Synthesis of well-aligned carbon nanotubes with open tips

Large amounts of well-aligned carbon nanotubes (CNTs) with open tips have been produced by pyrolysis of iron(II) phthalocyanine. The aligned CNTs have an average length about 10 μm and diameters ranging from 92 to 229 nm. Some of produced CNTs showed Y-junction structure due to the self-joint growth of two neighboring CNTs. The well-aligned CNTs indicated a bamboo-shaped multiwalled structure and fairly good crystallinity. The aligned CNTs follow tip growth mechanism.     

Synthesis of narrow-diameter carbon nanotubes from acetylene decomposition over an iron-nickel catalyst supported on alumina

Carbon nanotubes (CNTs) were synthesized by the catalytic decomposition of acetylene over 40Fe:60Al₂O₃, 40Ni:60Al₂O₃ and 20Fe:20Ni:60Al₂O₃ catalysts. High density CNTs of 20 nm diameter were grown over the 20Fe:20Ni:60Al₂O₃ catalyst, whereas low growth density CNTs of 40 and 50 nm diameter were found over 40Fe:60Al₂O₃ and 40Ni:60Al₂O₃ catalysts. Smaller catalyst particles enabled the synthesis of highly dense, long and narrow-diameter CNTs. It was found that a homogeneous dispersion of the catalyst was an essential factor in achieving high growth density. The carbon yield and the quality of CNTs increased with increasing temperature. For the 20Fe:20Ni:60Al₂O₃ catalyst, the carbon yield reached 121% after 90 min at 700 °C. The CNTs were grown according to the tip growth mode. Based on reports regarding hydrocarbon adsorption and decomposition over different faces of Ni and Fe, the growth mechanism of CNTs over the 20Fe:20Ni:60Al₂O₃ catalyst are discussed.     

Synthesis of carbon nanotubes on pulse plated Ni nanocrystalline substrate in ethanol flames

A novel process for synthesizing carbon nanotubes (CNTs) in ethanol flames is described. The CNTs grow on a nanocrystalline Ni layer which was electro-deposited on a Ni substrate using periodic reverse (PR) pulse plating. The grain size of the plating and CNT morphology were revealed using XRD, SEM, TEM and Raman spectroscopy. It was found that the quality of the plating and the corresponding CNTs were related to two plating parameters: output pulse frequency (f) and duty cycle (r). The growth mechanism of CNTs in this process is discussed.     

Diameter control of carbon nanotubes by changing the concentration of catalytic metal ion solutions

We have developed a simple new method to control the diameter of carbon nanotubes (CNTs) using catalytic nanoparticle arrays fabricated by filling the pores of well-ordered porous anodic aluminum oxide (AAO) templates with a metal ion solution. Fe ion solution was used to fill the pores in which Co had been deposited electrochemically, and then the template was dried naturally on a magnet. After this process, the pores were widened in NaOH solution. Well-graphitized multi-walled CNTs were grown from almost all the pores and were very long in length and homogeneous in diameter. We were able to control the diameter of CNTs, simply, by changing the concentration of iron ion solution. For example, the average outer diameters of the CNTs are 7 ± 1.5, 13 ± 1, and 17 ± 1 nm when the concentrations of Fe ion in their mother solutions were 1.0 × 10⁻³, 3.0 × 10⁻³, and 6.0 × 10⁻³ M, respectively. The inner diameters of these CNTs corresponded to the calculated diameters of Fe nanoparticles by assuming that all Fe ions contained in each pore are reduced to a single nanoparticle. This means that homogeneous nanoparticles are made in each pore. Our new method could be used to fabricate homogeneous nanoparticles from most metal ion solutions.     

Synthesis of carbon nanocapsules containing Fe, Ni or Co by arc discharge in aqueous solution

A simple, inexpensive and one-step synthesis method of metal-containing carbon nanocapsules using an arc discharge in aqueous solution is reported. It was found that Ni, Co and Fe nanoparticles could be in situ encapsulated in carbon shells when the arc was performed respectively in aqueous solutions of NiSO₄, CoSO₄ and FeSO₄. Transmission electron microscopy, energy dispersive X-ray spectroscopy and electron diffraction patterns of selected areas were used to determine the crystalline phase of the metal cores. To explain the formation mechanism of metal-containing carbon nanocapsules, a model of discharge in solution is proposed. This result presents a simply controllable way to synthesize metal-containing carbon nanocapsules.     

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.     

Synthesis of vertically aligned carbon nanotubes on metal deposited quartz plates

Without plasma aid, we have successfully synthesized vertically aligned carbon nanotubes (CNTs) on iron-, cobalt- or nickel-deposited quartz plates by chemical vapor deposition with ethylenediamine as a precursor. The amine serves as both etching reagent for the formation of metal nanoparticles and carbon source for the growth of aligned carbon nanotubes. The carbon nanotubes were vertically aligned in high density on a large area of the plain silica substrates. The density and diameter of CNTs is determined by the thickness of the deposited metal film and the length of the tubes can be controlled by varying the reaction time. High-resolution transmission electron microscopy analysis reveals that the synthesized CNTs are multiwalled with a bamboo-like structure. Energy dispersive X-ray spectra demonstrate that the CNTs are formed as tip growths. Raman spectrum provides definite evidence that the prepared CNTs are multiwalled graphitic structure.     

Synthesis and structural characterization of thin multi-walled carbon nanotubes with a partially facetted cross section by a floating reactant method

Here we describe synthesis of very unusual multi-walled carbon nanotubes through a catalytic chemical vapor deposition method using a floating reactant method and subsequent thermal treatment up to 2600 °C in a large quantity. Main characteristics of these nanotubes are (1) relatively wide distribution of diameters ranging from 20 to 70 nm and linear, long macro-morphology (aspect ratio >100), (2) highly straight and crystalline layers, (3) high purity through removal of metallic impurity, (4) very low interlayer spacing (0.3385 nm) and low R value (I_D/I_G = 0.0717), (5) high G′ intensity over intensity of G band (G′/G = 0.85) and strongly negative magnetoresistance value of −1.08% at 77 K and 1 T. The unusual microstructure of thin multi-walled carbon nanotubes with a partially facetted cross-sectional shape caused by thermal treatment is mainly ascribed to abrupt density changes (from 1.89 to 2.1 g/cm³) within a confined nanosized space, accompanying with the phase separation.     

TEM image simulation study of small carbon nanotubes and carbon nanowire

Recent findings of extremely small diameter carbon nanotube and nanowire in the core of a multi-walled carbon nanotube (MWCNT) have attracted interests from broad range of researchers. Direct observation of carbon nanotube is usually done using a transmission electron microscope (TEM). When nanotubes become smaller, it becomes harder to correctly understand the TEM images, not only because of the weak scattering, but also due to the artifact that starts to appear because of the interference effect and the inappropriate defocus condition.In this study, we have shown that the artifact such as ghost fringes due to inappropriate defocus conditions of the TEM appear in the core of an MWCNT, and can be misinterpreted as either carbon nanowire or small carbon nanotube. It is also shown that, in the TEM image, it is hard to distinguish a single-walled nanotube bundle from a double-walled carbon nanotube bundle. Finally, we propose that the cross-sectional observation is necessary for the correct characterization of single- and double-walled carbon nanotube bundles.     

Pulsed laser deposition-assisted patterning of aligned carbon nanotubes modified by focused laser beam for efficient field emission

Patterned carbon nanotube (CNT) arrays have been synthesized on patterned substrates created via pulsed laser deposition (PLD) of the precursor catalyst films with a mask. Arrays of CNTs in square and hexagonal patterns with tube lengths of 8 μm and 16 μm were created on silicon or quartz substrates, respectively. Using the method of laser cutting, as-grown CNT patterns were pruned by focused He-Ne laser beam. It is found that after pruning, CNTs tend to cluster together and form welded junctions. The comparison of field emission properties of CNTs before and after pruning shows that laser modification of CNT morphologies effectively enhanced the emission currents.     

Iron particles in carbon nanotubes

Nanometer-size iron-rich particles in carbon nanotubes have been studied by transmission electron microscopy with and without in situ and ex situ heating. Several remarkable results were found; a high temperature phase (γ-Fe) of iron stable at low temperatures and preferential presence of iron and iron carbide in carbon nanotubes. Based upon these experimental results, thermodynamics of the Fe-C phase diagram and its kinetics were used to explain the non-uniform distribution of iron and iron carbide, which also yielded a deeper insight into the formation of carbon nanotubes. Some of the results also allowed describing the role of the graphitic structure in retaining the high temperature phase (γ-Fe) of iron at low temperatures. Furthermore, methods have been demonstrated with which γ-Fe can be produced in carbon nanotubes intentionally or in a large quantity. Selected area electron diffraction patterns of iron inside nanotubes demonstrated the crystallographic relationship of the iron to the nanotube axis along with phase changes of the iron. This paper summarizes the findings and draws further conclusions on the particle shape inside multiwalled carbon nanotubes.