Carbon dioxide as a carbon source for synthesis of carbon nanotubes by chemical vapor deposition

Carbon dioxide was successfully used as carbon source in the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) over Fe/CaO catalyst. The product was evaluated using both transmission electron microscopy (TEM) and Raman spectroscopy. Crooked and branching structures of multi-walled carbon nanotubes (MCNTs) with diameters of around 50 nm were observed on the TEM micrographs. Raman spectrum results show that the nanotubes have small defects, which is in agreement with the results of TEM. The influence of reaction variable such as furnace temperature and types of support media was also studied and the reaction mechanism was then discussed in this paper.     

SEM and raman spectroscopy of multiwalled carbon nanotubes grown by novel technique of ash supported catalysts

Multiwalled carbon nanotubes (MWCNTs) were grown on a novel ASC catalyst and on catalyst deposited by SCC method on silicon wafer, by thermal CVD of acetylene. Fe and Ni were used as catalyst for ASC. Samples were analyzed by SEM and Raman spectroscopy. SEM analysis shows that CNTs grown on ASC have narrower diameter distribution (64+/-6 nm) compared to CNTs grown on SCC (67+/-10.5 nm). However, SEM and Raman spectroscopy studies show CNTs grown on SCC are of better quality. The same samples were studied after standard purification procedure of oxidation after annealing at high temperatures. SEM and Raman spectroscopy show that overall quality of ensemble of CNTs has improved. After annealing, diameter decreases for larger diameter approximately 200 nm nanotubes while it increases for CNTs of smaller diameter approximately 70 nm. To explain the increase in diameter of approximately 70 nm CNT's, a phenomenological model has been proposed. The results of Raman spectroscopy and SEM corroborate the proposed model.     

碳纳米管/羟基磷灰石复合材料的制备及表征

以含钴介孔分子筛为催化剂、乙醇为碳源, 采用CVD法制备碳纳米管(CNTs)。通过原位合成法制备一系列不同碳纳米管含量的碳纳米管/羟基磷灰石(CNTs/HA)复合材料。分别采用XRD、FTIR、TEM、N₂吸附-脱附和Raman光谱等分析手段, 对所合成CNTs/HA复合材料的晶相、结构、形貌和比表面积等进行了表征。同时研究了碳纳米管的添加量对所合成CNTs/HA复合材料形貌的影响。XRD与Raman结果表明, 所得CNTs/HA复合粉体中仅有CNTs与HA两种物相, 纯度较高, 结晶度较好; TEM结果显示, CNTs/HA复合材料中CNTs表面均匀包裹着一层纳米级的针状HA晶粒, 两者形成了较强的界面结合, 且当CNTs与HA的质量比为3:17时, CNTs与HA形成最佳结合状态; N₂吸附-脱附表征结果表明, 与HA的比表面积相比, CNTs/HA复合材料具有较高比表面积。     

Influence of catalyst particles on multi-walled carbon nanotubes morphology and structure

Multi-walled carbon nanotubes (MWCNTs) have been successfully grown by Chemical Vapor Deposition (CVD) method. Elucidating the key characteristics of catalyst sources that affect carbon nanotubes growth is of great importance for improving and control MWCNTs morphology and structure. In this work we present a systematically study of CVD parameters, such as catalyst source, substrate morphology and temperature and how it affects carbon nanotubes synthesis. The novelty of this work lies on the catalyst composition. Two specific catalyst sources were analyzed: (i) Fe₂Co and (ii) Fe₂Co with ferrocene. Cyclic Voltammetry results confirmed the presence of Fe²⁺ in the Fe₂Co with ferrocene solution. X-Ray Diffraction analysis confirmed the presence of iron particles on the substrate surface after its submission to growth conditions. Raman results suggested an improvement in carbon nanotubes crystalline quality catalyzed by Fe₂Co with ferrocene. For tridimensional substrates such as fibers, the Fe₂Co with ferrocene provided aligned CNTs with lower defects density noticed in Raman spectra and SEM micrographs. Finally, we corroborated the Fe²⁺ encapsulation relation with the growth mechanism and MWCNTs formation.     

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.     

基于三元金属催化剂制备碳纳米管/三维石墨烯复合材料及电容性能

通过均匀沉淀法合成Ni-Mg-Al三元金属氧化物（TMO）,再通过一步化学气相沉积法（CVD）以CH₄为碳源、Ar为保护性气体,在原位还原的Ni上生长碳纳米管（CNTs）,在Mg和Al的金属氧化物上生长石墨烯（GR）,利用水热法刻蚀掉TMO,制备CNTs/三维石墨烯（3DGR）复合材料。基于CNTs与GR两种组分生长动力学的差异,通过控制Ni、Mg和Al三种金属离子的摩尔比、生长温度、生长时间,调控和优化CNTs/3DGR复合材料的结构及电容性能。借助TEM、SEM、EDS、Raman和XRD对CNTs/3DGR复合材料的结构、形貌、组分进行表征。结果表明,CNTs与GR协同作用为CNTs/3DGR复合材料提供了更多电子运输通道,可大幅提高导电性能,实现电容性能的提升,CNTs/3DGR复合材料的比电容最高可达20 F/g。      

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).     

Carbon nanotubes rooted montmorillonite (CNT-MM) reinforced nanocomposite membrane for PEM fuel cells

Nafion based nanocomposite membranes containing montmorillonite-carbon nanotubes (a binary hybrid material) were produced to develop high performance polymer electrolyte fuel cells. Multi walled carbon nanotubes were grown over 20 and 25 wt% iron loaded montmorillonite catalysts by CVD using acetylene as the carbon precursor. Growth experiments were carried out at optimised conditions to obtain highly selective crystalline carbon nanotubes. X-ray diffraction spectra of the catalysts were recorded for the structural characterisation and definition of particle size. The carbon nanotubes obtained were examined by various physico chemical characterisation studies such as SEM, TEM, Raman spectroscopy and TG analyses to understand the morphology and crystallinity of the CNTs. The MM-CNT hybrid material with I_D/I_G ratio of Raman spectral band as 0.53 represents the high selectivity towards CNTs. Thus the hybrid material produced was considered as the best nanofiller to develop polymer nanocomposites. Nafion based nanocomposite membranes were prepared by adding MM-CNT as nanofiller by solution casting method. A better dispersion of MM-CNT into the Nafion matrix was observed and the addition of the MM-CNT improved the thermal stability of the Nafion membrane.     

The influence of Ni catalyst on the growth of carbon nanotubes on Si substrates

This article treats the influence of the treatment of a Ni catalyst upon the growth of carbon nanotubes in alcohol catalytic chemical vapour deposition (AC CVD) equipment. Prior to the growth of diamond, a thin film of Ni was deposited on a silicon substrate by magnetron sputtering. We observed that a combination of annealing of the Ni catalyst in vacuum and NH₃ had a positive effect upon the growth of carbon nanotubes (CNTs). The prepared CNTs were analysed by scanning electron microscopy and Raman spectroscopy.     

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.     

Fabrication of flat capped carbon nanotubes using an arc-discharge method assisted with a Sm-Co catalyst

In this study, carbon nanotubes (CNTs) were fabricated using an arc-discharge method assisted with samarium-cobalt (Sm-Co) chloride as a catalyst. The optimal fabrication condition was determined through a series of experiments on various ambient conditions. Observations were completed using scanning electron microscopy (SEM), Raman spectroscopy, and tunneling electron microscopy (TEM); the main products we observed are well-structured multi-walled carbon nanotubes. By identifying the radial breathing modes (RBMs) of the Raman spectra with a TEM micrograph, we also observed a small number of single-walled carbon nanotubes. With the assistance of the Sm-Co chloride catalyst, the RBMs of the Raman spectra were measured in the ambient pressure of 760 torr. The TEM observations revealed that our nanotubes have good graphitic structures and almost no bamboo defects, which agrees with their Raman measurements with a high I_G/I_D ratio (~88). A perfect graphitic flat cap was found to be attached at the end of the nanotube. Simulation shows that by incorporating 5 carbon pentagons, it is possible to construct a flat capped carbon nanotube. The results of our experiment offer a unique approach to growing high quality CNTs. Such a flat capped structure may useful for further advanced application in nano-electronics and nano-optics.     

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.     

Growth of horizontally aligned dense carbon nanotubes from trench sidewalls

Horizontally aligned, dense carbon nanotubes (HADCNTs) in the form of CNT cantilevers/bridges were grown from selected trench sidewalls in silicon substrate by chemical vapor deposition (CVD). The as-grown CNT cantilevers/bridges are packed with multiwalled carbon nanotubes (MWCNTs) with a linear density of about 10 CNTs μm(-1). The excellent horizontal alignment of these CNTs is mainly ascribed to the van der Waals interactions within the dense CNT bundles. What is more, the Raman intensity ratio I(G)/I(D) shows a gradual increase from the CNT roots to tips, indicating a defect gradient along CNTs generated during their growth. These results will inspire further efforts to explore the fundamentals and applications of HADCNTs.     

Synthesis and purification of bimetallic catalysed carbon nanotubes in a horizontal CVD reactor

Carbon nanotubes (CNTs) were synthesised by a conventional chemical vapour deposition (CVD) method using acetylene as carbon source and a bimetallic catalyst of Fe–Co supported on a CaCO₃ support. The CNTs were characterised by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy (RS), energy dispersive X-ray spectroscopy (EDS) and thermogravimetric analysis (TGA). The TEM images show clustered CNTs and reveal the outer and inner diameters of these nanomaterials. The XRD analysis shows the characteristic broad peak of graphitised carbon; the RS indicates that these materials have a high degree of crystallinity while the TGA shows the high thermal stability of the materials. EDS analysis also indicates that the purification method employed was able to remove the impurities in the CNT samples.     

Study on the controllable scale-up growth of vertically-aligned carbon nanotube arrays

Vertically aligned carbon nanotubes (VA-CNTs) with high purity have been grown on quartz substrate via the gas phase catalytic chemical vapour deposition (CVD) by using ferrocene as the catalyst source and camphor as the carbon source. The effects of catalyst concentration, flow rate and water assistance on the morphology and structure of VA-CNTs are investigated by SEM, TEM, Raman and XPS characterizations. Under the optimized CVD conditions with modest ferrocene concentration and flow rate, dense and well VA-CNT arrays have been obtained. The water concentration should be controlled to improve CNTs alignment and impurity without damaging the walls of CNTs.     

Comparison of nanotubes produced by fixed bed and aerosol-CVD methods and their electrical percolation behaviour in melt mixed polyamide 6.6 composites

The electrical percolation behaviour of five different kinds of carbon nanotubes (CNTs) synthesised by two CVD techniques was investigated on melt mixed composites based on an insulating polyamide 6.6 matrix. The electrical percolation behaviour was found to be strongly dependent on the properties of CNTs which varied with the synthesis conditions. The lowest electrical percolation threshold (0.04 wt.%) was determined for as grown multi-walled carbon nanotubes without any purification or chemical treatment. Such carbon nanotubes were synthesised by the aerosol method using acetonitrile as ferrocene containing solvent and show relatively low oxygen content near the surface, high aspect ratio, and good dispersability. Similar properties could be found for nanotubes produced by the aerosol method using cyclohexane, whereas CNTs produced by the fixed bed method using different iron contents in the catalyst material showed much higher electrical percolation thresholds between 0.35 and 1.02 wt.%.     

Structural characterization of a mechanically milled carbon nanotube/aluminum mixture

The structural evolution of carbon nanotubes (CNTs) during mechanical milling was investigated using SEM, TEM, XRD, XPS and Raman spectroscopy. The study showed that milling of the CNTs alone introduces defects but preserves the tubular structure. When milling the CNTs with aluminum (Al) powder in order to produce a composite, Raman spectroscopy has shown that most of the nanotubes are destroyed. During sintering of the CNT/Al milled mixture, the carbon atoms available from the destruction of the nanotubes react with the Al to form aluminum carbide (Al₄C₃). The effect of milling on the Al matrix was also studied.     

催化裂解天然气于碳毡内低成本合成碳纳米管

基于制备碳/碳(C/C)复合材料的等温化学气相渗透(ICVI)技术,在1010～1100℃用Fe催化裂解工业天然气可在碳毡内原位合成出碳纳米管(CNTs).扫描电镜(SEM)观察结果表明,1060℃合成的CNTs具有较好的覆盖形貌和均匀管径(110～120nm)且纯净度高.高分辨率透射电镜(HRTEM)和Raman光谱测试结果进一步表明,该温度下合成的CNTs结晶度高,与碳纤维间结合力强.     

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.     

Synthesis and characterization of Ni-Si mixed oxide nanocomposite as a catalyst for carbon nanotubes formation

Ni-Si mixed oxide nanocomposite was prepared by co-precipitation method with Ni(NO₃)₂ · 6H₂O and tetraethylorthosilicate (TEOS) at pH = 10.5 under reflux condition for 6 days. It was then used as a catalyst for the formation of carbon nanotubes (CNTs) by CVD procedure. Characterization of the catalyst and the CNTs was carried out using X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results showed that Ni-Si mixed oxides nanorods with the average diameter of 3 to 4 nm play a key role in CNTs formation.