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.     

Role of catalysts in the surface synthesis of single-walled carbon nanotubes

We demonstrate the role of catalysts in the surface growth of single-walled carbon nanotubes (SWNTs) by reviewing recent progress in the surface synthesis of SWNTs. Three effects of catalysts on surface synthesis are studied: type of catalyst, the relationship between the size of catalyst particles and carbon feeding rates, and interactions between catalysts and substrates. Understanding of the role of catalysts will contribute to our ability to control the synthesis of SWNTs on various substrates and facilitate the fabrication of nanotube-based devices.      

定向碳纳米管的化学气相沉积制备法

报道了一种简便有效的合成定向碳纳米管 (CNTs)的化学气相沉积 (CVD)制备方法。以铁为催化剂 ,乙炔为碳源 ,采用单一反应炉 ,直接在石英基底上沉积催化剂颗粒薄膜 ,成功合成了定向性好、管径均匀的高质量大密度的碳纳米管     

Wafer scale synthesis of dense aligned arrays of single-walled carbon nanotubes

Here we present an easy one-step approach to pattern uniform catalyst lines for the growth of dense, aligned parallel arrays of single-walled carbon nanotubes (SWNTs) on quartz wafers by using photolithography or polydimethylsiloxane (PDMS) stamp microcontact printing (μCP). By directly doping an FeCl₃/methanol solution into Shipley 1827 photoresist or polyvinylpyrrolidone (PVP), various catalyst lines can be well-patterned on a wafer scale. In addition, during the chemical vapor deposition (CVD) growth of SWNTs the polymer layers play a very important role in the formation of mono-dispersed nanoparticles. This universal and efficient method for the patterning growth of SWNTs arrays on a surface is compatible with the microelectronics industry, thus enabling of the fabrication highly integrated circuits of SWNTs.     

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.     

Catalyst-free growth of pyramidal zinc sulfide nanostructure arrays on single walled carbon nanotubes

Uniform and ordered pyramidal zinc sulfide (ZnS) nanostructure arrays have been fabricated on the single walled carbon nanotube (SWNT) films by chemical vapor deposition without using any metal catalyst. Each ZnS pyramid has a 100 nm-sized base, a uniform length of 600 nm, and a sharp tip of 10 nm. The control of interspatial distance between ZnS nanostructures was achieved by creation of selective growth on the SWNTs in voids with the assistance of a close-packed silica particle monolayer as a template. Furthermore, this kind of morphology control of nanostructure arrays can play an important role for potential applications, such as high efficiency of field emission because of the strong correlation between shapes and functionalities of nanostructures.     

Synthesis of carbon nanotubes at low temperature by filament assisted atmospheric CVD and their field emission characteristics

Multiwalled carbon nanotubes (MWNTs) were synthesized using a hot filament assisted chemical vapor deposition (CVD) at the atmospheric pressure at a substrate temperature of 550 °C. The size of nanotubes was controlled by changing the size of catalyst particles. The structure and composition of these nanotubes were investigated using scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The electron field emission current of MWNTs was also measured. It was found that the nanotubes with smaller the diameter had higher the emission current levels though synthesis conditions except catalyst particles were the same. These as-grown MWNTs had emission current densities of 6.5 mA/cm² and 2.5 mA/cm² at 1 V/μm for 5-8 nm and 20 nm size carbon nanotube samples, respectively. The results indicated that the MWNTs synthesized had low emission threshold voltages and high emission current levels that are favorable properties for field emission-based display device applications.     

载气在CVD法制备纳米碳管工艺中的作用

纳米碳管是性能优异的具有准一维特征的纳米材料,CVD法是制备纳米碳管的典型工艺之一。本文以乙炔气体为原料气体、循环失效后的贮氢电极舍金材料作为反应催化剂,研究了在相同反应条件下,CVD法制备纳米碳管过程中载气对纳米碳管形貌和产率的影响。通过对产物TEM观察和TG分析发现,虽然载气不直接参与合成反应但对产物产率和形貌有很大的影响,氢气作为载气可以获得形貌和热稳定性更好的纳米碳管。     

用单壁纳米碳管制备葡萄糖生物传感器的研究

以单壁纳米碳管为代表材料,对利用纳米碳管制备葡萄糖生物传感器中纳米碳管的作用和纳米碳管修饰电极的方法、酶的固定化方法及电极种类等因素对传感器性能的影响进行了研究.研究结果表明,纳米碳管的加入能有效地改善传感器的电化学性能,利用二茂铁和单壁纳米碳管共同修饰电极所制得的传感器的性能要好于仅用单壁纳米碳管修饰电极制得的传感器.在酶的固定化方法中,戊二醛交联法要略好于明胶包埋法;而利用铂电极制备出的生物传感器对葡萄糖的响应电流要明显高于利用金电极和玻碳电极制备出的生物传感器.这些结论对于开发纳米碳管在生物传感领域及生命科学相关领域的应用有参考价值.     

用于制备优质单壁碳纳米管管束的MgO负载Fe3O4纳米粒子的合成

采用沉淀方法制备了直径分布狭窄的均匀Fe3O4纳米颗粒.Fe3O4纳粒形体几近一致,平均粒径为10.33 nm±2.99 nm(平均粒径±标准偏差).在超声作用下将MgO纳米颗粒分散在一定量Fe3O4纳米颗粒的水溶液中获得MgO负载Fe3O4的纳米颗粒.以甲烷为碳源,Fe3O4/MgO为催化剂,经化学气相沉积,在Fe3O4纳粒上制得了大量直径近乎均匀的单壁碳纳米管(SWCNTs)束.TEM显示:SWCNTs的平均直径1.22rm.热重分析显示:样品在400℃～600℃温度区间失重量约19％.拉曼光谱显示:SWCNTs的ID/IG的强度比为0.03,表明采用Fe3O4/MgO催化剂可制得高石墨化程度的单壁碳纳米管.     

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。     

Interaction study on DNA,single-wall carbon nanotubes and acridine orange

The fluorescence of acridine orange (AO) can be quenched significantly with addition of the single-wall carbon nanotubes (SWCNTs) solution, due to the formation of a hybrid complex between AO and SWCNTs. A fluorescence enhancement of approximately 18× can be observed after the addition of certain amount of DNA into the above mentioned solution. The fluorescence increase was linearly proportional to the amount of DNA added in the concentration range of 0–50.75 μM, and the DNA detection limit was down to 8.56 × 10⁻⁸ M. This method can be used to detect DNA in vitro.     

Deposition of amorphous hydrogenated carbon films on Si and PMMA by pulsed direct-current plasma CVD

A pulse-modulated direct-current methane plasma is used to deposit amorphous hydrogenated carbon (a-C:H) films on Si and polymethyl methacrylate (PMMA) substrates. The structure and mechanical properties of the films are examined by applying a negative pulse bias voltage of 0.5 to 3 kV to the substrate at a pulse bias period of 100 to 200 μs. The deposition rate on both Si and PMMA increases with increasing the net input power, independent of the pulse period. The Raman spectra demonstrate that the films on Si are diamond-like carbon (DLC), while those on PMMA are polymer-like or soft amorphous carbon because of higher crystallinity of the sp² phase and lower nanoscale hardness. The residual compressive stress of the films on PMMA is constantly low ranging from 0 to 2 GPa due exclusively to high flexibility of PMMA, which causes the easy relief of the stress and thus the density decrease in the films.     

Effect of single-walled carbon nanotubes on primary immune cells in vitro

Carbon nanotubes (CNTs) are emerging as innovative tools in nanobiotechnology. However, their toxic effects on environment and health have become an issue of great concern. The effect of single-walled carbon nanotubes (SWCNTs) on primary immune cells in vitro was studied in this paper. The results indicated that SWCNTs (25 and 50 μg/mL) could promote the proliferation of spleen cells. However, they had no significant effect on the proliferation of spleen cells at concentrations of 1 and 10 μg/mL. They also had no effect on T-lymphocyte proliferation stimulated by concanavalinA (ConA) at lower concentrations. Moreover, they turned to inhibit T-lymphocyte proliferation at higher concentrations. It was found that SWCNTs inhibited the B-lymphocyte proliferation stimulated by lipopolysaccharides (LPS) at concentrations of 1, 10, 25 and 50 μg/mL. What is more, they significantly decreased the Natural Killer (NK) cell activity compared with the control group at all tested concentrations. The results suggest that SWCNTs have possibly negative effects on immune cells in vitro.     

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.     

Demonstration of covalent sidewall functionalization of single wall carbon nanotubes by NMR spectroscopy: Side chain length dependence on the observation of the sidewall sp3 carbons

Carboxylic acid-functionalized single walled carbon nanotubes (SWNTs) prepared via the reaction of an amino acid, NH₂(CH₂) _n CO₂H where n = 1 (glycine, GLY), 5 (6-aminohexanoic acid, AHA), 10 (11-aminoundecanoic acid, AUDA), with fluorinated single walled carbon nanotubes (F-SWNTs) have been characterized by MAS ¹³C NMR spectroscopy. The ease of observing the aliphatic CH₂ groups and the resolution of the signal are dependent on the length of the amino acid’s aliphatic chain. We have proposed that where substituent chains are short (making NMR data collection difficult) chemical modification to extend the chain length should alleviate analysis problems. In this regard, we have investigated the esterification of the carboxylic acid termini. The amino acid-functionalized SWNTs were esterified with an appropriate alcohol to ensure parity of the overall substituent length, i.e., GLY-SWNT (C₁) + 1-dodecanol (C₁₂) = DOD-GLY-SWNT (1), AHA-SWNT (C₅) + 1-octanol (C₈) = OCT-AHA-SWNT (2), and AUDA-SWNT (C₁₀) + 1-propanol (C₃) = PRO-AUDA-SWNT (3). The ¹³C NMR shift for the sp³ nitrogen-substituted carbon atoms of the SWNT sidewall is observed at δ ≈ 75 ppm. Increasing the length of SWNT sidewall functional groups enhances the ability to observe the sidewall sp³ carbon. The methylene carbon signal intensity is less attenuated in the dipolar dephasing spectrum of the ester-functionalized SWNTs than their associated amino acid derivatives, suggesting more motional freedom of the side chain in the solid state. The confirmation of the dipolar dephasing spectral effects was assisted by the characterization of the ester of AUDA-SWNT with 1,3-propanediol: PPD-AUDA-SWNT (4). Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Study on effect of oxygen adsorption on characteristics of field electron emission from aligned carbon nanotubes grown by plasma-enhanced hot filament chemical vapor deposition

The characteristics of field electron emission (FE) from aligned carbon nanotubes (ACNTs) in a form of film, which were catalytically grown by plasma-enhanced hot filament chemical vapor deposition, were measured for many cycles. The results indicate that the FE characteristic for every measurement cycle is different and it follows the Fowler–Nordheim model in the low field region, but it deviates from the model in the high field region. The ACNTs were investigated by energy dispersive X-ray (EDX) and the EDX spectrum shows that oxygen is adsorbed on the ACNTs. The theory related to adsorption and space-charge effect was applied to analyze the experimental results.     

电泳沉积制备平行栅碳纳米管场发射阴极的研究

利用磁控溅射、光刻、湿法刻蚀和电泳技术在玻璃基片上成功制备平行栅场发射阴极阵列,用光学显微镜、场发射扫描电镜和拉曼光谱观察了碳纳米管的形貌和结构,并测试所制备的平行栅碳纳米管阴极的场发射性能.光学显微镜和场发射电子显微镜测试表明,平行栅结构阴极和栅极交替地分布,同一个平面内,CNTs有选择性地沉积在平行栅结构中的阴极表...     

Influence of Fe nanoparticles diameters on the structure and electron emission studies of carbon nanotubes and multilayer graphene

In this paper we report the effect of Fe film thickness on the growth, structure and electron emission characteristics of carbon nanotubes (CNTs) and multilayer graphene deposited on Si substrate. It is observed that the number of graphitic shells in carbon nanostructures (CNs) varies with the thickness of the catalyst depending on the average size of nanoparticles. Further, the Fe nanoparticles do not catalyze beyond a particular size of nanoclusters leading to the formation of multilayer graphene structure, instead of carbon nanotubes (CNTs). It is observed that the crystallinity of CNs enhances upon increasing the catalyst thickness. Multilayer graphene structures show improved crystallinity in comparison to CNTs as graphitic to defect mode intensity ratio (I_D/I_G) decreases from 1.2 to 0.8. However, I_2D/I_G value for multilayer graphene is found to be 1.1 confirming the presence of at least 10 layers of graphene in these samples. CNTs with smaller diameter show better electron emission properties with enhancement factor (γ_C = 2.8 × 10³) in comparison to multilayer graphene structure (γ_C = 1.5 × 10³). The better emission characteristics in CNTs are explained due to combination of electrons from edges as well as centers in comparison to the multilayer graphene.     

Influence of structural and preparation parameters of Fe2O3/Al2O3 catalysts on rate of production and quality of carbon nanotubes

The influence of catalytic and operational parameters on the rate of growth and quality of carbon nanotubes has been investigated. A series of Fe₂O₃/Al₂O₃ catalysts prepared by different methods were investigated under conditions of synthesis of CNTs via the process of CVD of ethylene. Deposition experiments were carried out in a thermogravimetric hot-wall reactor, which enables continuous monitoring of the evolution of carbon mass with time. Controlled explosive burning (CEB) of precursor compounds was found to be the most effective method of preparation of the catalyst with respect to rate of deposition and yield of CNTs. This result has been attributed to the presence of hematite particles of small diameter on the catalyst. The presence of hydrogen in the gas feed mixture, even at small concentration, proved to be beneficial for the rate of production of MWCNTs and to result in the synthesis of CNTs of narrower diameter distribution. Yield and quality of MWCNTs depend on the concentration of the carbon source (ethylene) in the feed mixture and on temperature of deposition. Under the present experimental conditions, the optimal reaction temperature was found to be 650 °C. The products of the deposition were characterized using scanning electron microscopy and Raman spectroscopy.