Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

Synthesis and characterization of highly-ordered barium-strontium titanate nanotube arrays fabricated by sol—gel method

Highly uniformed barium-strontium titanate nanotube arrays were fabricated using a porous anodic aluminum oxide template from a barium-strontium titanate sol--gel solution. Electron microscope results showed that nanotubes with uniform length and diameter were obtained. The diameters and lengths of these nanotubes were dependent on the pore diameter and the thickness of the applied anodic aluminum oxide template. High resolution transmission electron microscopy and the selected-area electron diffraction pattern investigations demonstrated the perovskite structure and the polycrystalline of the fabricated barium-strontium titanate nanotubes. The characterization of the electrical and dielectric properties had also been made. Compared to thin film material, the intrinsic leakage current density is almost the same. Besides, at 30~℃, the dielectric constant and dielectric loss of the fabricated nanotube is 80 and 0.027 at 1~MHz respectively.     

多壁碳纳米管太赫兹图谱研究

近年来碳纳米管是一个重要的研究领域,但研究重点主要是其电子、光学和机械等特性。尽管有关单壁碳纳米管的在远红外光谱已有诸多报道,但多壁碳纳米管这方面的研究却较少。试验采用太赫兹时域光谱系统对多壁碳纳米管进行表征,同时也用扫描电镜对其进行形貌检测和微区成分分析,以深入了解其特性。检测结果显示,在0.2～2.0 THz内,样品折射率随着频率的增加而减小,吸收系数却随着频率的增加而增加,并可以拟合斜率为1.92的直线;样品的内径为5～15 nm、外径为15～25 nm,且长度达到了微米级,样品含C量大约为94%,其他为O和Cl杂质元素。根据泰勒扩展式和麦克斯韦方程,得到了样品在该太赫兹频域内吸收的数学模型,该数学模型基本上与检测结果一致。该样品的太赫兹吸收特性主要取决于其化学组成和分子的大小,含C量不同的碳纳米管预示着具有不同的太赫兹图谱和独特的功能。     

Selective growth, characterization, and field emission performance of single-walled and few-walled carbon nanotubes by plasma enhanced chemical vapor deposition

Single-walled carbon nanotubes (SWCNTs) and few-walled carbon nanotubes (FWCNTs) have been selectively synthesized by plasma enhanced chemical vapor deposition at a relative low temperature (550 °C) by tuning the thickness of iron catalyst. The parametric study and the optimization of the nanotube growth were undertaken by varying inductive power, temperature, catalyst thickness, and plasma to substrate distance. When an iron film of 3-5 nm represented the catalyst thickness for growing FWCNT arrays, SWCNTs were synthesized by decreasing the catalyst thickness to 1 nm. The nanotubes were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. Electron field emission properties of the nanotubes indicate that the SWCNTs exhibit lower turn-on field compared to the FWCNTs, implying better field emission performance.     

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.     

Electron diffraction on graphite nanocrystals in the walls of carbon nanotubes

The structure and defects in the walls and cavities of carbon nanotubes were examined by electron diffraction, transmission electron microscopy, energy dispersive X-ray analysis and Raman spectroscopy. The predominating defects in the walls of the nanotubes are graphite nanocrystals having a preferential orientation in the direction of the nanotube axis, and another significant type of defects are particles of the catalyst in the nanotube cavities. In the cavities, also the presence of molybdenum was proved having its origin in the catalyst.     

Hydrogen-free spray pyrolysis chemical vapor deposition method for the carbon nanotube growth: Parametric studies

Spray pyrolysis chemical vapor deposition (CVD) in the absence of hydrogen at low carrier gas flow rates has been used for the growth of carbon nanotubes (CNTs). A parametric study of the carbon nanotube growth has been conducted by optimizing various parameters such as temperature, injection speed, precursor volume, and catalyst concentration. Experimental observations and characterizations reveal that the growth rate, size and quality of the carbon nanotubes are significantly dependent on the reaction parameters. Scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy techniques were employed to characterize the morphology, structure and crystallinity of the carbon nanotubes. The synthesis process can be applied to both semiconducting silicon wafer and conducting substrates such as carbon microfibers and stainless steel plates. This approach promises great potential in building various nanodevices with different electron conducting requirements. In addition, the absence of hydrogen as a carrier gas and the relatively low synthesis temperature (typically 750 °C) qualify the spray pyrolysis CVD method as a safe and easy way to scale up the CNT growth, which is applicable in industrial production.     

Differences in the catalyst removal from single- and double-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) and double-walled carbon nanotubes (DWCNTs) synthesized by a catalytic chemical vapor deposition method showed partially incorporated metal catalysts inside the graphene walls. In order to remove the metal catalysts, acid and thermal treatments were successively carried out. The methods for effective catalyst removal in SWCNTs and DWCNTs were examined by means of thermogravimetric analysis, electron microscopy, and electron paramagnetic resonance. The DWCNTs showed distinctly different metal catalyst removal behavior from that of SWCNTs due to the double-wall structure. The acid treatment is less efficient for catalyst removal from DWCNTs, while catalysts in SWCNTs are effectively removed by acid treatment. Additional thermal treatment is quite effective to remove metal catalysts from DWCNTs.     

Surface chemical functionalized single-walled carbon nanotube with anchored phenol structures: Physical and chemical characterization

Surface functionalization of single-walled carbon nanotube was carried out by introducing ylides groups containing anchored phenol structures. The functionalized nanotube is characterized using elemental analysis, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, Raman spectroscopy and zeta potential measurements. Elemental and FT-IR analysis reveal the successful functionalization of azomethine ylides. Raman spectroscopic studies corroborates that the surface functionalization does not affect the basic crystal domain size of the nanotubes. Functionalized carbon nanotubes exhibit higher zeta potential values showing its higher dispersant ability in water and acetone solvent in comparison to pure carbon nanotube.     

Synthesis, characterization and electrochemical behavior of polypyrrole/carbon nanotube composites using organometallic-functionalized carbon nanotubes

Thorn-like, organometallic-functionalized carbon nanotubes were successfully developed via a novel microwave hydrothermal route. The organometallic complex with methyl orange and iron (III) chloride served as reactive seed template, resulting in the oriented polymerization of pyrrole on the modified carbon nanotubes without the assistance of other oxidants. Morphological and structural characterizations of the carbon nanotube/methyl orange-iron (III) chloride and polypyrrole/carbon nanotube composites were examined using transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), infrared spectroscopy and X-ray diffraction (XRD). The electrochemical property of the polypyrrole/carbon nanotube composite was elucidated by cyclic voltammetry and galvanostatic charge-discharge. A specific capacitance of 304 F g⁻¹ was obtained within the potential range of −0.5-0.5 V in 1 M KCl solution.     

Synthesis and characterization of carbon nanotubes on carbon microfibers by floating catalyst method

In this paper, carbon nanotubes were synthesized on carbon microfibers by floating catalyst method with the pretreatment of carbon microfibers at the temperature of 1023 K, using C₂H₂ as carbon source and N₂ as carrier gas. The morphology and microstructure of carbon nanotubes were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The composition of carbon nanotubes was determined by energy dispersive X-ray spectroscopy (EDX). The results showed that the surface of treated carbon microfibers was thickly covered by carbon nanotubes with diameters of about 50 nm. EDX image indicated that the composition of carbon nanotubes was carbon. In comparison with the sample grown on untreated carbon microfibers surface, it was found that after carbon microfibers were boiled in the solution of sulfur acid and nitric acid (VH₂SO₄:VHNO₃ = 1:3) and immersed in the solution of iron nitrate and xylene, carbon nanotubes with uniform density can be grown on carbon microfibers surface. Based on the results, we concluded that the pretreatment of carbon microfibers had great effect on the growth of carbon nanotubes by floating catalyst method.     

Multiwalled carbon nanotubes mass-produced by dc arc discharge in He–H2 gas mixture

Uniform cathode deposits (longer than 15 mm), containing multiwalled carbon nanotubes (MWNTs) inside, were produced by dc arc discharge evaporation with a computer-controlled feeder of a pure-carbon electrode without a metal catalyst in a He–H₂ gas mixture. The purification of MWNTs was carried out to remove amorphous carbon and carbon nanoparticles. High-resolution transmission electron microscopy observations and Raman scattering studies show that the MWNTs possess a high crystallinity and a mean outermost diameter of ∼ ∼10 nm. It has been confirmed that the current density in the electron field emission from a purified MWNT mat can reach 77.92 mA/cm², indicating that the purified MWNTs are a promising candidate electron source in a super high-luminance light-source tube or a miniature X-ray source.     

170keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响

碳纳米管具有优异的导电性, 是未来电子元器件的理想候选材料, 应用前景广阔. 针对碳纳米管在空间电子元器件的应用需求, 本文研究了170 keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响. 采用扫描电子显微镜(SEM)、拉曼光谱仪(Raman)、X射线光电子能谱仪(XPS)及电子顺磁共振谱仪(EPR)对辐照前后碳纳米管试样的表面形貌和微观结构进行分析; 利用四探针测试仪对碳纳米管薄膜进行导电性能分析. SEM分析表明, 170 keV质子辐照条件下, 当辐照注量高于5×10¹⁵ p/cm² (protons/cm²)时, 碳纳米管薄膜表面变得粗糙疏松, 纳米管发生明显弯曲、收缩及相互缠结现象. 目前, 质子辐照纳米管发生的收缩现象被首次发现. 基于Raman和XPS分析表明, 170 keV质子辐照后碳纳米管的有序结构得到改善, 且随辐照注量增加, 碳纳米管的有序结构改善明显. 结构的改善主要是由于170 keV质子辐照碳纳米管所产生的位移效应导致缺陷重组. EPR分析表明, 随着辐照注量的增加, 碳纳米管薄膜内的非局域化电子减少. 利用四探针测试分析表明, 碳纳米管薄膜的导电性能变差, 这是由于170 keV质子辐照导致碳纳米管薄膜中的电子特性及形态发生改变. 本文研究结果有助于利用质子辐照对碳纳米管膜结构和性能进行调整, 从而制备出抗辐射的纳米电子器件.     

Evidence of multi-walled carbon nanotube fragmentation induced by sonication during nanotube encapsulation via bulk-suspension polymerization

The synthesis of multi-walled carbon nanotube/polystyrene composites, with nanotube concentrations of 0.04, 0.08 and 0.16 wt%, was carried out by in situ bulk-suspension polymerization with the assistance of sonication. By using this method both encapsulation and exfoliation of the nanotubes into the polymer host were achieved. Evidence of significant nanotube fragmentation was found by scanning electron microscopy; the cause of such fragmentation was attributed to the induction of strong cavitation due to the application of ultrasound during the synthesis. Infrared spectroscopy showed no evidence of the formation of covalent bonds between the nanotubes and the polystyrene during the process of synthesis. The thermal stability was not improved by the inclusion of the nanotubes, it was attributed to the low nanotube concentrations; however, composites glass transition temperature showed improvements.     

Catalytic activity of Fe, Co and Fe-Co-MCM-41 for the growth of carbon nanotubes by chemical vapour deposition method

Iron, cobalt and a mixture of iron and cobalt incorporated mesoporous MCM-41 molecular sieves were synthesised by hydrothermal method and used to investigate the rules governing their nanotube producing activity. The catalysts were characterised by XRD and N₂ sorption studies. The effect of the catalysts has been investigated for the production of carbon nanotubes at an optimised temperature 750 °C with flow rate of N₂ and C₂H₂ is 140 and 60 ml/min, respectively for a reaction time 10 min. Fe-Co-MCM-41 catalyst was selective for carbon nanotubes with low amount of amorphous carbon with increase in single-walled carbon nanotubes (SWNTs) yield at 750 °C. Formation of nanotubes was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Transmission electron microscope and Raman spectrum was used to follow the quality and nature of carbon nanotubes formed and the graphitic layers and disordered band, which shows the clear evidence for the formation of SWNTs, respectively. The result propose that the diameter of the nanotubes in the range of 0.78-1.35 nm. Using our optimised conditions for this system, Fe-Co-MCM-41 showed the best results for selective SWNTs with high yield when compared with Fe-MCM-41 and Co-MCM-41.     

Filling of single-walled carbon nanotubes by CuI nanocrystals via capillary technique

The present study is focused on the synthesis and investigation of the nanocomposite CuI@SWNT obtained by the filling of metallic single-walled carbon nanotubes (SWNTs) (inner diameter 1–1.4 nm) by wide-gap semiconducting CuI nanocrystals using so-called capillary technique. The method is based on the impregnation of pre-opened SWNTs by molten CuI in vacuum with subsequent slow cooling to room temperature. SWNTs and CuI@SWNT nanocomposites were studied by nitrogen capillary adsorption method, EDX microanalysis, HRTEM microscopy and Raman spectroscopy. The changing of electronic properties of CuI@SWNT as compare to row nanotubes was observed.     

Electrical properties of boron-doped MWNTs synthesized by hot-filament chemical vapor deposition

We have synthesized a large amount of boron-doped multiwalled carbon nanotubes (MWNTs) by hot-filament chemical vapor deposition. The synthesis was carried out in a flask using a methanol solution of boric acid as a source material. The scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy were performed to evaluate the structural properties of the obtained MWNTs. In order to evaluate the electrical properties, temperature dependence of resistivity was measured in an individual MWNTs with four metal electrodes. The Raman shifts suggest carrier injection into the boron-doped MWNTs, but the resistivity of the MWNTs was high and increased strongly with decreasing temperature. Defects induced by the plasma may cause this enhanced resistivity.     

Functionalization of carbon nanotubes with silver clusters

In this paper, an advanced method of one-step functionalization of single and multi walled carbon nanotubes (SWCNTs and MWCNTs) using γ-irradiation was described. Two synthesis procedures, related with different reduction species, were employed. For the first time, poly(vinyl alcohol) PVA is successfully utilized as a source to reduce silver (Ag) metal ions without having any additional reducing agents to obtain Ag nanoparticles on CNTs. The decoration of carbon nanotubes with Ag nanoparticles takes place through anchoring of (PVA) on nanotube's surface. Optical properties of as-prepared samples and mechanism responsible for the functionalization of carbon nanotubes were investigated using UV-vis and FTIR spectroscopy, respectively. Decorated carbon nanotubes were visualized using microscopic techniques: transmission electron microscopy and scanning tunneling microscopy. Also, the presence of Ag on the nanotubes was confirmed using energy dispersive X-ray spectroscopy. This simple and effective method of making a carbon nanotube type of composites is of interest not only for an application in various areas of technology and biology, but for investigation of the potential of radiation technology for nanoengineering of materials.     

Aligned growth and alignment mechanism of carbon nanotubes by hot filament chemical vapor deposition

Carbon nanotubes (CNTs) growth on Inconel sheets was carried out using hot filament chemical vapor deposition (HFCVD) in a gas mixture of methane and hydrogen. Scanning electron microscopy, transmission electron microscopy and field electron emission (FEE) measurement were applied to study the structure and FEE properties of the deposited CNTs. The effect of bias voltage and substrate surface roughness on the growth of vertically aligned carbon nanotubes was investigated. Well-aligned CNTs were synthesized by bias enhanced HFCVD. The results show that a bias of −500 V generates the best alignment. It has been observed that at the early growth stage, aligned and non-aligned CNTs are growing simultaneously on the unscratched sheets, whereas only aligned CNTs are growing on the scratched sheets. The results indicate that tip growth is not necessary for the electric field to align the CNTs, and larger catalyst particles created by scratching before the heat treatment can induce alignment of CNTs at the early growth stage. In addition, tree-like CNTs bundles grown on the scratched substrates exhibit better FEE performances than dense carbon nanotube forest grown on the unscratched substrates due to the reduced screen effect.     

钯金属吸附对半导体性碳纳米管电输运的影响

利用物理蒸发技术,在半导体性的碳纳米管上沉积钯金属,利用导电原子力显微镜检测钯吸附对碳纳米管电输运的影响.结果表明:沉积的钯在碳纳米管上形成纳米颗粒,随着钯颗粒密度的增加,半导体性碳纳米管逐渐向金属性转变.利用第一性原理计算了吸附有钯原子的半导体性单壁碳纳米管的能带结构.研究发现,钯的覆盖率越高,其禁带宽度越窄,直至为零,定性说明了实验结果的合理性. 关键词： 单壁碳纳米管 钯纳米颗粒 导电原子力显微镜 第一性原理计算