固体单相催化剂CVD法制备成束或分散MWCNT*

CVD法制备纳米碳管的催化剂多是以Al2 O3、SiO2 或MgO作载体 ,Fe、Ni或Co等过渡族金属为活性组分[1- 3] .催化剂与载体之间的关系存在多种形式[1] ,其中固溶体催化剂[4 ,5] 使过渡金属离子能均匀地分布在载体的内部和表面 .在后续反应过程中 ,均匀分布在表面或体内的金属离子被还原成具有催化活性的金属微粒 .此法称为“原位催化分解法 (insituCVD法 )” ,常用于制备直径分布较为均匀的纳米碳管 ,但以往的这些固溶体催化剂在制备纳米碳管的产量上并没有明显的改善 .本工作报道用燃烧法制备的Fe Mo Mg O固溶体 ,不但在用于CVD法生长…     

The effect of Fe and Ni catalysts on the growth of multiwalled carbon nanotubes using chemical vapor deposition

The effect of Fe and Ni catalysts on the synthesis of carbon nanotubes (CNTs) using atmospheric pressure chemical vapor deposition (APCVD) was investigated. Field emission scanning electron microscopy (FESEM) analysis suggests that the samples grow through a tip growth mechanism. High-resolution transmission electron microscopy (HRTEM) measurements show multiwalled carbon nanotubes (MWCNTs) with bamboo structure for Ni catalyst while iron filled straight tubes were obtained with the Fe catalyst. The X-ray diffraction (XRD) pattern indicates that nanotubes are graphitic in nature and there is no trace of carbide phases in both the cases. Low frequency Raman analysis of the bamboo-like and filled CNTs confirms the presence of radial breathing modes (RBM). The degree of graphitization of CNTs synthesized from Fe catalyst is higher than that from Ni catalyst as demonstrated by the high frequency Raman analysis. Simple models for the growth of bamboo-like and tubular catalyst filled nanotubes are proposed.     

燃烧法合成碳纳米管的实验方案设计

碳纳米管是一种新型的碳材料,其合成方法多种多样。燃烧法是一种新兴的合成方法,燃烧过程提供用于碳纳米管生长的高温环境,同时也提供足够的烃原料。目前,用于合成碳纳米管的原料包括气体燃料和液体燃料,火焰类型主要有层流扩散火焰、逆流扩散火焰和预混火焰等。影响炭纳米管火焰合成的因素主要有气体成分,温度,催化剂,燃氧比和采样条件。我们采用甲烷扩散火焰用于实验研究炭纳米管的合成条件。实验系统包括扩散火焰喷嘴,混和段,质量流量计,取样探针和基板,气源。内径5 mm的喷嘴与内径100 mm的钢筒同轴。实验测得在气量为0．20 SLM时火焰高度为 3．5 cm。涂覆有催化剂的基板水平朝下置于火焰中采样,并将采集的样品进行电镜分析。本文还对燃烧法合成碳纳米管的机理进行了分析。     

Morphology of carbon nanotubes prepared via chemical vapour deposition technique using acetylene: A small angle neutron scattering investigation

Small angle neutron scattering (SANS) has been utilized to study the morphology of the multi-walled carbon nanotubes prepared by chemical vapour deposition of acetylene. The effects of various synthesis parameters like temperature, catalyst concentration and catalyst support on the size distribution of the nanotubes are investigated. Distribution of nanotube radii in two length scales has been observed. The number density of the smaller diameter tubes was found more in number compared to the bigger one for all the cases studied. No prominent scaling of the structure factor was observed for the different synthesis conditions.      

Ru decorated Pt nanoparticles by a modified polyol process for enhanced catalytic activity for methanol oxidation

Ru decorated Pt nanoparticles on carbon nanotubes (MWCNTs) were prepared by a modified polyol synthesis method for enhanced catalytic activity for methanol oxidation. The characterizations for the electrocatalysts were carried out by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV) and chronoamperometry (CA). The modified polyol synthesis method promoted position-controlled nucleation and growth of Ru atoms near Pt, and resulted in improved durability against catalyst poisoning compared to PtRu/MWCNTs prepared by common polyol method. This concept also allowed a high loading and dispersion of the catalyst on the carbon supports with few agglomerations of catalyst nanoparticles, resulting in high catalytic activity.     

Carbon nanotubes and nanostructures grown from diamond-like carbon and polyethylene

We report a simple way to synthesize carbon nanotubes and nanostructures from the solid phase. Vacuum annealing of diamond-like carbon (DLC) films or polyethylene mixed with catalyst in argon atmosphere leads to the formation of nanotubes and nanostructures. High-resolution transmission electron microscopy studies reveal highly graphitized multi-walled nanotubes (MWNTs) or amorphous fibre-like structures, depending on the catalyst amount. This synthesis process may give a new approach to understanding the phase transition of different carbon allotropes into nanotubes or nanostructures. Received: 3 July 2001 / Accepted: 3 July 2001 / Published online: 2 October 2001     

A continuous synthesis of carbon nanotubes by dc thermal plasma jet

In this contribution we present a dc thermal plasma jet route for the continuous synthesis of single- and multi- walled carbon nanotubes. Our findings show the as produced product to be dependent on the plasma atmosphere and catalyst. Multi walled carbon nanotubes can be synthesized without a catalyst. Single walled carbon nanotubes require the presence of a catalyst (Ni-Ce) and the addition of hydrogen to the buffer gas. Increasing the amount of hydrogen added to the reaction significantly improves the nanotube yield. PACS 81.07.De; 36.40.Gk; 63.50.+x; 68.37.Lp; 68.37.Hk     

用微米级LaNi5为催化剂生长的碳管的ESR谱研究

用微米级LaNi₅合金粉末为催化剂, 以乙炔为原料, 采用化学气相沉积(CVD)法合成了多壁碳纳米管. 在100~290 K温度下测量了41 μm≤d≤150 μm粒径催化剂制备的不同直径分布的碳纳米管的电子自旋共振（ESR）谱,研究了测量温度、微米级催化剂粒径及制备过程的氢气氛对生成的碳纳米管的ESR谱线型、g因子、线宽的影响. 发现碳纳米管的g因子随其直径的增大而增大,分别为2.040 0（催化剂粒径41 μm≤d≤50 μm, 碳纳米管的直径分布为10 nm到20 nm）和2.089 8（催化剂粒径100 μm≤d≤150 μm,碳纳米管的直径分布为70 nm到120 nm）. 发现小管径纳米管的ESR谱图有一个峰, 而大管径纳米管的ESR谱图有两个峰A和B, 且随测量温度的升高, 峰B强度增大.     

Surface growth of single-walled carbon nanotubes from ruthenium nanoparticles

In this paper, we report that ruthenium is an active and efficient catalyst for growth of single-walled carbon nanotubes (SWNTs) by a chemical vapor deposition (CVD) process for the first time. High density random and horizontally superlong well-oriented SWNTs on substrate can be fabricated via CH₄ or EtOH as carbon source under suitable conditions. Scanning and transition electron microscopy investigations, Raman spectroscopy and atomic force microscopy measurements show the tubular structure, the high crystallinity, and the properties of the grown nanotubes. The results show that the SWNTs from ruthenium have better structural uniformity with less defects and provides an alternative catalyst for SWNTs growth. The successful growth of SWNTs by Ru catalyst provides new experimental information for understanding the growth mechanism of SWNTs, which may be helpful for their controllable synthesis.     

初始温度及碳源对碳纳米管气相爆轰法合成的影响

改变初始温度以及分别使用甲烷和乙炔气体作碳源时气相爆轰合成碳纳米管,研究了初始温度与不同碳源对碳纳米管的影响。利用X射线衍射(XRD)、透射电镜(TEM)、拉曼(Raman)光谱等对碳纳米管进行表征。结果表明,随着初始温度的升高,所合成的碳纳米管的产量减少且石墨化程度降低,但管壁会变得光滑且管径有所增加。当使用乙炔时,所合成的产物中没有碳纳米管,而是合成了石墨化程度较高的无定形碳,随着催化剂量的增加,产物中碳包覆颗粒增多且包覆层清晰可见,但存在结构缺陷。当初始温度在110~130 ℃时,使用甲烷气体运用气相爆轰的手段是合成碳纳米管的较佳方案。     

Investigation of Fe-Co catalyst active component during multi-walled carbon nanotube synthesis by means of synchrotron radiation X-ray diffraction

The investigation of the catalyst active component formation during multi-walled carbon nanotube (MWCNT) synthesis was carried out by means of in situ and ex situ synchrotron radiation X-ray diffraction. The data on phase composition transformations obtained with 1 s time-resolution allows optimization the carbon nanotubes synthesis in industrial fluidized bed reactors.     

The growth of carbon nanotubes on montmorillonite and zeolite (clinoptilolite)

Synthesis of carbon nanotubes described in the present work is based on activation of methane in a hot filament CVD reactor and subsequent creation of nanostructures on a catalyst pre-treated polished surface of silicon. An essential step of the synthesis is the use of natural minerals as catalysts. We have studied the catalyst parameters, the way of its application and the amount of Fe³⁺ cations on the surface of aluminosilicates on the quality of the grown nanotube layers. The growth of carbon nanotubes catalyzed by montmorillonite and zeolite (clinoptilolite) was confirmed by scanning electron microscopy and Raman spectroscopy.     

Functionalization of ultradispersed diamond for DNA detection

Carbon nanotubes have been synthesized by catalytic chemical vapour deposition of acetylene diluted with argon using three different catalysts, namely, nickel formate, cobalt formate and ferrocene. The synthesis was carried out at 700°C in a quartz reactor for 30 minutes. Thermal analysis was carried out in order to determine the yield of the nanotube. It was found that the deposit contains 86% nanotube, with nickel-based catalyst, which was the maximum. The yield of nanotube was 71 times that of the nickel loading. The TEM images reveal helical type of nanotubes with iron catalyst while cobalt and nickel catalysts yielded straight nanotubes. This technique can be explored for the bulk production of carbon nanotube in an economic way.     

Synthesis of single-walled carbon nanotubes in oxy-fuel inverse diffusion flames with online diagnostics

A novel technique for synthesis of single-walled carbon nanotubes (SWNTs) in diffusion flames is presented, as is a diagnostic tool that can provide online information about nanotube size, number density, and purity. An inverse diffusion flame with a high stoichiometric mixture fraction (Z_st) is used to produce SWNTs with an average length of 1 μm. The high Z_st flame allows nanotubes to be produced in a fuel-rich region that is void of soot and polycyclic aromatic hydrocarbons (PAH). In addition, by operating as an inverse diffusion flame the carbon nanotubes (CNTs) are not exposed to oxygen and thus, can be collected downstream. Consequently, this flame provides a potential approach to large-scale synthesis of pure SWNTs. In addition, a differential mobility analyzer (DMA) is employed as an online diagnostic tool. The DMA can distinguish between excess catalyst particles and CNTs due to the differences in their electrical mobilities. Thus, the presence of CNTs as well as their size, number density, and purity relative to excess catalyst particles can be identified from the size distribution of the aerosol sampled downstream of the flame. This tool allows for rapid identification of the effect of changing process variables on nanotube growth and thus, the production process can be quickly optimized.     

Synthesis of carbon nanotubes by CVD: Effect of acetylene pressure on nanotubes characteristics

The effect of acetylene partial pressure on the structural and morphological properties of multi-walled carbon nanotubes (MWCNTs) synthesized by CVD on iron nanoparticles dispersed in a SiO₂ matrix as catalyst was investigated. The general growing conditions were: 110 cm³/min flow rate, 690 °C synthesis temperature, 180 Torr over pressure and two gas compositions: 2.5% and 10% C₂H₂/N₂. The catalyst and nanotubes were characterized by HR-TEM, SEM and DRX. TGA and DTA were also carried out to study degradation stages of synthesized CNTs. MWCNTs synthesized with low acetylene concentration are more regular and with a lower amount of amorphous carbon than those synthesized with a high concentration. During the synthesis of CNTs, amorphous carbon nanoparticles nucleate on the external wall of the nanotubes. At high acetylene concentration carbon nanoparticles grow, covering all CNTs’ surface, forming a compact coating. The combination of CNTs with this coating of amorphous carbon nanoparticles lead to a material with high decomposition temperature.     

Formation of bamboo-shaped carbon nanotubes on carbon black in a fluidized bed

For the first time, bamboo-shaped multiwalled carbon nanotubes, having diameter of the order of 50 nm, have been grown on carbon black in a fluidized bed in bulk amount. The activation energy for the synthesis of the product was found out to be around 33 kJ/mol in the temperature range of 700−900 °C. The carbon nanotubes were separated from the carbon black by preferential oxidation of the later, the temperature of which was determined by thermogravimetry. The transmission electron microscopy revealed different features of the nanotubes such as “Y” junction, bend, and catalyst filling inside the nanotubes. Small angle neutron scattering was performed on the nanotubes synthesized at different temperatures. The data were fitted into a suitable model in order to find out the average diameter, which decreases with increase in synthesis temperature. The Monte Carlo simulation predicts the same behavior. Based on the above observations, a possible growth mechanism has been predicted. The oscillation in carbon saturation value inside the catalyst in the fluidized bed has been indicated as the responsible factor for the bamboo-shaped structure.     

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.     

采用旋转涂膜法制备基底生长的定向碳纳米管阵列

 采用化学气相沉积技术,利用旋转涂膜法制备催化剂基底材料,通过对涂膜过程中的角速度、旋转时间以及基底还原过程中温度的控制改变催化剂颗粒的分布状态,获得了粒径均匀分布的催化剂基底,该基底上催化剂颗粒集中分布在47～62 nm区间,再利用该基底生长出定向碳纳米管阵列。运用扫描电镜、透射电镜、拉曼光谱仪对样品进行了表征。结果表明旋转涂膜法制备的基底平整性好于普通的滴膜法,且较其它基底制备方法具有简单易控、可使催化剂均匀分散等特点。利用该基底制备的碳纳米管阵列定向性良好。     

Pulsed laser CVD investigations of single-wall carbon nanotube growth dynamics

The nucleation and rapid growth of single-wall carbon nanotubes (SWNTs) were explored by pulsed-laser assisted chemical vapor deposition (PLA-CVD). A special high-power, Nd:YAG laser system with tunable pulse width (>0.5 ms) was implemented to rapidly heat (>3×10⁴°C/s) metal catalyst-covered substrates to different growth temperatures for very brief (sub-second) and controlled time periods as measured by in situ optical pyrometry. Utilizing growth directly on transmission electron microscopy grids, exclusively SWNTs were found to grow under rapid heating conditions, with a minimum nucleation time of >0.1 s. By measuring the length of nanotubes grown by single laser pulses, extremely fast growth rates (up to 100 microns/s) were found to result from the rapid heating and cooling induced by the laser treatment. Subsequent laser pulses were found not to incrementally continue the growth of these nanotubes, but instead activate previously inactive catalyst nanoparticles to grow new nanotubes. Localized growth of nanotubes with variable density was demonstrated through this process and was applied for the reliable direct-write synthesis of SWNTs onto pre-patterned, catalyst-covered metal electrodes for the synthesis of SWNT field-effect transistors.     

Short time synthesis of high quality carbon nanotubes with high rates by CVD of methane on continuously emerged iron nanoparticles

We report the variation of yield and quality of carbon nanotubes (CNTs) grown by chemical vapor deposition (CVD) of methane on iron oxide-MgO at 900-1000 °C for 1-60 min. The catalyst was prepared by impregnation of MgO powder with iron nitrate, dried, and calcined at 300 °C. As calcined and unreduced catalyst in quartz reactor was brought to the synthesis temperature in helium flow in a few minutes, and then the flow was switched to methane. The iron oxide was reduced to iron nanoparticles in methane, while the CNTs were growing.TEM micrographs, in accordance with Raman RBM peaks, indicate the formation of mostly single wall carbon nanotubes of about 1.0 nm size. High quality CNTs with I_G/I_D Raman peak ratio of 14.5 are formed in the first minute of CNTs synthesis with the highest rate. Both the rate and quality of CNTs degrades with increasing CNTs synthesis time. Also CNTs quality sharply declines with temperature in the range of 900-1000 °C, while the CNTs yield passes through a maximum at 950 °C. About the same CNTs lengths are formed for the whole range of the synthesis times. A model of continuous emergence of iron nanoparticle seeds for CNTs synthesis may explain the data. The data can also provide information for continuous production of CNTs in a fluidized bed reactor.