Continuous synthesis of carbon nanotubes using a metal-free catalyst by CVD

This study demonstrates the first example of the use of a metal-free catalyst for the continuous synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD). In this paper silica nanoparticles produced from the thermal decomposition of PSS-(2-(trans-3,4-Cyclohexanediol)ethyl)-Heptaisobutyl substituted (POSS) were used as catalyst and ethanol was served as both the solvent and the carbon source for nanotube growth. The POSS/ethanol solution was nebulized by an ultrasonic beam. The tiny mists were continuously introduced into the CVD reactor for the growth of CNTs. The morphology and structure of the CNTs have been investigated by scanning electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. The obtained CNTs have a multi-walled structure with diameters mainly in the size range from 13 to 16 nm. Detailed investigations on the growth conditions indicate that the growth temperature and POSS concentration are important for achieving high-quality nanotubes, and that the existing of small amount of water in ethanol is effective to remove amorphous carbon species during the formation of CNTs. The mass production of CNTs without any metal contaminant will provide a chance for investing and understanding the intrinsic properties of CNTs and applications particularly in nanoelectronics and biomedicines.     

以NiZnAl催化剂制备碳纳米管及其反应活性的研究

采用FC化合物作为一种新型催化剂--NiZnAl催化剂的前驱物,以催化热解法合成出了碳纳米管.管状、竹节状、鱼骨状和分叉状等多种形态的碳纳米管均被观测到.在碳纳米管生长过程中位于其顶端的准液态金属颗粒是其形成多种形态碳纳米管的关键.Zn的添加可能使得经煅烧和还原后的Ni催化剂的活性产生了微妙的变化.     

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.     

High-quality single-walled carbon nanotubes synthesis by hot filament CVD on Ru nanoparticle catalyst

We investigated the single-walled carbon nanotubes (SWCNTs) growth on Ru nanoparticle catalyst via hot filament assisted chemical vapor deposition (HFCVD) with two independent W filaments for the carbon precursor (methane) and the hydrogen dissociation respectively. The Ru nanoparticles were obtained following a two-step strategy. At first the growth substrate is functionalized by silanisation, then a self assembly of a ruthenium porphyrin complex monolayer on pyridine-functionalized metal oxide substrates. We have studied the impact of the filaments power and we optimized the SWCNTs growth temperature. The as grown SWCNTs were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. It was found that the quality, density and the diameter of SWCNTs depends on the filament and growth temperature. Results of this study can be used to improve the understanding of the growth of SWCNTs by HFCVD.     

CVD synthesis of carbon nanotubes

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.     

浮动催化体系中碳纳米管的生长机理

提出了气相形核生长（VPN）机理解释浮动催化体系中碳纳米管的生长过程。浮动催化系统中生长碳纳米管的活性碳原子是由苯热解产生的,被硫原子部分覆盖的液态铁颗粒是单壁碳纳米管的形核中心,生成的单壁碳纳米管继续径向生长、逐渐石墨化后,得到多壁碳纳米管。气相形核生长机理能够解释浮动催化系统生长碳纳米管的结构特征。     

CoO/MgO气凝胶催化剂合成单壁纳米碳管

以Co(NO)3·6H2O和Mg(NO)3·6H2O为催化剂前驱体,采用溶胶凝胶和超临界干燥法制备了CoO/MgO气凝胶。用XRD、EDS和TEM对气凝胶的组成和微观结构进行了表征,并通过BET法计算其比表面积和孔体积分别为243 9m2/g和0 7245cm3/g。利用CoO/MgO气凝胶作为催化剂合成单壁纳米碳管,采用TEM、HRTEM、Raman对产物形貌和结构进行了表征,结果表明:产物主要是由高质量单壁纳米碳管组成。     

Ni-La-Mg上催化裂解甲烷生成碳纳米管的研究

采用气相沉积法催化合成碳纳米管，研究了反应条件及镍基催化剂中镧(La)的加入对合成碳纳米管的影响，并用TEM，XRD，BET表，正其形貌和结晶度，实验结果表明：Ni—La—Mg(摩尔比为1：0．1：1)催化剂在600℃反应60min时表现出最佳活性，镍基催化剂中加入La后，能使所合成的碳纳米管管径更细，石墨化程度更高，热稳定性更好．     

Preparation of Pt-Ru bimetallic catalyst supported on carbon nanotubes

The template carbonization of polyphenyl acetylene yields hollow, uniform cylindrical carbon nanotubes with outer diameter almost equal to pore diameter of the template used. High resolution transmission electron microscopic investigation reveals that Pt-Ru nanoparticles are highly dispersed inside the tube with an average particle size of 1.7 nm.     

浮动催化法制备竹节状碳纳米管的研究

报道了竹节状碳纳米管的浮动催化法合成,通过对生长因素的控制可以用浮动催化法连续合成竹节状碳纳米管.实验发现关键因素是采用正己烷为碳源,并且详细讨论了影响竹节状碳纳米管生长的其它重要因素.结果表明碳纳米管的形态结构与碳源分子有直接关系.     

Optimization of synthesis condition for carbon nanotubes by chemical vapor deposition on Fe-Ni-Mo/MgO catalyst

Catalyst and reaction conditions are the main affecting factors for the yield and quality of carbon nanotubes (CNTs) produced by the chemical vapor deposition (CVD) method. In this paper a ternary component catalyst based on Fe-Ni-Mo/MgO was explored using methane as precursor. The influences of temperature and methane concentration were investigated, and the as-produced CNTs were characterized by SEM, HRTEM, XRD and TGA. The diameter of the CNTs is in the range of 20-30 nm and the maximum carbon yield can reach up to 80 times of the catalyst under the selected condition. The purity of the as-prepared CNTs is over 93%. Our results indicated that this novel tercomponent catalyst presented a good catalytic activity for manufacturing high quality and quantity of CNTs.     

Growth of double-walled carbon nanotubes using a conditioning catalyst

Here we describe the effect of different synthetic conditions on the quality and purity of double-walled carbon nanotubes (DWNTs) with the aid of a conditioning catalyst. By lowering the reaction temperature down to 875 degrees C and utilizing a conditioning catalyst, increased purity and a decreased inner diameter of the DWNTs was achieved, while adverse results were observed with increasing reaction temperature. Based on detailed high-resolution transmission electron microscopy studies on the diameter distribution of the tubes, preferential growth conditions for DWNTs over single-wall carbon nanotubes are identified solely from increased carbon solubility considerations (caused by an increased portion of active carbon species by use of Mo) for the same distribution of metal particles.     

Large-scale synthesis of BN nanotubes using carbon nanotubes as template

Boron nitride nanotubes (BN-NTs) were synthesized in large scale by the reaction of NaBH₄ and NH₄Cl in the temperature range of 500-600 °C for 10-18 h, where carbon nanotubes (CNTs) were mixed together with the reactants to serve as template. Pure BN-NTs were obtained by oxidizing the product at about 800 °C in air atmosphere. The structure and morphology of the product with a surface area of 106.635 m²/g were characterized by X-ray diffraction, transmission electron microscopy, Fourier transformation infrared spectroscopy, and thermogravimetric analysis. Large scale preparation of BN-NTs could be realized by this simple and effective route.     

Role of the catalyst in the growth of single-wall carbon nanotubes

Classical molecular dynamics simulations are carried out to analyze the physical state of the catalyst, and the growth of single-wall carbon nanotubes under typical temperature and pressure conditions of their experimental synthesis, emphasizing the role of the catalyst/substrate interactions. It is found that a strong cluster/substrate interaction increases the cluster melting point, modifying the initial stages of carbon dissolution and precipitation on the cluster surface. Experiments performed on model Co-Mo catalysts clearly illustrate the existence of an initial period where the catalyst is formed and no nanotube growth is observed. To quantify the nature of the Co-Mo2C interaction, quantum density functional theory is applied to characterize structural and energetic features of small Co clusters deposited on a (001) Mo2C surface, revealing a strong attachment of Co-clusters to the Mo2C surface, which may increase the melting point of the cluster and prevent cluster sintering.     

铁填充碳纳米管的原位合成

以无水三氯化铁为催化剂前驱体,乙烯为碳源,采用浮游催化法成功大量合成铁填充型碳纳米管.系统地考察了催化剂输入浓度及载气种类对产物的影响.利用环境扫描电子显微镜、透射电子显微镜、X-射线衍射、拉曼光谱和振动磁强计等多种技术手段对产物进行了表征.结果表明:三氯化铁可以替代传统上惯用的有机金属化合物二茂铁作为催化剂前驱体,具有廉价、可控性好等优点,得到的碳纳米管内腔填充有连续的Fe纳米线;这些Fe填充纳米管具有超顺磁性.     

Recent advances in laser synthesis of single-walled carbon nanotubes

Very shortly following the discovery of single-walled carbon nanotubes laser-based methods emerged as reliable ways to produce moderate quantities with very consistent composition and properties. They have also proven to be good platforms for the systematic investigation of various synthesis parameters in the hope of better understanding the growth process. Several variations exist with differences such as laser wavelength, number of lasers, background temperature, and target composition. A number of common elements have emerged for the production of both high quality and high yields of SWNT, such as the effectiveness of bimetal catalysts like CoNi and NiY, and the need for high process temperatures and controlling the rate of cooling. Combined with the growing amount of in situ diagnostic and computational modelling data we are slowly making progress towards understanding the growth process. This article will present an overview of recent advancements in laser-based synthesis methods and what information can be extracted about the growth process.     

碳纳米管在催化反应中的应用

综述了近年来碳纳米管用作催化剂或者载体的研究进展,与传统的催化剂相比,碳纳米管作催化剂或载体都表现出更好的活性、选择性和稳定性.     

A self-assembled synthesis of carbon nanotubes for interconnects

We report a novel approach to grow highly oriented, freestanding and structured carbon nanotubes (CNTs) between two substrates, using microwave plasma chemical vapour deposition. Sandwiched, multi-layered catalyst structures are employed to generate such structures. The as-grown CNTs adhere well to both the substrate and the top contact, and provide a low-resistance electric contact between the two. High-resolution scanning electron microscope (SEM) images show that the CNTs grow perpendicular to these surfaces. This presents a simple way to grow CNTs in different, predetermined directions in a single growth step. The overall resistance of a CNT bundle and two CNT-terminal contacts is measured to be about 14.7?k Ω. The corresponding conductance is close to the quantum limit conductance G(0). This illustrates that our new approach is promising for the direct assembly of CNT-based interconnects in integrated circuits (ICs) or other micro-electronic devices.     

Inner-diameter enlargement of multi-walled carbon nanotubes by adding HBO3 in catalyst

Multi-walled carbon nanotubes (MWCNTs) with large inner diameter were synthesized by the catalytic chemical vapor deposition method using HBO₃ as the accessorial catalyst in reaction precursors. A ratio D_in/D_out is defined as an index to evaluate the hollow degree of MWCNTs, where D_in and D_out are the inner and outer diameter of one CNT, respectively. When no HBO₃ was added in the reaction mixtures, the MWCNTs are straight with thick wall. The average D_in/D_out value is only 0.08 ± 0.02. The X-ray diffraction (XRD) result shows the relatively low crystallinity. When HBO₃ was added in the reaction precursors, the MWCNTs have large inner cavity and the average D_in/D_out value reaches 0.57 ± 0.10. The crystallinity was also improved remarkably. These results indicate that HBO₃ in the catalyst system has great influence on the growth of MWCNTs.