调变Ni／Mo／MgO催化剂中Ni／Mo比例可控合成薄壁碳纳米管

采用摩尔分数1%Ni及负载少量Mo的Ni/MO/MgO催化剂裂解甲烷合成薄壁碳纳米管.通过SEM、TEM、XRD和Raman光谱表征方法研究了碳纳米管直径和催化剂中Ni/Mo比例关系.实验发现:通过控制Ni/Mo比例可以调变催化剂颗粒大小以及活性相.TEM及XRD表征发现,随着Ni/Mo比例的降低,金属Mo相逐渐从NiMo合金相中析出.NiMo合金相对应的活性组分颗粒很小,容易催化裂解甲烷形成薄壁碳纳米管;而后析出的Mo相则主要形成了大管径厚壁的碳纳米管.当Ni/Mo比例为6时可以高选择性地获得窄分布,内径为1.3nm,外径为3.0nm的溥壁碳纳米管.Raman光谱进一步验证了碳纳米管含有较少的缺陷.薄壁碳纳米管形成的关键因素主要体现为碳在其表而的快速扩散以及小颗粒的碳纳米管催化剂活性相控制.     

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.     

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。     

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.     

A simple method of producing single-walled carbon nanotubes from a natural precursor: Eucalyptus oil

Single-walled carbon nanotubes (SWNTs) have been synthesized by catalytic decomposition of eucalyptus oil, on a high silica-zeolite support impregnated with Fe/Co catalyst at 850 °C by the spray pyrolysis method. Catalyst with 5 wt.% (molar ratio of Co:Fe = 1:1), impregnated in zeolite was suitable for effective formation of carbon nanotubes (CNTs). As-grown CNTs were characterized by SEM, TEM and Raman spectroscopy. Raman spectroscopy reveals that as-grown CNTs are well graphitized. Raman spectroscopy also reveals that the as-prepared SWNTs have a diameter of about 0.79-1.71 nm.     

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 of carbon nanotubes using Ni95Ti5 nanocrystalline film as a catalyst

Carbon nanotubes (CNTs) were synthesized by low-pressure chemical vapour deposition (LPCVD) using N2:C2H2:H2 gas mixtures on nanocrystalline Ni95Ti5 film. This nanocrystalline film was deposited on silicon substrate using vapour condensation method. The growth temperature and growth time was kept at 800 degrees C and 30 mins, respectively and the pressure was maintained at 10 Torr. The growth mechanism of CNTs was investigated using FESEM, TEM, HRTEM, and Raman Spectroscopy. From FESEM image of Ni95Ti5 nanocrystalline film, it is clear that the particle size varies from 5-10 nm. EDX analysis suggests that Ni95Ti5 alloy contains Ni and Ti both. It is clear from TEM images that CNTs are multiwalled with the diameter varying from 10-30 nm and length of several micrometers. HRTEM image shows that the structure of these multi-walled nanotube (MWNTs) is bamboo-shaped and the catalyst exists at the tip of MWNTs. Fourier Transform Raman Spectroscopy confirmed that graphitic structure of as-prepared CNTs. Field emission measurements reveal that the carbon nanotubes grown for 30 mins showed a turn-on field of 7.2 V/microm, when the current density achieves 10 microA/cm2. The field enhancement factor was calculated to be 708.50 for carbon nanotubes grown for 30 mins.     

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).     

Structural Investigation of Catalytically Grown Carbon Nanotubes

Carbon nanotubes (CNTs) having diameters in the range of 30–50 nm and few micrometers in length were synthesized in one step through a chemical-reduction route under autogenous pressure of H₂/CO₂. The synthesized materials prepared under different experimental conditions were characterized using different techniques. Results showed that V₂O₅ used as a catalyst for the nucleation of CNTs become carburized to vanadium carbide (V₈C₇) and provides a site for growth of CNTs. At high temperature, carbide particles thus formed become encapsulated at the tip of nanotube followed by the growth of CNTs through the tip-growth mechanism. Thermogravimetric analysis results showed that the CNTs obtained after the longer reaction time are more stable at high temperatures. Raman analysis showed a well-ordered graphite structure.     

Conversion of plastic waste into CNTs using Ni/Mo/MgO catalyst—An optimization approach by mixture experiment

A combustion technique is used to study the synthesis of carbon nano tubes from waste plastic as a precursor and Ni/Mo/MgO as a catalyst. The catalytic activity of three components Ni, Mo, MgO is measured in terms of amount of carbon product obtained. Different proportions of metal ions are optimized using mixture experiment in Design expert software. D-optimal design technique is adopted due to nonsimplex region and presence of constraints in the mixture experiment. The activity of the components is observed to be interdependent and the component Ni is found to be more effective. The catalyst containing Ni_0.8Mo_0.1MgO_0.1 yields more carbon product. The structure of catalyst and CNTs are studied by using SEM, XRD, and Raman spectroscopy. SEM analysis shows the formation of longer CNTs with average diameter of 40–50 nm.     

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.     

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.     

Influence of Mo or Cu doping in Fe/MgO catalyst for synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of methane

A series of mono-, bi- or tri-metallic Fe–Mo-Cu/MgO catalysts with the same metal loading of 6 wt% were prepared by impregnation method and used as catalysts for synthesis single-walled carbon nanotubes (SWCNTs) via methane decomposition. XRD, H₂-TPR, and nitrogen physisorption techniques were used to characterize the freshly calcined catalysts, while HRTEM, Raman spectroscopy and TGA were employed to investigate the morphology and microstructure of the SWCNTs product. The obtained results indicated that the introduction of Mo or Cu in the Fe/MgO catalyst enhanced the catalytic growth activity. TEM images showed that both bundles and isolated SWCNTs were obtained over Mo containing catalysts, whereas only SWCNTs bundles were grown over the Fe-Cu/MgO catalyst. The obtained SWCNTs having a diameter of around 0.9–2.4 nm. Raman analysis illustrated that all promoted catalysts produced high quality of SWCNTs compared to the unpromoted Fe/MgO catalyst.     

Effect of Co and Ni nanoparticles formation on carbon nanotubes growth via PECVD

The effect of cobalt (Co) and nickel (Ni) nanoparticle catalysts on the growth of carbon nanotubes (CNTs) were studied, where the CNTs were vertically grown by plasma enhanced chemical vapour deposition (PECVD) method. The growth conditions were fixed at a temperature of 700 °C with a pressure of 1000 mTorr for 40 minutes with various thicknesses of sputtered metal catalysts. Only multi-walled carbon nanotubes are present from the growth as large average diameter of outer tube (～10–30 nm) were measured for both of the catalysts used. Experimental results show that high density of CNTs was observed especially towards thicker catalysts layers where larger and thicker nanotubes were formed. The nucleation of the catalyst with various thicknesses was also studied as the absorption of the carbon feedstock is dependent on the initial size of the catalyst island. The average diameter of particle size increases from 4 to 10 nm for Co and Ni catalysts. A linear relationship is shown between the nanoparticle size and the diameter of tubes with catalyst thicknesses for both catalysts. The average growth rate of Co catalyst is about 1.5 times higher than Ni catalyst, which indicates that Co catalyst has a better role in growing CNTs with thinner catalyst layer. It is found that Co yields higher growth rate, bigger diameter of nanotube and thicker wall as compared to Ni catalyst. However, variation in Co and Ni catalysts thicknesses did not influence the quality of CNTs grown, as only minor variation in I_G/I_D ratio from Raman spectra analysis. The study reveals that the catalysts thickness strongly affects not only nanotube diameter and growth rate but also morphology of the nanoparticles formed during the process without influencing the quality of CNTs.     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。     

Synthesis of sea urchin-like carbon nanotubes on nano-diamond powder

Carbon nanotubes (CNTs) have unique atomic structure and properties, such as a high aspect ratio and high mechanical, electrical and thermal properties. On the other hand, the agglomeration and entanglement of CNTs restrict their applications. Sea urchin-like multiwalled carbon nanotubes, which have a small aspect ratio, can minimize the problem of dispersion. The high hardness, thermal conductivity and chemical inertness of the nano-diamond powder make it suitable for a wide range of applications in the mechanical and electronic fields. CNTs were synthesized on nano-diamond powder by thermal CVD to fabricate a filler with suitable mechanical properties and chemical stability. This paper reports the growth of CNTs with a sea urchin-like structure on the surface of the nano-diamond powder. Nano-diamond powders were dispersed in an attritional milling system using zirconia beads in ethanol. After the milling process, 3-aminopropyltrimethoxysilane (APS) was added as a linker. Silanization was performed between the nano-diamond particles and the metal catalyst. Iron chloride was used as a catalyst for the fabrication of the CNTs. After drying, catalyst-attached nano-diamond powders could be achieved. The growth of the carbon nanotubes was carried out by CVD. The CNT morphology was examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The mean diameter and length of the CNTs were 201 nm and 3.25 microm, respectively.     

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).     

Effect of ferrocene catalyst particle size on structural and morphological characteristics of carbon nanotubes grown by microwave oven

The influence of catalyst particle size on the formation and diameter of carbon nanotubes (CNTs) is investigated. Ferrocene catalyst with an average diameter of 19.7, 21.4, 23.6 and 27.0 µm is used for the growth of CNTs by a cost-effective and facile method using microwave oven. Morphological observations by transmission electron microscopy and field emission scanning electron microscopy reveal consistently that smaller catalyst diameter generates CNTs with smaller diameter. Raman spectroscopy indicates that the full width at half maximum of G-, D- and 2D-bands decreases gradually with increasing CNTs diameter; meanwhile, G-band/D-band intensity ratio is found to be sensitive to crystal defects, showing a drop for CNTs diameter in the range 25–40 nm then followed by a slight increase for higher diameters. This may be associated with CNTs curvature and strain which developed along tube walls. X-ray diffraction analysis demonstrates an increase in d ₍₀₀₂₎ interlayer spacing with decreasing CNTs diameter. Furthermore, CNTs diameter is found to be inversely proportional to (002) linewidth. Finally, the energy band gap estimated from UV–NIR–Vis measurements increases slightly with CNTs diameter, 5.69–5.84 eV.     

Growth of carbon nanotubes over Fe-Co and Ni-Co catalysts supported on different phases of TiO2 substrate by thermal CVD

The aim of this work is to examine the properties of CNTs formed on Fe-Co and Ni-Co bimetallic catalysts supported on different phases of TiO₂ (anatase and rutile) by wet impregnation method. The CNTs are grown from decomposition of acetylene via Thermal CVD at 700°C using the prepared catalysts. The nanomaterials were characterized by XRD, Xmap, BET, FESEM, TEM, and Raman spectroscopy. It was found that the catalyst samples supported on rutile TiO₂ have higher specific surface area, smaller catalytic nanoparticles with denser distribution and very more activity compared to anatase ones. Consequently, the CNTs nucleated from nanoparticles supported on rutile TiO₂ possess higher density, smaller average diameters and narrower diameter distribution compared to grown CNTs on anatase samples. Moreover, it was observed that the Fe-Co bimetallic catalysts regardless of TiO₂ support phase, possesses more catalytic activity and higher average growth rate of CNTs in compare with Ni-Co catalysts.     

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.