Ni-deposited multi-walled carbon nanotubes by electrodeposition

Multi-walled carbon nanotubes (MWNTs), having a diameter around 100-200 nm, were used as host material for electrodeposition of Ni using a Ni plating bath containing homogeneously dispersed MWNTs. Ni-deposited or coated MWNTs with a skewered dumpling shape accumulated on the Cu cathode electrode. A model representing the growth process of these electrodeposits, which possess such a skewered dumpling shape, is presented. These electrodeposits were separated easily from the cathode electrode by ultrasonic irradiation in an acetone bath to yield a Ni-deposited or coated MWNTs powder. The amount of Ni deposited on the MWNTs can be controlled by selecting the appropriate electroplating conditions.     

Fabrication of superhydrophobic surfaces with non-aligned alkyl-modified multi-wall carbon nanotubes

Films of superhydrophobic multi-wall carbon nanotubes (MWCNTs) have been obtained by using alkyl-modified MWCNTs (MWCNT(COOC₁₈H₃₇)_n) and a simple and effective preparation method. The films show both a high contact angle and a small sliding angle for water droplets. A particular characteristic is that on the superhydrophobic surface the alkyl-modified MWCNTs are not intentionally aligned, thus avoiding the preparation techniques using aligned carbon nanotubes to produce the same effect.     

Multi-walled carbon nanotubes on amorphous carbon films

Nanotubular structures composed of layered graphite sheets or other layered materials have been studied intensely by both scanning and transmission electron microscopy. In this paper, we will show how graphite structures, that are inherent to the production process of the amorphous carbon support films, used for both SEM and TEM studies can be easily mistaken for the actual sample structures. We will further report that these artifacts appear in both commercial as well as homemade holey carbon support films on copper grids, and suggest that to successfully study the “real” nanotubular structures only support films made from materials other than carbon should be used.     

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.     

Functionalization of single-walled carbon nanotubes by using alkyl-halides

In this paper we demonstrate the functionalization of single-walled carbon nanotubes prepared by chemical vapor deposition. The chosen functionalization agents were alkyl-halides such as trifluoromethane (TFM) and trichloromethane (TCM); or double bond containing alkyl-halides as tetrachloroethylene (TCE) and hexafluoropropene (HFP) that can easily form radicals. Functionalization of samples was carried out under mild conditions, by ball milling of nanotubes in an atmosphere of functionalization agent, at room temperature. For the sake of comparison, chlorination was also performed by chlorine gas. In this process the cleavage of nanotube C-C bonds results in active sites, which can activate molecules in gas phase or adsorbed on the surface of carbon nanotubes. Halogenated samples were characterized by means of particle induced γ-ray emission, transmission electron microscopy, thermogravimetry, and X-ray photoelectron spectroscopy. We concluded that this method gives functionalized single-walled carbon nanotubes in the range of 0.3-3.5 wt.% of fluorine and 5.5-17.5 wt.% of chlorine.     

Synthesis of carbon nanotubes on metallic substrates by a sequential combination of PECVD and thermal CVD

Carbon nanotubes were synthesized from acetylene and hydrogen gas mixture directly on stainless steel plates by sequential combination of rf PECVD and thermal CVD. PECVD was used for nucleation and initial growth of carbon nanotubes while thermal CVD was utilized for further growth of them. In this way decoupling of nucleation and growth of carbon nanotubes was realized, and growth of carbon nanotubes was enhanced compared to growth by PECVD. Synthesized carbon nanotubes were curly in shape, and proper pretreatment of the substrate surface was required for the satisfactory growth of carbon nanotubes. Carbon nanotubes could be fabricated into electrodes for electric double layer capacitors without any further treatment. With an electrolyte composed of lithium hexafluorophosphate, ethylene carbonate and diethyl carbonate, charge/discharge test showed specific capacitance in the range of 33-82 F/g.     

Prevention of Si-contaminated nanocone formation during plasma enhanced CVD growth of carbon nanotubes

We investigated the growth behavior and morphology of vertically aligned carbon nanotubes (CNTs) on silicon (Si) substrates by direct current (DC) plasma enhanced chemical vapor deposition (PECVD). We found that plasma etching and precipitation of the Si substrate material significantly modified the morphology and chemistry of the synthesized CNTs, often resulting in the formation of tapered-diameter nanocones containing Si. Either low bias voltage (∼500 V) or deposition of a protective layer (tungsten or titanium film with 10-200 nm thickness) on the Si surface suppressed the unwanted Si etching during growth and enabled us to obtain cylindrical CNTs with minimal Si-related defects. We also demonstrated that a gate electrode, surrounding a CNT in a traditional field emitter structure, could be utilized as a protection layer to allow growth of a CNT with desirable high aspect ratio by preventing the nanocone formation.     

Growing pillars of densely packed carbon nanotubes on Ni-coated silica

We report the growth of pillar-like cylindrical structures consisting of densely packed and vertically aligned multiwalled carbon nanotubes by exposing Ni-coated oxidized-Si (001) substrates to a xylene-ferrocene mixture. The nanotube pillars have a diameter between 10 and 100 μm, and lengths of several tens of micrometres. Formation of circular microcracks in the film allows ferrocene and xylene molecules to reach the underlying SiO₂ layer where pillars nucleate and grow out of the plane of the film surface. The nanotube pillars are attractive for applications such as energy storage, electrodes, and composite reinforcements.     

BETA zeolite nanowire synthesis under non-hydrothermal conditions using carbon nanotubes as template

The properties of carbon nanotubes, used as a nanometric template and as a reactor for the synthesis of BETA zeolite, have been investigated. The confinement effect of the carbon nanotubes, induced by the high aspect ratio of the tubes could be effectively used for the synthesis of one-dimensional nanowire zeolitic materials under non-hydrothermal macroscopic conditions. Zeolite material is easily recovered by combustion of the nanotubes. The average sizes of the zeolite particles are about 20 nm. The BETA zeolite was successfully used as a catalyst for benzoylation of anisol. The zeolite catalyst exhibits a high activity compared to a commercial BETA, essentially due to its high external surface area.     

Synthesis and characterisation of medium surface area silicon carbide nanotubes

Silicon carbide nanotubes with medium surface area (30-60 m²/g) were successfully prepared by reaction between carbon nanotubes and SiO vapor according to the shape memory synthesis (SMS). The gross morphology of the carbon nanotubes was maintained during the carburization process. A calcination in air at 600 °C was performed to remove unreacted carbon domains in order to obtain pure carbon-free SiC nanotubes. The synthesized SiC nanotubes had a mean outer diameter of 100 nm and lengths up to several tens of micrometres.     

Scrolls and nested tubes in multiwall carbon nanotubes

Recent high-resolution transmission electron microscopy (HREM) studies of multiwalled carbon nanotubes (MWCNTs) reveal a class of defects analogous to edge dislocations in a crystal. These defects are believed to mark the transition from scrolls on one side to nested tubes on the other. On the tube side, layer spacing becomes irregular. Analysis of the helicity of the tubes shows a strong correlation between diameter and helicity. This suggests that the organizing principle for the tubes is not Van der Waals forces, as in the case of graphite or turbostratic carbon, but preservation of helicity. Based on these observations and total energy calculations, the authors speculate that graphene monolayers initially form scrolls and subsequently transform into multiwall nanotubes through the progression of defects. Scrolls and nested tubes thus coexist within a single MWNT.     

Functionalization of carbon nanobeads and their use as metal ion adsorbents

Ethylenediamine, dithiocarbamate and thioureido ligand functionalized nanoparticles, with average diameters ranging from 4 to 8 nm and containing 1.06 to 1.26 mmol of ligand/g, are readily obtained when carbon nanobeads are modified with a silane coupling agent,and then functionalized with carbon disulfide and phenylisothiocyanate. Their sorption characteristics for transition metal cations have been studied. The nanometer metal ion adsorbents exhibit very high selectivities, capacities and rates of complexing. This study demonstrates that these nanoparticles have potential applications as catalyst supports.     

Thionine-mediated chemistry of carbon nanotubes

Thionine can be employed as a kind of useful functional molecule for the non-covalent functionalization of carbon nanotubes, as it shows a strong interaction with either SWNTs or MWNTs. Attachment of thionine molecules onto the sidewalls of carbon nanotubes would improve the solubility and lower the thermal stability of original carbon nanotubes. More importantly, it may functionalize the surface of carbon nanotubes with rich NH₂ groups and therefore open up more opportunities for the surface chemistry of carbon nanotubes. It has been proved that through the modification of small thionine molecules, other kinds of species such as cytochrome C and TiO₂ nanoparticles could be easily and selectively introduced onto the surface of carbon nanotubes. With this approach, SWNTs or MWNTs can be tailored with desired functional structures and properties.     

In-situ formation of carbon nanotubes in an alumina-nanotube composite by spray pyrolysis

Alumina (Al₂O₃)-carbon nanotube composite materials were synthesized by spraying a slurry of ferrocene (Fe(C₅H₅)₂) and alumina in xylene, at 1000±50 °C, using argon (≤1.5 bar) as carrier gas. The as-prepared materials were formed in large flakes (ca. 2 cm) and consist of nanotubes intricately matted in a glassy alumina matrix. Based on the structural and microstructural investigations done by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM), a possible growth mechanism has been suggested.     

Synthesis of carbon nanotubes over Fe catalyst on aluminium and suggested growth mechanism

Carbon nanotubes (CNTs) have been grown by the decomposition of C₂H₂ over a thin catalyst film in order to investigate the growth mechanism of CNTs by chemical vapour deposition (CVD). The catalyst was prepared from an iron nitrate precursor solution that was spin-coated on an aluminium substrate. The density (mg cm⁻²) and the length of the CNTs were greatly influenced by the precursor concentration, the time of deposition, the temperature and the ratio of C₂H₂:N₂. Scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction measurements have been carried out in order to investigate the behaviour of the catalyst before and during the growth process. The iron nitrate film formed an amorphous iron oxide layer that transformed to crystalline Fe₂O₃, which was reduced to Fe₃O₄ and FeO in contact with the C₂H₂: N₂ reaction atmosphere. The CNTs synthesis took place on small iron carbide (Fe₃C) particles that were formed from the FeO.