Synthesis of Heterogenous Multi-Walled Carbon Nanotubes in a Carbon Arc in Water

Boron-doped multi-walled carbon nanotubes (MWCNTs) were generated by arc discharge in water by using B-doped graphite electrodes. The product morphology was studied by SEM and HRTEM microscopy. The electronic features were determinated by Raman and EELS spectroscopy. Optical emission spectroscopy (OES) was used to evaluate the temperature and C₂ content distributions in arc plasma.     

Catalyst effect on the preparation of single-walled carbon nanotubes by a modified arc discharge

Single-walled carbon nanotubes (SWCNTs) were prepared by a modified arc discharge furnace using 500?Torr helium as buffer gas at 600?°C. The effect of the catalyst type on the production of SWCNTs was studied by transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The experimental results indicated that the catalyst composition plays an important role in the production rate and purity of the SWCNTs product. Fe-Ni-Mg and Co-Ni powder catalysts demonstrated excellent catalytic effect at a catalyst content of 3?wt%. The soot production rate was up to 15?g/hr and the mean diameter of SWCNTs was about 1.3?nm.     

Conversion of toluene into carbon nanotubes using arc discharge plasmas in solution

In order to form nanocarbon materials, an arc discharge plasma method in hydrocarbon solvent is developed. In the case that the arc discharge is performed in toluene with nickel electrodes, tube-like nanocarbons were formed from toluene. The catalysis of the metal electrodes is found to be an important factor for the formation of the nanocarbons by the arc discharge in toluene. This method has a possibility of forming carbon nanotubes from liquid state solvents as a new carbon source by using catalyst ingredient as discharge electrodes.     

Synthesis of carbon nanotubes by arc discharge in open air

In this work Carbon nanotubes have been synthesized by arc discharge in open air. A TIG welding ac/dc inverter was used as the power source for arc discharge. During each run of the arc discharge based synthesis, the anode was a low purity (approximately 85% C by weight) graphite rod. The effect of varying the atmosphere on the yield of soot of the carbon nanotube containing carbon soot has been studied. Various soots were produced, purified by oxidation and characterized to confirm formation of carbon nanotubes and their relative quality, using transmission electron microscopy, Raman spectroscopy, and XRD. It was found that the yield of soot formed on the cathode is higher when synthesis is carried out in open air than when carried out in a flowing argon atmosphere. When synthesized in open air, using a 7.2-mm-diameter graphite rod as anode, the yield of soot was around 50% by weight of the graphite consumed. Current and voltage for arcing were at identical starting values in all the experiments. This modified method does not require a controlled atmosphere as in the case of a conventional arc discharge method of synthesis and hence the cost of production may be reduced.     

Effect of Rh and Pt on growth and structure of single-walled carbon nanotubes

This work studied a new method to prepare single-walled carbon nanotubes (SWCNTs). The key of this method is to add two kinds of platinum family metals as catalysts to a graphite rod to make a composite graphite anode. The arc discharge was carried out in helium gas, and the collected product was observed and analyzed using high-resolution transmission electron microscopy and Raman spectroscopy. The results showed that straight SWCNTs with uniform diameter could be obtained without the inclusion of any magnetic metal catalysts. This offers the possibility of studying the SWCNT-polymer magnetic functional material. The structure and the growth mechanism of the SWCNTs prepared by this new method were also analyzed. The text was submitted by the authors in English.     

Carbon Nanotubes Grown on the Surface of Cathode Deposit by Arc Discharge

Carbon nanotubes prepared by de arc discharge of graphite electrodes in He and CH₄ gas took markedly different morphology. Thick nanotubes embellished with many carbon nanoparticles were obtained by evaporation under high CH₄ gas pressure and high arc current. Thin and long carbon nanotubes were obtained under a CH₄ gas pressure of 50Torr and an arc current of 20A for the anode with a diameter of 6mm.     

Efficient strategy to Cu/Si catalyst into vertically aligned carbon nanotubes with bamboo shape by CVD technique

Bamboo-shaped vertically aligned carbon nanotubes (bs-VACNTs) were fabricated on Cu/Si catalyst by chemical vapour deposition (CVD) technique under the atmospheric pressure. The catalytic material (Cu/Si) played a vital role in attaining bs-VACNTs, which is synthesized by drop cast method in a cost-effective manner. Using this catalytic support, we have achieved the tip growth bs-VACNTs at low temperature with well graphitization. The as-grown carbon material was then characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) analyzer, high-resolution transmission electron microscope (HRTEM) and Raman spectroscopy. XRD technique confirms the formation of hexagonal graphitic carbon planes of carbon nanotubes (CNTs). The surface morphology of the material was characterized by SEM, which clearly infer vertically aligned CNTs. The nature, diameter and crystallinity were noticed by HRTEM and Raman spectroscopy, respectively. Further, we have also studied the electrochemical properties of the bs-VACNTs and it seems to be proved as highly electroconductive when compared to multi-walled carbon nanotubes (MWCNTs).     

Anisotropies in Carbon Nanotube Synthesis by the Hydrogen Arc Plasma Jet Method

Single-wall carbon nanotubes were prepared under hydrogen gas atmosphere with a DC arc discharge maintained between the tip of a sharpened graphite cathode and an anode formed by a catalytic mixture of graphite, FeS, Ni, Fe and Co compressed powders. The cathode is placed with an inclination with respect to the anode, so that the plasma jet of the discharge is deviated towards the empty space of the growth chamber. Samples were classified and analyzed according to their type and growth positions relative to the direction of the plasma jet flow. Characterization of the samples was performed with mass spectrometry, Raman spectroscopy and transmission electron microscopy. A subtle variation is found in the properties of the nanotubes obtained in different locations due to the directionality of the plasma jet flow. Observed differences in sample properties may be qualitatively understood in terms of accepted mechanisms of SWNT growth.     

Coral-like amorphous carbon nanotubes synthesized by a modified arc discharge

A coral-like amorphous carbon nanotube was prepared by a modified arc discharging furnace in hydrogen atmosphere with a mixture of Mo-Co₂O₃-Mg powders as catalyst at 600°C. This carbon nanotube presented a microscopic coral-like by SEM observation and amorphous structure of nanotubes by HRTEM observation. The XRD diffraction and Raman pattern presented noncrystal characteristics compared to the normal graphite structure. We believed that these results may be affected by the “synergistic” effect of catalyst, atmosphere, and temperature in the synthesis process. The possible explanations to the formation mechanism of this novel carbon nanotube have also been proposed.     

Growth and characterization of bamboo-shaped carbon nanotubes using nanocluster-assembled ZnO:Co thin films as catalyst

Bamboo-shaped carbon nanotubes (CNTs) had been successfully fabricated by a plasma enhanced chemical vapor deposition method, in which nanocluster-assembled ZnO:Co thin film was used as catalyst. It was found that bamboo-shaped CNTs were generally grown in a direction perpendicularly to the substrate surface with the tops of CNTs dominated by the droplet-like catalyst covered by the carbon layer. The diameter of CNTs was ranged from 20-50 nm. High resolution of TEM image showed that the typical CNT had a multi-walled structure with an inner core presented. The ordered graphite layers were inclined to an axis of CNT about 18 degrees and the interlayer space of a CNT was about 0.35 nm. Two peaks in Raman spectrum at 1586 cm(-1) and 1372 cm(-1) were identified as G-band and D-band for graphite, respectively. The results showed that catalyst based on ZnO:Co thin films could be used for the growth of CNTs with bamboo-shaped structure.     

Bulk preparation and characterization of mesoporous carbon nanotubes by catalytic decomposition of cyclohexane on sol–gel prepared Ni–Mo–Mg oxide catalyst

Multiwalled carbon nanotubes were synthesized using Ni–Mo–Mg oxide catalyst prepared by sol–gel technique. Carbon nanotubes were formed in situ by the reduction of nickel oxide (NiO) and molybdenum oxide (MoO₃) to Ni and Mo by a gas mixture of nitrogen, hydrogen and cyclohexane at 750 °C. Scanning Electron Microscopy (SEM) was used to confirm the formation of carbon nanotubes (CNTs). The pore size distribution of carbon nanotubes (CNTs) was investigated by N₂ adsorption and desorption. It was found that the pore size fell into the mesopore range: 2 < d < 50 nm. Interpretation was also made using Raman spectroscopy, Diffuse reflectance spectroscopy, X-ray diffraction and ESR spectra. This method is found to produce a very high yield weighing over 20 times of the catalyst. Based on the experimental conditions and results obtained a possible growth mechanism of the carbon nanotubes is proposed.     

Preparation and modification of carbon nanotubes

Carbon nanotubes (CNTs) were prepared by the catalytic decomposition of methane at 680 °C for 120 min, using nickel oxide–silica binary aerogels as the catalyst. The morphological structure of CNTs was investigated by transmission electron microscopy (TEM), X-ray Diffraction (XRD) and Raman spectroscopy. The results revealed that CNTs with diameter 40–60 nm showed high quality, uniform diameter and high length/diameter ratio, the wall structure of CNTs was similar with that of highly oriented pyrolytic graphite (HOPG), and some metal catalyst particles were encapsulated at the tip of CNTs. Different methods were compared to modify CNTs. Investigated by TEM, XRD, Raman spectroscopy and nitrogen adsorption/desorption for modified CNTs, it was confirmed that after modification treatment by immersion in diluted HNO₃ solution with ultrasonic and then milling by ball at a high velocity, the metal catalyst particles at the tip of CNTs disappeared, the unique cylinder wall structure remained, the CNT length became short, the cap at the tip of nanotube was opened, and thus the internal surface area could be effectively used, leading to the increase of the specific surface area and pore volume. This technique is relatively simple and effective for modifying CNTs which can be scaled up for industrial applications.     

Synthetic Routes to Novel Nanomaterials

Soon after the bulk production of carbon nanotubes was achieved, using arc discharge techniques, other methods involving gas phase processes (i.e. combustion ami pyrolysis of hydrocarbons, laser irradiation of graphite) were developed. Nowadays, it is possible to generate nanotubes and fullerene-related nanostructures from layered materials such as WS₂, MoS₂, BN, BC₂N and BC₃. Recently, a new technique, involving electrolysis of graphite electrodes in molten ionic salts, has been developed which may open up new synthetic routes to nanotubes in the liquid phase. In this paper, possible growth mechanisms for such processes are reviewed and other routes to nanstructures are discussed.     

工业级原料制备碳纳米管的研究

为降低碳纳米管批量制备的原料成本,以焦化苯和二茂铁为主要原料(工业级),采用浮游催化热解法制备碳纳米管,用TEM、SEM、Raman、XRD等对产物的形貌和结构进行观察和表征,着重讨论了二茂铁的分解温度和苯的挥发温度对碳纳米管的制备及其形貌的影响,并对其影响机理进行了分析.研究表明:在噻吩体积分数为0.55 mL/100 mL苯、炉膛反应温度为1170℃的前提下,当二茂铁的分解温度为150℃、苯的挥发温度为50℃时,用工业级原料完全可以制备出碳纳米管,此时,碳纳米管的内径分布在0.88~1.15 nm.     

Structure of multiwalled carbon nanotubes grown by chemical vapor deposition

Carbon nanotubes have been grown by chemical vapor deposition at 650°C in an argon atmosphere using a butane-propane mixture and a nickel catalyst and have been characterized by scanning and transmission electron microscopy and Raman spectroscopy. The results indicate that the multiwalled nanotubes have an imperfect graphite-like structure with a conical supramolecular configuration. A phenomenological technique is proposed for statistical analysis of the state of carbon nanotubes in measurements of the intensity of the defect zone D in their Raman spectra.     

Moderate temperature synthesis of single-walled carbon nanotubes on alumina supported nickel oxide catalyst

A simple nickel oxide catalyst has been developed in synthesizing single-walled carbon nanotubes (SWNTs) at moderate temperature. The catalyst used in the experiment was without a preceding reduction in hydrogen flow. The synthesis of SWNTs was performed at a temperature of 700 °C, which represents a moderate reaction temperature. The presence of SWNTs on the catalyst was confirmed by transmission electron microscope (TEM) and Raman spectroscope. The Raman spectrum shows a strong intensity at the radial breathing mode, indicating that the occurrence of SWNTs was dominant. Raman data further reveals that the synthesized SWNTs had the diameters in the range from 0.58 to 2.02 nm.     

Hydrogen-acetylene gas ratio and catalyst thickness effect on the growth of uniform layer of carbon nanotubes

Effect of catalyst thickness (2, 4, and 6 nm) and acetylene-hydrogen gas ratio (1/4, 2/4, and 3/4) on the synthesis of carbon nanotubes is reported in this article. Synthesized nanotubes are characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy, and Raman effect. From SEM results, nanotubes growth is less for higher thickness, as at higher thickness catalyst nanoparticles agglomerate which suppress the growth of nanotubes. Raman spectroscopy results reveal that at higher thickness defects density increases. Nanotube of better crystallinity and graphitic outer walls grows for lower acetylene-hydrogen gas ratio and at smaller thickness of catalyst layer. The sheet resistance of carbon nanotube thin film is measured by using Hall effect measurement systems. Smallest sheet resistance among synthesized multi-walled carbon nanotubes sample is obtained for nanotubes grown on 2 nm thick catalyst film and is 0.9 kΩ/square.     

高分散度非晶态NiB／CNTs催化剂制备及其催化加氢性能

利用苯胺、曲拉通分别对氨气热处理的碳纳米管进一步功能化，修饰碳纳米管表面，促进碳纳米管分散。采用超声波辅助的浸渍-化学还原法制备非晶态NiB／CNTs合金催化剂，平均粒径为14nm、10nm的非晶态NiB颗粒均匀分布在苯胺、曲拉通处理的碳纳米管表面。苯胺、曲拉通功能化处理使催化剂的Ni负载量分别提高了10．4％、14．6％，同时提高了催化剂的乙炔加氢活性和乙烯选择性。将苯胺和曲拉通的处理效果比较，发现无论是NiB颗粒的分散度还是催化剂的加氢性能，曲拉通处理的效果明显优于苯胺。     

Electron Microscopic Study of Heat-Treated Carbon Nanotubes

Carbon nanotubes, which were made by DC arc discharge of a graphite electrode, were heat-treated at about 250°C in intermediate vacuum of 10^-4 Torr and 10^-2 Torr. Considerable thickening of carbon nanotubes and periodic morphology like that of living organisms were observed by scanning electron microscopy.     

Electric field-oriented growth of carbon nanotubes and Y-branches in a needle-pulsed arc discharge unit: mechanism of the production

Carbon nano-onions, multiwall carbon nanotubes and Y-branched nanotubes are synthesised in a simple production apparatus. A pulsed plasma is generated by discharging a high voltage needle pulse between two graphite electrodes. A strong electric field is presented along anode and cathode electrodes. The pulse width is 0.3 μs. Acetone vapour, as a precursor, is introduced to the plasma through a graphite nozzle in the cathode assembly. A magnetic field, perpendicular to the plasma path, is provided. The possibility of carbon nanotube production through a short-pulsed arc discharge technique is investigated in this article. The results show that adding an electric field between electrodes prevents carbon ions’ dispersion, facilitates charge transferring between ions and electrodes, orients the growth of carbon nanotubes along the applied electric field and finally makes it possible to produce functionalised carbon nanoparticles such as Y-branch nanotubes and nanoknees. In this work, the growth mechanism of carbon nanotubes in a needle-pulsed arc-discharge reactor is discussed. And a possible explanation is provided for the synthesis of Y-branch carbon nanotubes. The products are examined by using scanning probe microscopy technique.