Oxygen functionalization of multiwall carbon nanotubes by Ar/H2O plasma treatment

To increase the applicability of multiwall carbon nanotubes (MWCNTs), oxygen-containing functional groups were introduced on the surfaces of MWCNTs by using microwave-excited Ar/H₂O surface-wave plasma. X-ray photoelectron spectroscopy and Raman spectroscopy were used to determine dependencies of Ar/H₂O gas partial pressure, treatment time and microwave power. The oxygen functionalization of MWCNTs by plasma can be achieved very rapidly, about 10 min. The C-O and O-C═O fractions firstly increase and then decrease with increasing Ar partial pressure. The C-O and O-C═O fractions increase with increasing microwave power from 400 W to 700 W. A slight increase of the R (I_D/I_G ratio) value for the treated MWCNTs indicated disordering in the surface microstructure of MWCNTs coincident with the introduction of surface oxygen. The oxygen-containing groups introduced on the surfaces of MWCNTs by plasma treatment are hydrophilic. The dispersion of plasma treated MWCNTs is therefore improved.     

Field emission properties of N2 and Ar plasma-treated multi-wall carbon nanotubes

We modify multi-wall carbon nanotubes (MWCNTs) by plasma treatment with N₂ and Ar for varying durations and measure their field emission characteristics. The N₂ treated MWCNTs showed significant improvement in field emission properties, while the Ar treated MWCNTs displayed poorer field emission characteristics compared to untreated MWCNTs. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Raman spectroscopy and work function measurements are used to investigate the field emission mechanisms after plasma treatments.     

Aligned carbon nanotubes by catalytic decomposition of C2H2 over Ni–Cr alloy

High density, well-aligned carbon nanotubes (CNTs) were prepared by thermally decomposing acetylene at 700 °C with the help of Ni–Cr alloy as catalyst in a thermal chemical vapor deposition system. The density and alignment of CNTs were characterized by scanning electron microscope (SEM). It was found that the density of the CNTs could be remarkably increased and the alignment could be improved with the decrease of the thickness ratio of Ni:Cr. Also found in our experiment was that the catalyst encapsulated in CNT was single crystal Ni, which was confirmed by high-resolution transmission electron microscopy (HRTEM) and electron dispersion X-ray spectrum (EDX). Finally, the growth mode of CNTs was discussed based on the Ni–Cr alloy catalysts under our experimental conditions. The results are helpful in providing a better understanding of the acting of catalyst and the controlling of the desirable density and alignment of CNTs for various applications.     

C60 encapsulation inside single-walled carbon nanotubes using alkali-fullerene plasma method

It is reported that alkali-fullerene plasmas consisting of positive alkali-metal ions, negative fullerene ions, and residual electrons are effective in encapsulating fullerenes inside single-walled carbon nanotubes (SWNTs). When positive or negative bias-voltages are applied to SWNTs in plasmas, accelerated negative fullerene or positive alkali-metal ions are irradiated to the SWNTs through the plasma sheath, respectively. Field emission gun transmission electron microscopy (FEG-TEM) clearly shows that drastic structural modifications such as severe bending of SWNT bundles, tube dislocation, and tube tip termination take place after the ion irradiation. Energy dispersive X-ray spectrometry (EDS) confirms the existence of the alkali-metal elements in the sample after the alkali-metal irradiation. In addition to this, the SWNTs encapsulating fullerene molecules are directly observed after only 1 h fullerene-ion irradiation. These results suggest that our experimental system could permit us to intercalate not only fullerenes but also other elements inside the SWNTs by the applied-bias control. Raman scattering spectroscopy is also adopted for the purpose of evaluating pure SWNTs and fullerene encapsulated SWNTs.     

A comparison of O2 and CO2 oxidation of glassy carbon surfaces

We have studied the reactive adsorption of O₂ on the edge surface of graphite. At 300°C the efficiency of oxygen uptake showed a strong coverage-dependent reactive adsorption coefficient. In general, the efficiencies were low (< 10⁻⁹) over the majority of the coverage range. In contrast, the uptake of oxygen from O₂ and H₂O on sputter-damaged graphite was far more rapid. Sputter-damaged carbon surfaces exhibit greatly enhanced reactivity and are poor models of edge carbon activity. Thermal stability studies on the resultant oxidized edge graphite surfaces provide information about the energetics of product formation in gasification reactions. CO was the dominant product. A fraction of the oxygen on the surface is very tightly bound with energies greater than 85 kcal/mole. The energy decreases to 70 kcal/mole over a wide coverage range. At the highest attainable coverages representing a small fractional population, the energy decreases further down to 58 kcal/mole. Our results show that increasing the amount of oxygen surface coverage decreases the energy barrier for gaseous CO formation but increases the barrier for O₂ dissociation.     

Removal of SO2 by activated carbon fibers in the presence of O2 and H2O

This work describes the potential capability of activated carbon fibers (ACFs) in continuously removing SO₂ from inert atmosphere without requiring further regeneration. A tubular reactor packed with ACF was used to study the conversion of SO₂ into H₂SO₄ in the presence of O₂ and H₂O with varying concentrations of SO₂ (3000-10,000 ppm), O₂ (10-20%), and H₂O (10-70%) and temperatures (313-348 K). The experiments were carried out on two precursors (viscose rayon and phenolic resin) based ACFs. The breakthrough data revealed that the steady-state SO₂ concentration levels at the reactor exit increased with increasing inlet SO₂ concentration and decreased with increasing concentration levels of O₂ as well as H₂O. Increase in the reaction temperature was found to moderately enhance the steady-state exit concentration levels of SO₂. The viscose rayon-based ACF exhibited higher SO₂ removal activity in comparison to the phenolic resin-based ACF. A mathematical model was developed to predict the gas concentration profiles in the reactor, incorporating the mass transfer in the bed as well as within the ACF pores, along with the surface reactions on the ACF. The model predictions agreed reasonably well with the data.     

Carbon nanotubes and onions from carbon monoxide using Ni(acac)2 and Cu(acac)2 as catalyst precursors

New catalyst precursors (copper and nickel acetylacetonates) have been used successfully for the synthesis of carbon nanotubes and onion particles from carbon monoxide. Catalyst nanoparticles and carbon products were produced by metal-organic precursor vapour decomposition and catalytic disproportionation of carbon monoxide in a laminar flow reactor at temperatures between 705 and 1216 °C. Carbon nanotubes (CNTs) were formed in the presence of nickel particles at 923-1216 °C. The CNTs were single-walled, 1-3 nm in diameter and up to 90 nm long. Hollow carbon onion particles (COPs) were produced in the presence of copper particles at 1216 °C. The COPs were from 5 to 30 nm in diameter and consisted of several concentric carbon layers surrounding a hollow core. The results of computational fluid dynamics calculations to determine the temperature and velocity profiles and mixing conditions of the species in the reactor are presented. The mechanisms for the formation of both CNTs and COPs are discussed on the basis of the experimental and computational results.     

Growth of conformal single-walled carbon nanotube films from Mo/Fe/Al2O3 deposited by electron beam evaporation

We discuss growth of high-quality carbon nanotube (CNT) films on bare and microstructured silicon substrates by atmospheric pressure thermal chemical vapor deposition (CVD), from a Mo/Fe/Al₂O₃ catalyst film deposited by entirely electron beam evaporation. High-density films having a tangled morphology and a Raman G/D ratio of at least 20 are grown over a temperature range of 750-900 °C. H₂ is necessary for CNT growth from this catalyst in a CH₄ environment, and at 875 °C the highest yield is obtained from a mixture of 10%/90% H₂/CH₄. We demonstrate for the first time that physical deposition of the catalyst film enables growth of uniform and conformal CNT films on a variety of silicon microstructures, including vertical sidewalls fabricated by reactive ion etching and angled surfaces fabricated by anisotropic wet etching. Our results confirm that adding Mo to Fe promotes high-yield SWNT growth in H₂/CH₄; however, Mo/Fe/Al₂O₃ gives poor-quality multi-walled CNTs (MWNTs) in H₂/C₂H₄. An exceptional yield of vertically-aligned MWNTs grows from only Fe/Al₂O₃ in H₂/C₂H₄. These results emphasize the synergy between the catalyst and gas activity in determining the morphology, yield, and quality of CNTs grown by CVD, and enable direct growth of CNT films in micromachined systems for a variety of applications.     

A modified composite film electrode of polyoxometalate/carbon nanotubes and its electrocatalytic reduction

Keggin-type polyoxometalate (H₄SiMo₁₂O₄₀) and carbon nanotubes (CNTs) coated by poly(allylamine hydrochloride) (PAH) were alternately deposited on glassy carbon (GC) electrodes by an electrochemical growth method in acidic aqueous solution. The preparation of the film electrode was simple and convenient. Thus-prepared multilayer films and the electrochemical behavior of the composite film modified electrode were characterized by UV–vis spectroscopy and cyclic voltammetry. It was shown that the multilayer films are uniform and stable. The resulting multilayer film modified electrode behaves as an electrochemical sensor because of its low overpotential for the catalytic reduction of S₂O₈ ²⁻ and NO₂ ⁻ in acidic aqueous solution.     

Modification of vertically aligned carbon nanotubes with RuO2 for a solid-state pH sensor

In this work, a novel type electrode based on RuO₂ nanoparticles-modified vertically aligned carbon nanotubes (RuO₂/MWCNTs) was prepared by magnetron sputtering deposition. This RuO₂/MWCNTs electrode not only shows a high capacity nature, but also possesses a good response to the pH value. The pH sensor based on the RuO₂/MWCNTs nanocomposite electrode exhibits some advantages over the conventional pH sensors. It shows good reproducibility, long-term storage stability (over 1 month) and linear response in the whole pH range (2-12) of Britton-Robinson (B-R) buffer solutions with near-Nernstian response (about −55 mV/pH). The hysteretic widths of the nanocomposite electrode are 6.4 mV, 5.1 mV and 10.2 mV in pH 7-4-7-10-7, pH 7-10-7-4-7 and pH 2-8-12-8-2 loop cycles, respectively. Moreover, the RuO₂/MWCNTs electrode displays an excellent anti-interference property and fast response time (less than 40 s). According to the electrochemical impedance measurements, the pH sensing properties of the RuO₂/MWCNTs electrode were also discussed.     

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.     

Growing carbon nanotubes on patterned submicron-size SiO2 spheres

Growing carbon nanotubes (CNTs) perpendicularly to the surface of submicron-size SiO₂ spheres by pyrolyzing iron(II) phthalocyanine (FePc) is reported for the first time in this paper. The large curvature isolates the nanotubes and forms unique structures. The density, lengths and morphology of CNTs on SiO₂ spheres can be controlled by varying the experimental conditions. A method of growing CNTs on patterned SiO₂ spheres on conducting surface by photolithography is further developed based on the selective growth of CNTs. This may offer an effective way to control the density of patterned, aligned CNTs on conducting substrates for various applications, particularly for field emission.     

Microstructural and electrochemical characterization of RuO2/CNT composites synthesized in supercritical diethyl amine

A simple and efficient route to decorate carbon nanotubes (CNTs) with nanocrystalline RuO₂ has been developed. In this method, RuCl₃ · 3H₂O was oxidized into RuO₂ by oxygen in supercritical diethyl amine, and the produced RuO₂ deposited on CNTs, resulting in RuO₂/CNT nanocomposites. The as-prepared composites were structurally and morphologically characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy (TEM). TEM images showed that RuO₂ nanoparticles attached on CNTs had uniform shape and a narrow particle size distribution. The loading content and the size of RuO₂ particles on CNTs could be tuned by changing the mass ratio of RuCl₃ · 3H₂O/CNT. Electrochemical measurements by cyclic voltammetry demonstrated a substantial increment of the specific capacitance of CNTs due to a pseudocapacitance originated from the deposited RuO₂ nanoparticles.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.     

Pt-WO3 supported on carbon nanotubes as possible anodes for direct methanol fuel cells

The carbon nanotube (CNT) synthesised by the template carbonisation of polypyrrole on alumina membrane has been used as the support for Pt-WO₃, Pt-Ru, and Pt. These materials have been used as the electrodes for methanol oxidation in acid medium in comparison with E-TEK 20 wt% Pt and Pt-Ru on Vulcan XC72R carbon. The higher electrochemical surface of the carbon nanotube (as evaluated by cyclic voltammetry) has been effectively used to disperse the catalytic particles. The morphology of the supported and unsupported CNT has been characterised by scanning electron micrograph and high-resolution transmission electron micrograph. The particle size of Pt, Pt-Ru, and Pt-WO₃ loaded CNT was found to be 1.2, 2, and 5 nm, respectively. The X-ray photoelectron spectra indicated that Pt and Ru are in the metallic state and W is in the +VI oxidation state. The electrochemical activity of the methanol oxidation electrode has been evaluated using cyclic voltammetry. The activity and stability (evaluated from chronoamperometric response) of the electrodes for methanol oxidation follows the order: GC/CNT-Pt-WO₃-Nafion>GC/E-TEK 20% Pt-Ru/Vulcan Carbon-Nafion>GC/CNT-Pt-Nafion>GC/E-TEK 20% Pt/Vulcan carbon-Nafion>Bulk Pt. The amount of nitrogen in the CNT plays an important role as observed by the increase in activity and stability of methanol oxidation with N₂ content, probably due to the hydrophilic nature of the CNT.