Effect of adding W to Fe catalyst on the synthesis of SWCNTs by arc discharge

Combining iron (Fe) and tungsten (W) as a bimetallic catalyst, we synthesized high-yield single-wall carbon nanotubes (SWCNTs) of narrow diameter distribution by a hydrogen–argon arc discharge method. Raman spectra indicate that the diameters of SWCNTs prepared using the Fe–W catalysts are about 0.5 nm smaller than those using Fe catalyst alone. The transmission electron microscopy and X-ray diffraction studies show that the SWCNTs prepared by the bimetallic catalyst coexist with few graphite flakes and other amorphous carbon. At the W content of 2–4 at%, tungsten cannot be found in the SWCNT samples. Thus by using a simple two-step purification process, high-purity SWCNT samples can be obtained. We have demonstrated the growth mechanism for the high melting metal (such as W, Mo)–Fe catalyst synthesis of SWCNTs by the arc discharge method.     

A parametric study of the synthesis and purification of single-walled carbon nanotubes using the high-pressure carbon monoxide process

Single-walled carbon nanotubes (SWCNTs) were synthesized using the high-pressure carbon monoxide disproportionation process. The SWCNT diameter, diameter distribution and yield can be varied depending on the process parameters. Important parameters are the temperature, the pressure, the CO gas flow rate and the nozzle injection velocity and geometry for the injection of reactant gas into the reaction zone. Carbon nanotubes as small as 1.0 nm in diameter have been produced. The purity and yield of the deposited material were increased with increasing CO gas flow by means of rapid heating of the gas mixture and using an optimum injection profile. Highly pure SWCNTs were produced at 1250 K, pressures between 5 and 10 bar and gas in the turbulent flow regime in the cold line of 2000–2500 sccm CO. The raw materials were purified by oxidation in high vacuum at 523 K in wet Ar/20 vol. % O₂ to remove SWCNT carbon-like impurities and to oxidize the iron catalyst nanoparticles. The iron oxides were removed by chemical treatment in concentrated HCl/C₂H₅OH mixture solution. The SWCNTs were analyzed by scanning electron microscopy, high-resolution transmission electron microscopy, atomic absorption spectroscopy and optical absorption spectroscopy to determine the purity, the diameter and diameter distribution, the chemical composition and the catalyst morphology, as well as the optical properties of deposited SWCNTs in dependence on the synthesis parameters. PACS 29.30.-h     

Pulsed KrF-laser synthesis of single-wall-carbon-nanotubes: effects of catalyst content and furnace temperature on their nanostructure and photoluminescence properties

In this article, we report on the use of a pulsed KrF-laser (248 nm, 20 ns) for the synthesis of single wall carbon nanotubes (SWCNTs) from the ablation of a graphite target loaded with Co/Ni catalyst, under various growth conditions. By varying the Co/Ni catalyst load of the graphite target, from 0 to 2.4 at.%, the laser synthesized SWCNTs, under a furnace temperature (T _f) of 1,100 °C, were found to be decorated by C₆₀ buckyballs, of which the density decreases as the catalyst content is increased. The effect of the catalyst content of the laser-ablated graphite target on the produced carbon nanostructures (C₆₀ vs. SWCNTs) was systematically investigated by means of various characterization techniques, including Raman spectroscopy, thermogravimetry, and SEM/HR-TEM microscopies. A [Co/Ni] ≥ 1.2 at.% was identified as the optimal concentration for the production of SWCNTs without any detectable presence of C₆₀ buckyballs. Thus, under the optimal growth conditions (i.e., [Co/Ni] = 1.2 at.% and T _f = 1,100 °C), the produced SWCNTs were found to be characterized by a very narrow diameter distribution (centered on 1.2 nm) with lengths in excess of 10 μm. By increasing T _f from 900 to 1,150 °C, the diameter of the SWCNTs can be varied from ~0.9 to ~1.3 nm. This nanotube diameter variation was evidenced by Raman and UV–Vis absorption measurements, and its effect on the photoluminescence of the SWCNTs is presented and discussed.     

Effects of composition of catalysts on the preparation of single-walled carbon nanotubes synthesized over W–Co–MgO catalysts

A series of W–Co–MgO catalysts were prepared for the first time by decomposing a mixture of magnesium nitrate, ammonium paratungstate, citric acid, and cobalt nitrate. Single-walled carbon nanotubes (SWCNTs) were synthesized over these W–Co–MgO catalysts and the effects of the quantity of metal in the catalysts on the synthesis of SWCNTs were investigated by Raman spectroscopy and transmission electron microscopy (TEM). The results show that, among W–Co–MgO catalysts, the W1–Co5 catalyst was found to be most effective for synthesizing SWCNTs. The diameter distribution of as-grown SWCNTs prepared over the W1–Co5 catalyst was estimated to range from 0.72–1.64 nm. When the molar ratios of W:MgO and Co:MgO in the catalysts are more than 2:100 and 5:100, respectively, the amorphous carbon content or defect concentration of SWCNTs may be increased with the increase of the quantity of metal in the catalysts. The dependence of the diameter distribution of SWCNTs on the quantity of W in the catalysts is small. However, the proportion of SWCNTs with larger diameter is increased as the quantity of Co in the catalysts is increased owing to the increase in the number of larger active sites.     

Role of thermal treatment on the structural behavior of the arc SWCNTs in the purification system process

The role of thermal oxidation before acid treatment and post high-temperature vacuum annealing of single walled carbon nanotube (SWCNTs) was studied by scanning electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analyses and Raman spectroscopy. An efficient procedure is developed for the purification of SWCNTs with minimal damage to the walls and minimal modification in the length of the tubes. SWCNTs are employed in this study, are synthesized by arc-discharge method containing impurity of amorphous carbon, carbon shells, graphitic particles, metallic nanoparticles and metallic nanoparticles encapsulated inside the amorphous carbon or graphite.     

Purification and fractionation of single-walled carbon nanotubes

This study presents the approach to the purification and subsequent metallic/semiconductive (M/S) fractionation of single-walled carbon nanotubes (SWCNTs) with diameter from 1.04 to 1.60 nm produced via laser ablation. SWCNTs were purified through 3-fold refluxing processes in nitric acid followed by the multiple washings with sodium hydroxide and hydrochloric acid. The purified-annealed SWCNTs sample was divided into seven batches. One batch was dispersed in acetone as a reference sample. Each of the remaining batches were dispersed in one of the following surface agents: sodium dodecyl sulfate, sodium cholate acid (SCA), sodium deoxycholate, cetrimonium bromide, cetylpyridinium chloride, and benzalkonium chloride (BKC). SWCNT suspensions were fractionated via free solution electrophoresis technique. The recovered fractions from electrode and control areas were analyzed via optical absorption spectroscopy in UV–Vis–NIR range to evaluate the efficiency of the separation process. Raman spectroscopy was applied to analyze the purity of the samples. The catalyst content was estimated by atomic absorption spectroscopy. The morphology of the investigated samples was observed via high-resolution transmission electron microscopy. This contribution clearly shows that among the investigated surfactants there are two promising candidates (SCA and BKC) which can efficiently enrich the bulk sample in one electronic type of carbon nanotubes when FSE is applied.     

Non-covalent interaction of benzonitrile with single-walled carbon nanotubes

We have studied the interaction of benzonitrile with as-prepared and purified single-walled carbon nanotubes (SWCNTs). As-prepared SWCNTs, when suspended in benzonitrile, lead to a red colored dispersion which contains fragments composed mostly of amorphous carbon and carbon-coated catalyst, thus suggesting that benzonitrile is a solvent that can be used as one step of the purification process. Optical spectroscopic data (infrared, Raman, absorption) showed that purified carbon nanotubes interact weakly with benzonitrile. These experimental results are confirmed by first principles calculations that predict a very weak adsorption process through π–π interaction instead of through the free electron pair of the nitrile.     

Atmospheric pressure chemical vapour synthesis of silicon–carbon nanoceramics from hexamethyldisilane in high temperature aerosol reactor

Silicon–carbon nanoceramics have been synthesised from hexamethyldisilane (HMDS) by the atmospheric pressure chemical vapour synthesis (APCVS). Direct aerosol phase synthesis enables continuous production of high purity materials in one-stage process. The particle formation is based on the decomposition of the precursor in a high temperature reactor. Reaction of the gas phase species leads to homogeneous nucleation and formation of the nanoparticles with a narrow size distribution (geometric mean diameter range of particle number size distribution 160–200 nm with 1.5–1.6 geometric standard deviation at reaction temperatures 800–1200 °C). A systematic investigation of the influence of the process temperature on the powder characteristics, including the particle size, crystallinity, chemical structure, surface and bulk composition and surface morphology, was carried out. At the reactor temperature of 800 °C, the synthesised nanoparticles were amorphous preceramics containing mostly SiC₄, Si–CH₂–Si and Si–H units. The composition of the powder turned towards nanocrystalline 3C–SiC (crystal size under 2 nm) when the reaction temperature was increased to 1200 °C. The reaction temperature appeared to be a key parameter controlling the structure and properties of the synthesised powders.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

Effects of deposition temperature and post-annealing on structure and electrical properties in (La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>)CoO<Subscript>3</Subscript> films grown on silicon substrate

(La_0.5Sr_0.5)CoO₃ (LSCO) thin films have been fabricated on silicon substrate by the pulsed laser deposition method. The effects of substrate temperature and post-annealing condition on the structural and electrical properties are investigated. The samples grown above 650°C are fully crystalline with perovskite structure. The film deposited at 700°C has columnar growth with electrical resistivity of about 1.99×10⁻³ Ω cm. The amorphous films grown at 500°C were post-annealed at different conditions. The sample post-annealed at 700°C and 10⁻⁴ Pa has similar microstructure with the sample in situ grown at 700°C and 25 Pa. However, the electrical resistivity of the post-annealed sample is one magnitude higher than that of the in situ grown sample because of the effect of oxygen vacancy. The temperature dependence of resistivity exhibits semiconductor-like character. It was found that post-annealing by rapid thermal process will result in film cracks due to the thermal stress. The results are referential for the applications of LSCO in microelectronic devices.     

Improved performance of porous LiFePO4/C as lithium battery cathode processed by high energy milling comparison with conventional ball milling

Porous LiFePO₄ is synthesized and coated with amorphous carbon by using high energy nano-mill (HENM) processed solid-state reaction method. FeCl₃ (38%) containing water solution which is originated from pickling of steel scrap (waste liquid) is used as a source material in this study. The result indicates that LiFePO₄ powders are well coated with the amorphous carbon. HENM process successfully produces the porous LiFePO₄ with homogeneously distributed pores and a well networked carbon web, which delivers an enhanced electrochemical rate capability. HENM process is incorporated as an effective route for reducing particle size, distributing particle homogeneously and averting agglomeration of particles of precursor in this study. X-ray diffraction, scanning electron microscopy with elemental mapping, transmission electron microscopy with selected area (electron) diffraction, Raman spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge are employed to characterize the final product. Electrochemical measurement shows that the synthesized LiFePO₄/C composite cathode delivers an initial discharge capacity of 161 mAhg⁻¹ at 0.1C-rate between 4.2 and 2.5 V. Remarkably, the cathode delivers 101.9 mAhg⁻¹ at high charge/discharge rate (10 C).     

Study on the effect of the metal–support (Fe-MgO and Pt-MgO) interaction in alcohol-CVD synthesis of carbon nanotubes

This study presents the effect of the metal–support interaction in two systems: (1) iron particle, and (2) platinum particles, being supported on magnesium oxide (MgO) nanopowder in alcohol-CVD process for carbon nanotubes (CNTs) growth. The employment of the different metals but the same substrate (with equal molar ratio) resulted in the synthesis of single-walled CNTs (SWCNTs) or double-walled CNTs (DWCNTs), using iron and platinum, respectively. Furthermore, along with the prolongation of the process time, the decrease of the mean nanotubes diameter in case of iron-catalyzed materials was detected. Interestingly, the extention of the growth time in the synthesis using Pt/MgO resulted in the synthesis of the thicker mean nanotubes diameter. However, for both applied catalytic systems the reduction of the diameter distribution of the tubes and the increase of relative purity of the samples upon the growth time increase were detected.     

Carboxylated single-walled carbon nanotubes induce an inflammatory response in human primary monocytes through oxidative stress and NF-κB activation

A mechanistic understanding of interactions between carbon nanotubes (CNTs) and living systems has become imperative owing to the growing nanomedicine applications and the mounting societal concerns on nanosafety. The addition of different chemical groups leads to a significant change in the properties of CNTs, and the resulting functionalized CNTs are generating great interest in many biological applications, such as biosensors and transporters. This study aimed to assess the toxicity exhibited by carboxylic acid functionalized single-walled CNTs (SWCNTs) (with a diameter of 1–2 nm and mean length of 500 nm) and to elucidate possible molecular mechanisms underlying the biological effects of carboxylated SWCNTs in human primary monocytes. The results demonstrated that carboxylated SWCNTs were cytotoxic, triggering apoptosis and G₂/M phase arrest in human primary monocytes. Flow cytometric and confocal microscopic analysis indicated that internalized carboxylated SWCNTs were mainly accumulated in the cytoplasm. Exposure of human primary monocytes to carboxylated SWCNTs led to interleukin-8 (IL-8) and interleukin-6 (IL-6) expression, reactive oxygen species (ROS) production, and nuclear factor-kappa B (NF-κB) activation in human primary monocytes. Pretreatment of human primary monocytes with antioxidants or NF-κB-specific inhibitor before exposure to carboxylated SWCNTs significantly abolished carboxylated SWCNTs-induced IL-8 and IL-6 expression. These results provide novel insights into the carboxylated SWCNTs-mediated chemokine induction and inflammatory responses in vitro.     

Crystal microstructure of annealed nanocrystalline Chromium studied by synchrotron radiation diffraction

The microstructure of electrodeposited nanocrystalline chromium (n-Cr) was studied by using synchrotron radiation (SR) diffraction, SEM, TEM, and EDX techniques. The as-prepared n-Cr samples show the standard bcc crystal structure of Cr with volume-averaged column lengths varying from 25 to 30 nm. The grain growth kinetics and the oxidation kinetics were studied by time resolved SR diffraction measurements with n-Cr samples annealed at 400, 600, and 800 °C. The grain growth process is relatively fast and it occurs within the first 10 min of annealing. The final crystallite size depends only on the annealing temperature and not on the initial grain size or on the oxygen content. The final volume-averaged column lengths observed after 50 min annealing are 40(4), 80(1), and 120(2) nm for temperatures 400, 600, and 800 °C, respectively. It is shown that annealing ex situ of n-Cr at 800 °C both under vacuum and in air gives a grain growth process with the same final crystallite sizes. The formation of the Cr₂O₃ and CrH phases is observed during annealing.     

Mg–Al LDH reinforced PMMA nanocomposites: a potential material for packaging industry

Poly-methylmethacrylate/Mg–Al layered double hydroxide (PMMA/LDH) based nanocomposites have successfully been synthesised with varying LDH content by in situ polymerisation technique and systematically studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT IR), UV-Visible spectroscopy and microscopic (FE SEM and HR TEM) analysis. In particular, thermogravimetric analysis (TGA) and gas barrier properties measurement were carried out to assess the suitable application of these materials. The thermal property of PMMA/LDH composites was compared with neat PMMA and an enhancement in thermal stability was noticed with gradual increase in LDH content in the composite. Gas permeability measurement data showed significant decrease in oxygen permeability value of the PMMA/LDH nanocomposites in comparison to the pristine PMMA. Enhancement in thermal stability along with significant reduction in oxygen permeability of PMMA upon composite formation indicate the possible application of these materials in packaging industries.     

Multiwall carbon nanotubes synthesized by RF-CCVD on novel CaO supported catalysts

Multiwall carbon nanotubes were synthesized on the FeCoCaO and FeMoCaO catalysts by RF-CCVD at 750 °C, 850 °C and 950 °C, using acetylene as the carbon source. Analytically, it was found that the nanotubes are well crystallized, with outside diameters ranging between 10 and 60 nm and a ratio of the outside to the inside diameters of 2 to 3. The nanotubes did not present amorphous carbon and their purity increased with the temperature of synthesis. A relatively large number of metallic nanoparticles of various dimensions and shapes encapsulated inside the nanotubes were observed by TEM in most of the nanotube samples.     

Inclusion of SWCNTs in Nb/Pt co-doped TiO2 thin-film sensor for ethanol vapor detection

Nb-Pt co-doped TiO₂ and the hybrid SWCNTs/Nb-Pt co-doped TiO₂ thin films have been prepared by the sol–gel spin-coating process for gas-sensor fabrication. Field emission scanning electron microscope (FE-SEM, TEM and X-ray diffraction (XRD) characterizations indicated that the SWCNTs inclusion did not affect the morphology of the TiO₂ thin film and the particle size. Additionally, the SWCNTs were well embedded in the TiO₂ matrix. The gas-sensing properties of Nb–Pt co-doped TiO₂ thin films with and without SWCNTs inclusion were investigated. The hybrid sensors with the inclusion of different SWCNTs contents are examined to elucidate the effect of SWCNTs content on the gas-sensing properties. Experimental results revealed that the responses to ethanol of Nb–Pt co-doped TiO₂ sensors with SWNCTs inclusion increase by factors of 2–5 depending on the operating temperature and the ethanol concentration, compared to that of the sensor without SWCNTs inclusion. Moreover, all hybrid sensors can operate with high sensitivity and stability at a relatively low operating temperature (<335 °C). The responses of the hybrid sensors are greatly affected by SWCNTs content inclusion. The optimized SWCNTs content of 0.01% by weight was obtained for our experiment. The improved gas-sensing performance should be attributed to the additional formation of the p/n junction between SWCNTs (p-type) and TiO₂ (n-type).     

Quality improvement of single-walled carbon nanotubes by doping B in Fe/MgO catalyst

We demonstrate that the quality of the as-grown single-walled carbon nanotubes (SWCNTs) can be effectively improved by the addition of the B ingredient in the Fe/MgO catalyst. The as-grown SWCNTs were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. The SWCNTs prepared by the pure Fe/MgO catalyst have relatively low graphite crystallinity and are coated by much amorphous carbon. The intensity ratio of the D- and G-bands (I_D/I_G) in Raman spectra is relatively high (0.098 for laser 532 nm and 0.075 for laser 785 nm). The SWCNTs grown from the Fe/MgO catalyst doped with 0.1 part of B have more regular graphite structure with little amorphous carbon. The I_D/I_G values reduced remarkably (0.041 for laser 532 nm and 0.040 for laser 785 nm). The effect would be attributed to the inhibitory action of the doped B on the formation of radical hydrocarbon species for the formation of SWCNTs.     

Elemental distribution analysis of type I collagen fibrils in tilapia fish scale with energy-filtered transmission electron microscope

Elemental distribution of calcium, phosphorus, oxygen, and carbon in a single collagen fibril obtained from tilapia fish scales was identified with an electron energy-loss spectroscopy and an energy-filtered transmission electron microscopy, for the first time. The carbon intensity profile of the single collagen fibril showed the specific D-periodic pattern at 67 nm of type I collagen fibrils. The calcium L_2,3-edge and oxygen K-edge peak positions were detected at 347/350 eV and 137 eV, respectively, and these positions were identical to those of hydroxyapatite. Calcium, phosphorus, and oxygen were present in the hole zones as the amorphous phase, while carbon was present in the overlap zone. Our results indicated that the hole zones preferentially attract calcium and phosphate ions and thus serve as possible nucleation sites for mineralization.     

Anatase nanotubes as support for platinum nanocrystals

Anatase nanotubes were successfully produced via the sol–gel process involving organic titanium precursors and multi-walled carbon nanotubes as template. Controlled heat treatments were carried out in order to remove any solvents and to crystallise the initial amorphous titania coating into anatase. In order to use these structures for catalyst support, platinum particles were formed by the impregnation with hexachloroplatinic acid and subsequent calcination and reduction to obtain a final loading of 4 wt% platinum. This impregnation step was carried out either with the carbon nanotube former still present with subsequent heat treatment to remove the carbonaceous template (sample A) or with the carbon nanotube former already removed (sample B). The materials were characterised by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.