Effective Synthesis of Vertically Aligned Boron Nitride Nanotubes via a Simple CCVD

A simple catalytic chemical vapor deposition technique based on the combined logic of previously synthesized vertically aligned carbon nanotubes and pattern growth of boron nitride nanotubes (BNNTs) along with a few simple modifications in the experimental setup is successfully used for the synthesis of vertically aligned BNNTs. Field emission scanning electron microscope images show the top and side view of the as grown pure BNNTs. High-resolution transmission electron microscope images confirm the tubular structure as well as the highly crystalline nature of the tubes. X-ray photon spectroscopy and Raman spectroscopy indicate h-BN as a main constituent of BNNTs synthesized in the present work.     

A one-step technique to prepare aligned arrays of carbon nanotubes

A simple effective pyrolysis technique has been developed to synthesize aligned arrays of multi-walled carbon nanotubes (MWCNTs) without using any carrier gas in a single-stage furnace at 700?°C. This technique eliminates nearly the entire complex and expensive machinery associated with other extensively used methods for preparation of CNTs such as chemical vapour deposition (CVD) and pyrolysis. Carbon source materials such as xylene, cyclohexane, camphor, hexane, toluene, pyridine and benzene have been pyrolyzed separately with the catalyst source material ferrocene to obtain aligned arrays of MWCNTs. The synthesized CNTs have been characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and Raman spectroscopy. In this technique, the need for the tedious and time-consuming preparation of metal catalysts and continuously fed carbon source material containing carrier gas can be avoided. This method is a single-step process where not many parameters are required to be monitored in order to prepare aligned MWCNTs. For the production of CNTs, the technique has great advantages such as low cost and easy operation.     

化学气相沉积法合成碳纳米管及其导电性能研究

以二甲硫醚为碳源前驱体,Co/MgO为催化剂,采用化学气相沉积法生长出碳纳米管及Y形碳纳米管,此法稳定性及重现性较好.通过扫描电子显微镜、透射电子显微镜、拉曼光谱及X射线衍射对产品形态和结构进行了分析和表征,结果表明,所制备的碳纳米管形态较规整、纯度较高,具有较好的石墨微晶结构;导电性能测试结果显示,Y形碳纳米管各分支均呈现出典型的金属性导电性能.     

One-step synthesis of carbon nanotubes–copper composites for fabricating catalyst supports of methanol electrooxidation

One-step synthesis of carbon nanotubes–copper composites was established by catalytic chemical vapor deposition (CCVD) of acetylene over Co–Cu–Al mixed metal oxides derived from layered double hydroxides (LDHs). Power X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), Raman spectra, thermogravimetric and differential thermal analysis (TG-DTA) and N₂ adsorption–desorption measurements revealed that multi-walled carbon nanotubes were synthesized during cobalt-catalyzed CCVD, and copper nanoparticles were simultaneously in situ formed in CNTs matrix. Electrodes modified with platinum particles supported on as-fabricated CNTs–Cu composites showed much higher electrocatalytic activity for the oxidation of methanol than that modified with Pt particles supported on the commercial CNTs. The present study greatly enlarges the practical application of hybrid CNTs-based nanocomposites.     

Mo-Co catalyst nanoparticles: Comparative study between TiN and Si surfaces for single-walled carbon nanotube growth

Highly pure single-walled carbon nanotubes (SWNT) were synthesized by alcohol catalytic chemical vapor deposition on silicon substrates partially covered by a thin layer of TiN. The TiN coating selectively prevented the growth of carbon nanotubes. Field emission scanning electron microscopy and Raman spectroscopy revealed the formation of high purity vertically aligned SWNT in the Si region. X-ray Photoelectron Spectroscopy and Atomic Force Microscopy indicated that Co nanoparticles are present on the Si regions, and not on the TiN regions. This clearly explains the obtained experimental results: the SWNT only grow where the Co is presented as nanoparticles, i.e. on the Si regions.     

Influence of co-catalyst on growth of carbon nanotubes using alcohol catalytic CVD method

This paper describes the influence of a co-catalyst on growth of carbon nanotubes (CNTs) by alcohol catalytic chemical vapour deposition (ACCVD) method. Silicon wafers covered with thermal oxide or polycrystalline diamond thin film were used as substrates. Ni thin film supported with Al, Cu or Ti was used as a catalyst. The films were deposited by pulsed laser deposition technique. Comparison of the various types of the co-catalyst (Al, Cu, Ti) leads to the conclusion that Cu co-catalyst is suitable for producing very thin single wall carbon nanotubes (SWCNTs) and combination of Al and Ni provide a good condition to the catalytic growth of CNTs. In addition, we observed also the influence of the various diffusion barriers (thermal oxide and polycrystalline diamond) on growth of CNTs. Prepared samples were analysed by Raman spectroscopy (RS) and scanning electron microscopy (SEM).     

Large scale synthesis of bundles of aligned carbon nanotubes using a natural precursor: turpentine oil

Bundles of aligned carbon nanotubes (ACNTs) have been synthesised by spray pyrolysis of turpentine oil (inexpensive precursor) and ferrocene mixture at 800°C. Turpentine oil (C₁₀H₁₆), a plant-based precursor was used as a source of carbon and argon as a carrier gas. The bundles of ACNTs have been grown directly inside the quartz tube. The as-grown ACNTs have been characterised through X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopic techniques. Scanning electron microscope images reveal that the bundles of ACNTs are densely packed and are of ～70–130?µm in length. High-resolution transmission electron microscopy and Raman spectroscopy observations indicate that as-grown multi-walled carbon nanotubes (CNTs) are well graphitised. These CNTs have been found to have outer diameters between ～15 and 40?nm. This technique suggests a low-cost route for the large-scale formation of ACNTs bundles.     

不同压力下碳纳米管的电弧法合成及其表征(英文)

采用电弧放电法在氦气/乙炔混合气氛中,在不同压力下合成了碳纳米管.运用场发射扫描电镜、场发射透射电镜、X-射线衍射仪和拉曼光谱对碳纳米管的形貌进行了表征.采用可见发射光谱对碳纳米管的形成过程进行了原位诊断研究.场发射扫描电镜结果表明,在氦气/乙炔气氛中合成的碳纳米管的长度大于50微米,许多碳颗粒沉积在碳纳米管壁上.场发射透射电镜结果表明,在0.100MPa下合成的碳纳米管的壁厚明显大于0.035MPa下合成的碳纳米管的壁厚.可见发射光谱诊断结果表明,CH和C2物种可能作为碳纳米管形成的前驱体,其中,以H原子作为无定形炭的刻蚀物种.阳极消耗速率和产物在阴极的沉积速率随着反应器中压力的增加而增加.因此,可以通过加强阳极和乙炔的蒸发速率及CH和C2物种的沉积速率而增加碳纳米管的形成速率.     

Carbon nanotube synthesis from propane decomposition on a pre-treated Ni overlayer

Growth of carbon nanotubes (CNTs) was performed by atmospheric pressure chemical vapour deposition (APCVD) of propane on Si(111) with a pre-treated Ni overlayer acting as a catalyst. Prior to the growth of CNTs, a thin film of Ni was deposited on Si(111) substrate by evaporation and heat treated at 900°C. The growth of nanotubes was carried out at 850°C using propane as a source of carbon. Distribution of the catalyst particles over the Si substrate was analysed before and after heat treatment by atomic force microscopy (AFM). The X-ray diffraction (XRD) pattern of the grown material revealed that they are graphitic in nature. Field emission scanning electron microscopy (FESEM) was used to investigate the growth process and it was found that a catalytic particle was always situated at the tip of the tube thus implying a tip growth mechanism. Evidence for the presence of radial breathing mode from multi-wall nanotubes (MWNTs) in the grown sample was obtained from micro-Raman analysis. Finally, high-resolution transmission electron microscopic (HRTEM) analysis confirmed that the graphene layers of the CNTs are well ordered with typical 0·34 nm spacing.     

机磨热加工法合成碳纳米管

机磨热加工法是批量制取碳纳米管(CNTs)的方法之一.在氩气氛中研磨鳞片石墨为无定形的纳米炭粉,而后在1350℃～1380℃下退火获得碳纳米管(CNTs).用XRD,SEM,FE-TEM,HRTEM和拉曼光谱对纳米炭粉及CNTs进行表征.发现:CNTs具有不同的形貌,长度约几毫米,直径为30nm～70nm.螺旋状多壁碳纳米管有高的长径比(～1000)和高的结晶度(ID/IG:～0.03).     

自组装和分散可逆的碳纳米管圆片

通过加热碳纳米管和强酸的混合物,使碳纳米管的憎水表面发生氧化.加热含经处理的碳纳米管的悬浮液,使之脱水,得到自组装的碳纳米管圆片,该圆片可直接分散.扫描电镜图显示该圆片由局部规则排列的碳纳米管构成;红外光谱和光电子谱分析表明在化学处理过程中,碳纳米管的表面产生了含氧官能团;虽然拉曼谱测出处理过程增加了缺陷,但是X射线衍射结果表明碳纳米管类似石墨的层状结构得到保留;同时研究了经处理的碳纳米管的热稳定性.这种自组装且可分散的碳纳米管圆片为研究碳纳米管结构材料和碳纳米管复合材料提供了有效途径.     

Electrodeposited carbon nanotube thin films

A successful attempt to grow carbon nanotubes (CNTs) by electrodeposition technique for the first time is reported here. Carbon nanotubes were grown on Si (001) substrate using acetonitrile (1% v/v) and water as electrolyte at an applied d.c. potential ∼20 V. The films were characterized by X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Raman, optical absorbance, Fourier Transform Infra Red spectroscopy (FTIR) and Electron Spin Resonance (ESR) measurements. The effect of magnetic field on the growth of nanotubes was studied critically. It was found that the presence of magnetic field during electro-deposition played a crucial role on the growth of carbon nanotubes and hence the electronic properties. Photoluminescence (PL) studies indicated band edge luminescence ∼0.72-0.83 eV. Field emission studies indicated lower turn-on voltage and higher current density for films deposited with magnetic field.     

Synthesis and characterization of large area well-aligned carbon nanotubes by ECR-CVD without substrate bias

Large area, well-aligned carbon nanotubes (CNTs) were synthesized on porous silicon by electron cyclotron resonance chemical vapor deposition (ECR-CVD). No bias was applied on the substrate in this experiment. CH₄ and H₂ were used as source gases and Fe₃O₄ nanoparticles as the catalyst. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), and Raman spectrum were used to evaluate the structure and composition. The results show that these CNTs have varying outer diameters from 10 to 90 nm and uniform length over 10 μm. They display hollow tubular and chain structures. The possible formation mechanism of aligned CNTs is discussed.     

Synthesis of carbon nanotubes on metal mesh in inverse diffusion biofuel flames

In this study, renewable biofuels (ethanol and n-butanol) were utilized to synthesize carbon nanotubes on substrate of inexpensive metal mesh (copper alloy and nickel) using inverse diffusion flame. The effects of metal mesh, synthesis time and flame temperature on growth of carbon nanotubes (CNTs) were investigated in details. The morphology and structure of CNTs were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The results showed that there were no CNTs formed on nickel mesh. When the substrate was copper alloy mesh, the yield of CNTs increased from 2?min and reached maximum at about 15?min as the synthesis time increased. Under the condition of 15?min, CNTs synthesized in ethanol flame of 1023?K and in n-butanol flame of 1273?K had higher degree of graphitic structure. In addition, multi-walled carbon nanotubes (MWCNTs) with straight tube wall were synthesized in ethanol flame of 1023?K and 1273?K when the synthesis time was 15?min. For these experiments, CNTs with excellent quality could be synthesized effectively in ethanol flame with temperatures of 1023?K and 1273?K when the synthesis time was 15?min and the substrate was copper alloy mesh.     

Precise control of the number of walls formed during carbon nanotube growth using chemical vapor deposition

We demonstrate a one-step approach for selecting the number of walls formed during carbon nanotube (CNT) growth by catalytic decomposition of CH(4) over Fe-Mo/MgO catalysts. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), thermal gravimetric analysis (TGA) and Raman spectroscopy analyses indicate that high purity single-walled, double-walled and triple-walled carbon nanotubes can be synthesized by tuning the Fe:Mo atomic ratio of catalysts. The results reveal that the concentration of Mo in the catalyst plays an important role in the size of catalyst particles and in the deposition rate of carbon atoms during CNT growth. Thus, the wall numbers of CNTs can be controlled precisely.     

Effect of mixture ratios and nitrogen carrier gas flow rates on the morphology of carbon nanotube structures grown by CVD

We report on the growth of carbon nanotubes (CNTs) by thermal Chemical Vapor Deposition (CVD) and investigate the effects of nitrogen carrier gas flow rates and mixture ratios on the morphology of CNTs on a silicon substrate by vaporizing the camphor/ferrocene mixture at 750 °C in a nitrogen atmosphere. Carbon layers obtained after each CVD growth run of 15 min are characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Growth of CNTs is found to occur on silicon substrates. The SEM micrographs helped better understand the nanotube growth morphology while Raman Spectroscopy was used to detect the presence of nanotubes and also identify their nature vizely semiconducting or metallic, single-walled or multi-walled. Raman Spectra was also useful to estimate the quality of the samples as a ratio of nanotube to non-nanotube content. The length and diameters of the aligned CNTs were found to depend on the pyrolysis temperatures, mixture ratio, and the nitrogen carrier gas flow rates.     

Fabrication, structural characterization and formation mechanism of multiferroic BiFeO3 nanotubes

Multiferroic BiFeO3 (BFO) nanotubes have been successfully fabricated by the modified sol-gel method within the nanochannels of porous anodic aluminum oxide (AAO) templates. The morphology, structure and composition of the nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), selected-area electron diffraction (SAED), high resolution TEM, (HRTEM) and energy-dispersive X-ray spectroscopy (EDX). Postannealed (650 degrees C for 1 h), BFO nanotubes were polycrystalline and X-ray diffraction study revealed that they are of the rhomohedrally distorted perovskite crystal structure. The results of SEM and TEM revealed that BFO nanotubes possessed a uniform length (up to 60 microm) and diameter (about 200 nm), which were controlled by the thickness and the pore diameter of the applied AAO template, respectively and the thickness of the wall of the BFO nanotube was about 15 nm. Y-junctions in the BFO nanotubes were observed. EDX analysis demonstrated that stoichiometric BiFeO3 was formed. HRTEM analysis confirmed that the obtained BFO nanotubes made up of nanoparticles (3-6 nm). The possible formation mechanism of BFO nanotubes was discussed.     

催化化学气相沉积法制备螺旋形多壁碳纳米管(英文)

以乙炔为碳源、FeMo/MgO催化剂为模板,采用催化化学沉积法制备了螺旋状多壁碳纳米管(hs-MWC-NTs)。其中FeMo/MgO模板,由作为发泡和助燃剂的柠檬酸燃烧而制成。FeMo/MgO催化剂的XRD谱图揭示其具有微晶的通性。应用SEM、TEM和Raman光谱剖析了合成的炭材料。SEM和TEM观察表明获得了hs-MWC-NTs;Raman光谱的D峰和G峰确认了所获碳纳米管(CNTs)的结晶状态。结果表明:此法乃是合成直径10nm～20nm螺旋形多壁碳纳米管的最容易和简便方法。     

Synthesis and electrocatalytic activity of multi-walled carbon nanotubes/Cu–Ag nanocomposites

Cu–Ag bimetallic nanoparticles with atomic ratio of 2.1:1 and diameter in the range of 15–30 nm were decorated on acid-treated multi-walled carbon nanotubes by a chemical reduction method, which was characterized by transmission electron microscope (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). The Cu–Ag/MWNTs nanocomposites were used to construct a modified electrode toward biosensing of H₂O₂ with a high sensitivity. The catalytic ability of MWNTs/Cu–Ag toward H₂O₂ was much better than that of MWNTs/Cu and MWNTs/Ag, which indicated that there is a cooperation effect between Cu and Ag.     

Preparation of high yield multi-walled carbon nanotubes by microwave plasma chemical vapor deposition at low temperature

Vertically-aligned carbon nanotubes(CNTs) with multi-walled structure were successfully grown on a Fe-deposited Si substrate at low temperature below 330°C by using the microwave plasma chemical vapor deposition of methane and carbon dioxide gas mixture. This is apparently different from the conventional reaction in gas mixtures of hydrogen and methane, hydrogen and acetylene, and hydrogen and benzene ... etc. High quality carbon nanotubes were grown at lower temperature with CO₂ and CH₄ gas mixture than those used by the previous. After deposition, the microstructure morphology of carbon nanotubes was observed with scanning electron microscope and high-resolution transmission electron microscope. The characteristics of carbon nanotubes were analyzed by laser Raman spectroscopy. The results showed the variation of the flow rate ratio of CH₄/CO₂ from 28.5 sccm/30 sccm to 30/30 sccm and the DC bias voltage from –150 V to –200 V, at 300 W microwave power, 1.3–2.0 kPa range of total gas pressure, and substrate temperatures between 300°C and 350°C. Vertically aligned carbon nanotubes with the diameter of about 15 nm and multi-walled structure were illustrated by SEM and HRTEM. However, the highest yield of carbon nanotubes of about 50% was obtained at low temperature below 330°C by MPCVD for the CH₄/CO₂ gas mixture with properly controlled parameters.