties

The thermal decomposition of ferrocene combined with a catalyst-assisted structuring of a Si-substrate surface is a favourable way to produce Fe-filled carbon nanotubes in good quality and in high yields. In this work we have studied the growth of such aligned filled nanotubes on iron and cobalt pre-coated Si-substrates and their dependence on the deposition time. The nanotube diameter depends on the used catalyst metal on the substrate surface. Magnetization measurements were carried out perpendicular (along tube axis) and parallel to the substrate and show excellent coercivities, a strong uniaxial anisotropy (ratios of H_c,per/H_c,par up to 6) and high saturation magnetization moments per substrate square. The magnetic behavior has been also interpreted as a function of deposition time and of the catalyst metal on the substrate. These investigations were complemented by X-ray diffraction, which revealed a majority fraction of α-Fe and a small amount of Fe₃C.     

Decoration of carbon nanotubes with chitosan

In this letter, a non-destroyable surface decoration of carbon nanotubes with biopolymer chitsoan via a controlled surface-deposition and crosslinking process is described. The method utilizes the emulsifying capacity of chitosan, the completely different water-solubility of chitosan in acidic and basic solutions, and the crosslinking reaction among chitosan polymers. As the pristine structures of the carbon nanotubes are not recomposed under those treatments, the unique properties of the pristine carbon nanotubes have not been compromised. Combining the properties of carbon nanotubes and the versatility and biocompatibility of chitosan, these chitosan surface-decorated carbon nanotubes could find potential applications in biosensing, gene and drug delivering as well as other chemical and biological applications.     

Synthesis of carbon nanotubes on carbon fibers by means of two-step thermochemical vapor deposition

The present study aimed at development of a method for synthesizing multi-walled carbon nanotubes (CNTs) on carbon paper substrates (CP) at densities as high as those so far reported for CNTs formed on quartz substrates. Applying conditions optimized for CNTs synthesis on quartz substrates, in which CP was heated at 1073 K, being placed parallel to the flow of m-xylene/ferrocene vapor, resulted in formation of extremely few deposits on CP. Forced vapor flow through the CP greatly improved the frequency and homogeneity of deposition of the Fe-bearing nanoparticles, but these became encapsulated by carbon and deactivated. The addition of H₂S to the vapor further enhanced nanoparticle deposition. Moreover, it enabled the subsequent formation of CNTs at densities as high as 2-6 × 10⁹ cm⁻². In order to realize such high population densities, it was found essential to perform CVD in a two-stage sequence commencing with nanoparticles deposition at 1073 K followed by the formation and growth of CNTs at 1273 K, with the H₂S concentration in the vapor phase optimized throughout within a range of 0.014-0.034 vol%.     

Induction plasma synthesis of fullerenes and nanotubes using carbon black–nickel particles

The existence of fullerenes (as allotropes of carbon) was established in the mid-1980s and during the last 15–18 years, systematic efforts have been devoted to improve the methods of their synthesis, including plasma-based system methods. The work presented here is focused on the investigation of fullerenes synthesis, using a radio frequency plasma reactor. The main objectives were to explore the use of induction plasma technology for the synthesis in-continuo of carbon fullerenes and to predict their formation conditions through conduct of theoretical studies. Thus, a thermodynamic study was carried out to predict the equilibrium composition of fullerenes produced at several combinations of operating conditions. Additionally, a statistical factorial design experiment, employing four factors at two levels, was also developed, in order to study the influence of the system’s operating parameters on the eventual C₆₀ fullerene yield. The results obtained showed that the reactor pressure, the electrical power and the raw material feed rates all have an important effect on the synthesis of fullerenes. The highest C₆₀ concentration in the products was found to be about 7.7 wt.%. Various other carbon nanostructures, such as nanotubes and nano-onions, were also successfully produced.     

Solutal Bénard-Marangoni instability as a growth mechanism for single-walled carbon nanotubes

In the past few years, considerable progress has been achieved in understanding the growth mechanism of single-walled carbon nanotubes (C-SWNTs). Nevertheless, the nucleation of C-SWNTs still remains partially unexplained by these models. A study of the critical synthesis parameters in the plasma torch process and a review of existing growth mechanisms lead us to propose a new growth mechanism for bundles of C-SWNTs, based on the Bénard-Marangoni instability. It is shown that the conditions occurring at the surface of the catalyst nanoparticle (NP) during the growth of the C-SWNTs give rise to the solutal BMI, which in turn results in a pattern of hexagonal convection cells in the liquid layer on the surface of the NP. The vortex ring flow pattern within these cells is then responsible for the structured growth of the C-SWNT bundles. This model highlights the important parameters required to optimize the synthesis of C-SWNTs.     

Growth and characterization of filled carbon nanotubes with ferromagnetic properties

Strong vertically aligned Fe-filled multiwalled nanotubes have been synthesised by decomposition of ferrocene in a liquid source CVD process. By varying the reaction parameter such as deposition time, reaction temperature and precursor concentration we determined the influences on the length, diameter and filling yield of the carbon nanotubes. The length and the diameter of the nanotubes are only controlled by the ferrocene concentration in the gas phase and there is no influence on the deposition time. The filling yield achieved about 45 wt.%. Using alternating gradient magnetometry measurements really high coercivities, high magnetization moments and strong magnetic anisotropies with an easy magnetic axis parallel to the aligned nanotubes are observed. In addition, this LSCVD is highly suited for the high scale production of filled multiwalled carbon nanotubes with selected properties.     

Aligning vapor-grown carbon fibers in polydimethylsiloxane using dc electric or magnetic field

A trace amount of vapor-grown carbon fibers (VGCFs), which, as received, had an aggregated lump form, was completely dispersed in polydimethylsiloxane, a nonpolar viscous liquid, at room temperature by mechanical stirring. Using this uniformly dispersed sample as a starting material, a dc electric or magnetic field was applied to induce the formation of an aligned structure. In situ transmission optical microscopy was carried out to observe the structural development of VGCFs in polydimethylsiloxane under the dc electric or magnetic field, which was applied both parallel and perpendicular to the observation direction. Upon application of a dc electric field, an aligned ramified network structure of VGCFs developed between the electrodes. In the formation of the network structure, ends of VGCFs became connected to ends of other VGCFs, which was followed by rotation and orientation of the VCGFs. On the other hand, upon application of a magnetic field, the VGCFs were only rotated, without the formation of a network. The electric resistivity of the network structure was evaluated. Additionally, the influence of the viscosity of the polydimethylsiloxane matrix on the structural formation process was examined.     

Third-order optical nonlinearity in single-wall carbon nanotubes

The third-order optical nonlinearity in carbon nanotubes (CNT) exposed to an intensive external electromagnetic field has been investigated. The analysis is based on the quantum kinetic equations for the density matrix of π-electrons in CNT. In the regime of weak driving field, the kinetic equations have been solved by the perturbation method and the third-order nonlinear polarizability of different achiral CNTs has been calculated. The theory elaborated has been used for the evaluation of nonlinear susceptibility of CNT-based composites. Comparison with available experimental data has been presented. In the case of high intensive driving field a nonperturbative numerical simulation of the process has been carried out in the time domain. The axial current density in CNT has been calculated. Excitation of π-plasmons in CNTs has been analyzed.     

Synthesis of carbon nanotubes over gold nanoparticle supported catalysts

The synthesis of carbon nanotubes (CNTs) through the catalytic decomposition of acetylene was carried out over gold nanoparticles supported on SiO₂-Al₂O₃. Monodispersed gold nanoparticles with 1.3-1.8 nm in diameter were prepared by the liquid-phase reduction method with dodecanethiol as protective agent. The carbon products formed after acetylene decomposition consist of multi-walled carbon nanotubes with layered graphene sheets, carbon nanofilaments (CNFs), and carbon nanoparticles encapsulating gold particles. The observed CNTs have outer diameters of 13-25 nm under 850 °C. The influence of several reaction parameters, such as kind of carriers, reaction temperature, gas flow rate, was investigated to search for optimum reaction conditions. The CNTs were observed at a relatively low temperature (550 °C). The silica-alumina carrier showed higher activity for the formation of CNTs than others used in the screening test. With increasing temperature, the CNTs showed cured structures having thick diameters and inside compartments. When Au content on the support was over 5 wt.%, the gold nanoparticles coagulated to form large ones >20 nm in diameter and became encapsulated with graphene layers after decomposition of acetylene.     

Electro-catalytic oxidation of CO on Pt catalyst supported on carbon nanotubes pretreated with oxidative acids

Characteristics of nanosized Pt electro-catalyst deposited on carbon nanotubes (CNTs) were studied with CO-stripping voltammogram and chronoamperometry measurements. The CNTs were pretreated by oxidation in HNO₃, mixed HNO₃ + H₂SO₄ and H₂SO₄ + K₂Cr₂O₇ solution, respectively, to enable surface modification. Well-homogenized Pt particles (average size: ≈3 nm) were loaded onto the pretreated CNT samples by a modified colloidal method. TEM, BET, FTIR and XRD techniques were used to characterize the physicochemical properties of the pretreated CNT samples. In the electro-oxidation of CO, all the Pt/CNT samples showed lower on-set as well as peak potentials than the conventional Pt/XC-72 electro-catalyst, indicating that the Pt/CNT samples were more resistant to CO poisoning and could be superior anode electro-catalyst for the proton exchange membrane fuel cells (PEMFCs). Moreover, we found that the pretreatment of CNTs in mixed HNO₃ + H₂SO₄ solution was very beneficial for the performance enhancement of Pt/CNT electro-catalyst; the catalyst obtained as such gave the lowest peak potential and the highest catalytic activity for the electro-oxidation of CO. Larger amount of oxygen-containing functional groups, higher percentage of mesopores, and higher graphitic crystallinity of the pretreated CNTs were considered crucial for the performance enhancement, e.g., by strengthening the interaction between Pt nanoparticles and the CNT support and enhancing the mass diffusion in the electro-chemical reaction.     

Semi-continuous production of multiwalled carbon nanotubes using magnetic field assisted arc furnace

A high-temperature arc furnace with an applied external magnetic field has been used to grow carbon nanotubes. The magnetic field was able to spread and stabilize the plasma enabling the use of larger electrodes than could be used successfully with no magnetic field. By having a stable plasma across the entire anode surface, larger amounts of carbon black were able to be transformed into carbon nanotubes. In addition, a multiple-pronged anode was designed. The use of the pronged anode created a semi-continuous process which allowed for the amount of nanotubes produced per run to increase.