Structural and morphological dependence of carbon nanotube arrays on catalyst aggregation

Catalyst aggregation affects the growth of carbon nanotube (CNT) arrays in terms of tubular structures, waviness, entanglement, lengths, and growth density etc., which are important issues for application developments. We present a systematic correlation between the aggregation of catalyst on the SiO₂/Si substrate and the structure and morphology of CNT arrays. The thickness of the catalyst film has a direct effect on the areal density of the catalytic particles and then the alignment of the CNT array. Introducing alumina as buffer layer and annealing the catalyst film at low pressure are two effective approaches to downsize the catalyst particles and then the diameter, wall number of the CNTs. Both the size and areal density of the catalyst also change with the CNT growth in accordance with Ostwald ripening process, with the bottom of the CNT array varying from well-aligned to disordered and adhesion between catalyst particles and the substrate getting enhanced. Strategies including tuning the thickness of the catalyst film, changing buffer layer, controlling on the growth time and the system pressure were used to regulate the aggregation of the catalyst. CNT arrays from disordered to well-aligned, from multi-walled to few-walled and further to single-walled were reproducibly synthesized by chemical vapor deposition of acetylene.     

生长参数对碳纳米管阵列制备的影响

利用化学气相沉积法在沉积铁纳米颗粒的硅衬底上制备了垂直方向高度有序的碳纳米管阵列．扫描电子显微镜的观测发现，碳纳米管阵列的形貌受到若干生长参数的影响，包括催化剂颗粒大小、反应温度和反应气体的分压等．研究发现，当反应温度升高，或反应气体中碳源气体含量增加时，碳纳米管变粗、变短．当催化剂薄膜的厚度减小时，碳纳米管的直径随之减小而纳米管阵列的高度则先增后减，有一个最大值．这些结果表明，碳纳米管的直径和阵列的高度可通过选择合适的反应温度、匀胶机转速和反应气比率来调节．     

Electric field-induced unzipping of hydrogenated carbon nanotubes into graphene nanoribbons

We have investigated the electric field effect on horseshoe-shape carbon nanotubes (CNTs) resulting from hydrogen adsorption on the single-wall armchair (n,n)CNTs with 6 ≤ n ≤ 16 by using the density functional theory calculations. The horseshoe-shape CNT is completely unzipped into a graphene nanoribbon upon applying a critical electric field, which decreases with increasing CNT diameter, thus enabling one to select a nanoribbon width. A simple model based on the tensile force exerted on the tube walls by the applied electric field was introduced to understand the CNT-diameter dependence of the critical field.     

Preparation of NiO decorated CNT/ZnO core-shell hybrid nanocomposites with the aid of ultrasonication for enhancing the performance of hybrid supercapacitors

Supercapacitor (SC) electrodes fabricated with the combination of carbon nanotubes (CNTs) and metal oxides are showing remarkable advancements in the electrochemical properties. Herein, NiO decorated CNT/ZnO core-shell hybrid nanocomposites (CNT/ZnO/NiO HNCs) are facilely synthesized by a two-step solution-based technique for the utilization in hybrid supercapacitors. Benefitting from the synergistic advantages of three materials, the CNT/ZnO/NiO HNCs based electrode has evinced superior areal capacity of ~67 µAh cm⁻² at a current density of 3 mA cm⁻² with an exceptional cycling stability of 112% even after 3000 cycles of continuous operation. Highly conductive CNTs and electrochemically active ZnO contribute to the performance enhancement. Moreover, the decoration of NiO on the surface of CNT/ZnO core-shell increases the electro active sites and stimulates the faster redox reactions which play a vital role in augmenting the electrochemical properties. Making the use of high areal capacity and ultra-long stability, a hybrid supercapacitor (HSC) was assembled with CNT/ZnO/NiO HNCs coated nickel foam (CNT/ZnO/NiO HNCs/NF) as positive electrode and CNTs coated NF as negative electrode. The fabricated HSC delivered an areal capacitance of 287 mF cm⁻² with high areal energy density (67 µWh cm⁻²) and power density (16.25 mW cm⁻²). The combination of battery type CNT/ZnO/NiO HNCs/NF and EDLC type CNT/NF helped in holding the capacity for a long period of time. Thus, the systematic assembly of CNTs and ZnO along with the NiO decoration enlarges the application window with its high rate electrochemical properties.     

Synthesis of single-walled carbon nanotubes in oxy-fuel inverse diffusion flames with online diagnostics

A novel technique for synthesis of single-walled carbon nanotubes (SWNTs) in diffusion flames is presented, as is a diagnostic tool that can provide online information about nanotube size, number density, and purity. An inverse diffusion flame with a high stoichiometric mixture fraction (Z_st) is used to produce SWNTs with an average length of 1 μm. The high Z_st flame allows nanotubes to be produced in a fuel-rich region that is void of soot and polycyclic aromatic hydrocarbons (PAH). In addition, by operating as an inverse diffusion flame the carbon nanotubes (CNTs) are not exposed to oxygen and thus, can be collected downstream. Consequently, this flame provides a potential approach to large-scale synthesis of pure SWNTs. In addition, a differential mobility analyzer (DMA) is employed as an online diagnostic tool. The DMA can distinguish between excess catalyst particles and CNTs due to the differences in their electrical mobilities. Thus, the presence of CNTs as well as their size, number density, and purity relative to excess catalyst particles can be identified from the size distribution of the aerosol sampled downstream of the flame. This tool allows for rapid identification of the effect of changing process variables on nanotube growth and thus, the production process can be quickly optimized.     

Molecular dynamics of reactions between (4,0) zigzag carbon nanotube and hydrogen peroxide under extreme conditions

ABSTRACT

Single-wall carbon nanotubes (CNTs) have been suggested as potential materials for use in next-generation gas sensors. The sidewall functionalisation of CNTs facilitates gas molecule adsorption. In this study, density functional theory (DFT)-based ab initio molecular dynamics simulations are performed for a periodic zigzag single-wall (4,0) CNT surrounded by a monolayer of hydrogen peroxide molecules in an attempt to find conditions that favour sidewall functionalisation. The dependency of dynamics on charge states of the system is examined. It is found negative charges favour reactions that result in the functionalisation of the CNT. First principles molecular dynamics of defect formation yields chemically reasonable structure of stable defects, which can be reproduced in CNTs of any diameter and chirality. The explored hydroxyl and hydroperoxyl defects increase conductivity in a large diameter (10,0) CNT, while decrease conductivities in a small diameter (4,0) CNT.     

Improved emission uniformity and stability of printed carbon nanotubes in electrolyte

In this paper, we studied the effect of NaCl electrolyte as a surface treatment on improving the uniformity and stability of field emission of screen-printed carbon nanotubes (CNTs). A short period of the electrolyte treatment of CNT films remarkably increase emission uniformity and stability. Furthermore, the field emission characteristics of screen-printed carbon nanotubes (CNTs) such as low turn-on field, high emission current density and strong adhesion of the CNT film on the substrate were also reinforced after post-treated. SEM, TEM and Raman spectrum study revealed that uniformity and stability of field emission is enhanced by two factors. Firstly, the electrolyte treatment appeared to render the CNT surfaces more actively by exposing more CNTs form the CNT paste, which dominates initial uniformity and stability of field emission. Secondly, the number of opened CNTs and defects CNTs of CNT film were increased by electrical current energy.     

关于碳纳米管反常反斯托克斯拉曼(AASR)光谱现象的研究

在碳纳米管中观察到了反常反斯托克斯拉曼（ＡＡＳＲ）光谱现象,并发现ＡＡＳＲ现象与碳纳米管的管层数和碳材料的片层样结构无关,因而揣测它可能只与碳纳米管的管状结构有联系。     

Growth of multiwalled carbon nanotube arrays by chemical vapour deposition over iron catalyst and the effect of growth parameters

Multiwalled carbon nanotube (CNT) arrays were grown by catalytic thermal decomposition of acetylene, over Fe-catalyst deposited on Si-wafer in the temperature range 700-750 °C. The growth parameters were optimized to obtain dense arrays of multiwalled CNTs of uniform diameter. The vertical cross-section of the grown nanotube arrays reveals a quasi-vertical alignment of the nanotubes. The effect of varying the thickness of the catalyst layer and the effect of increasing the growth duration on the morphology and distribution of the grown nanotubes were studied. A scotch-tape test to check the strength of adhesion of the grown CNTs to the Si-substrate surface reveals a strong adhesion between the grown nanotubes and the substrate surface. Transmission electron microscopy analysis of the grown CNTs shows that the grown CNTs are multiwalled nanotubes with a bamboo structure, and follow the base-growth mechanism.     

沉积工艺参数对碳纳米管薄膜场发射性能的影响

利用微波等离子体化学气相沉积(MWPCVD)方法,在不锈钢衬底上直接沉积碳纳米管膜。通过SEM、拉曼光谱和XRD表征,讨论了制备温度和甲烷浓度对碳纳米管膜场发射的影响。结果表明:不同条件下制备的碳纳米管膜的场发射性能有很大差异,保持氢气的流量(100sccm)、生长时间(10min)、反应室压力不变,当甲烷流量为8sccm、温度为700~800℃时,场发射性能最好,开启场强仅为0.8V/μm,发射点分布密集、均匀。     

Effects of doping, Stone Wales and vacancy defects on thermal conductivity of single-wall carbon nanotubes

The thermal conductivity of carbon nanotubes with certain defects (doping, Stone-Wales, and vacancy) is investigated by using the non-equilibrium molecular dynamics method. The defective carbon nanotubes (CNTs) are compared with perfect tubes. The influences of type and concentration of the defect, length, diameter, and chirality of the tube, and the ambient temperature are taken into consideration. It is demonstrated that defects result in a dramatic reduction of thermal conductivity. Doping and Stone-Wales (SW) defects have greater effect on armchair tubes, while vacancy affects the zigzag ones more. Thermal conductivity of the nanotubes increases, reaches a peak, and then decreases with increasing temperature. The temperature at which the thermal conductivity peak occurs is dependent on the defect type. Different from SW or vacancy tubes, doped tubes are similar to the perfect ones with a sharp peak at the same temperature. Thermal conductivity goes up when the tube length grows or diameter declines. It seems that the length of thermal conductivity convergence for SW tubes is much shorter than perfect or vacancy ones. The SW or vacancy tubes are less sensitive to the diameter change, compared with perfect ones.     

LPCVD法制备碳纳米管薄膜及其场发射性能的研究

采用低压化学气相沉积法(LPCVD)在镍片上直接制备碳纳米管(CNTs)薄膜,系统地研究了生长温度(500~800℃)对碳纳米管薄膜形貌、结构及场发射性能的影响,并对此方法的生长机理进行了分析。当温度从500℃升高到650℃时,碳纳米管的生长速率随着温度升高而增大,而温度继续上升,速率则明显减小。利用扫描电镜(SEM)和拉曼光谱仪表征和检测了碳纳米管薄膜的形貌和结构。碳纳米管的管径、长度、一致性和晶化程度随温度都有明显的变化。同时还对碳纳米管薄膜的场发射特性进行了测试,对其场发射机理进行了深入地探讨,表明温度对碳纳米管的性能有很大影响,并存在最优化的温度条件。实验结果表明碳纳米管薄膜的形貌、结构及其场发射性能可通过生长温度进行一定范围的控制。     

Structure of Lennard–Jones nanowires encapsulated by carbon nanotubes

Molecular dynamics simulations have been performed to investigate the structures of Lennard–Jones(LJ) nanowires(NWs) encapsulated in carbon nanotubes(CNTs). We find that the structures of NWs in a small CNT only adopt multi-shell motifs, while the structures of NWs in a larger CNT tend to adopt various motifs. Among these structures, three of them have not been reported previously. The phase boundaries among these structures are obtained regarding filling fractions, as well as the interaction between NWs and CNTs.     

大电流密度碳纳米管场致发射阴极阵列的研制

 设计了一种由TiN，Al，Fe和牺牲层构成的堆栈式催化剂层结构，采用微波等离子体化学气相沉积法实现碳纳米管阵列高速笔直生长。SEM和TEM结果表明，生长出来的碳纳米管为典型的多壁碳纳米管，长度和直径均匀，排列整齐并垂直于基底，生长速率大于5 μm/min，晶格缺陷少。场致发射测试结果表明：碳纳米管的发射阵列具有良好的电流发射稳定性，最大电流密度大于6 A/cm2。紫外光电子能谱法（UPS）测试出碳纳米管的功函数为4.59 eV，则相应的场致发射陈列的场增强因子大于1 400。     

Structural,electronic and magnetic properties of hcp Fe,Co and Ni nanowires encapsulated in zigzag carbon nanotubes

The structural, electronic and magnetic properties of hcp transition metal (TM = Fe, Co or Ni) nanowires TM₄ encapsulated inside zigzag nanotubes C(m, 0) (m = 7, 8, 9, 10, 11 or 12), along with TM _n (n = 4, 10 or 13) encapsulated inside C(12, 0), have been systematically investigated using the first-principle calculations. The results show that the TM nanowires can be inserted inside a variety of zigzag carbon nanotubes (CNTs) exothermically, except from the systems TM₄@(7, 0) and TM₁₃@(12, 0) which are endothermic. The charge is transferred from TM nanowires to CNTs, and the transferred charge increases with decreasing CNT diameter or increasing nanowire thickness. The magnetic moments of hybrid systems are smaller than those of the freestanding TM nanowires, especially for the atoms on the outermost shell of the nanowires. The magnetic moment per TM atom of TM/CNT system increases with increasing CNT diameter or decreasing nanowire thickness. Both the density of states and spin charge density analysis show that the spin polarization and the magnetic moments of all hybrid systems mainly originate from the TM nanowires, implying these systems can be applied in magnetic data storage devices.     

Optimization of a thermal-CVD system for carbon nanotube growth

We illustrate the optimization of the operation of a thermal chemical vapor deposition (CVD) system for the growth of carbon nanotubes (CNT). We have studied the deposition parameters using the Taguchi matrix robust design approach. The CVD system, which employs solid precursors (camphor and ferrocene) carried by nitrogen gas flow through a hot deposition zone, where the deposition of carbon nanostructures takes place, involves a large number of tunable parameters that have to be optimized.With the aim of getting the best configuration for the development of massive and well-oriented CNT carpets, the Taguchi method allowed us to improve our system leading to the growth of extremely long CNTs (few millimeters) at a high deposition rate (500 nm/s) and yield (30% in weight of the carbon precursors feedstock), which were characterized by electron microscopy.We found that the growth temperature had the most important influence on the CNT diameter, whereas the substrate tilt wit respect to gas flow did not influence their growth (i.e. CNTs grow on every side of the silicon wafer substrates, always normal to the substrate surface). The carrier gas flow and catalyst concentration both showed a secondary impact on CNT growth, though they showed a consistent correlation to the growth temperature.     

Comparative study on diameter distribution of single-walled carbon nanotubes using growth templates with different pore sizes: Zeolite-L,ZSM-5, and MCM-41

We report a comparative study on diameter distribution of single-walled carbon nanotubes (SWNTs) grown using nanoporous templates having different pore sizes, namely, zeolite-L, ZSM-5, and MCM-41. The change in the tube diameter based on catalytic film thickness and growth temperature was systematically investigated. We prepared very thin Fe catalyst films with nominal thicknesses of 0.5, 0.7, 1, and 2 Å, and the growth temperature was varied from 850 to 925 °C. We found that the SWNT mean diameter and size distribution width decreased with decreasing catalyst film thickness, growth temperature, and pore sizes of the templates. In addition, all SWNTs grown from the nanoporous templates have narrower diameter distribution compared to the SWNTs grown from SiO₂ planar surface. The obtained results are straightforward and suggest that the template growth has potential for SWNT growth with very narrow diameter distribution.     

Temperature and carbon source effects on methane–air flame synthesis of CNTs

We have conducted experimental and numerical studies on flame synthesis of carbon nanotubes (CNTs) to investigate the effects of three key parameters – selective catalyst, temperature and available carbon sources – on CNT growth. Two different substrates were used to synthesize CNTs: Ni-alloy wire substrates to obtain curved and entangled CNTs and Si-substrates with porous anodic aluminum oxide (AAO) nanotemplates to grow well-aligned, self-assembled and size-controllable CNTs, each using two different types of laminar flames, co-flow and counter-flow methane–air diffusion flames. An appropriate temperature range in the synthesis region is essential for CNTs to grow on the substrates. Possible carbon sources for CNT growth were found to be the major species CO and those intermediate species C₂H₂, C₂H₄, C₂H₆, and methyl radical CH₃. The major species H₂, CO₂ and H₂O in the synthesis region are expected to activate the catalyst and help to promote catalyst reaction.     

The morphologies of Lennard-Jones liquid encapsulated by carbon nanotubes

Using molecular dynamics simulations, we studied the morphologies of Lennard-Jones liquid encapsulated in carbon nanotubes (CNTs) for a wide range of liquid–CNT interaction, system size and temperature. The morphology of liquid is found to be sensitive to the filling ratio of liquid (a ratio of liquid volume to the available volume of CNT pore) and the liquid–CNT interaction. The ‘phase diagram’, namely by the morphologies versus the liquid–CNT interaction and the filling ratio, is obtained. In most cases, the liquid inside CNTs forms a thin liquid shell attached to a carbon wall when the filling ratio is small. With the increasing of the filling ratio, liquid tends to form droplet. As the filling ratio increases further, liquids form a cylinder with finite length. Finally, the whole inner space of CNT was filled with liquid when the filling ratio is large enough. Current studies could shed light on the adsorption and flow of liquid inside CNTs.     

Coating curly carbon nanotubes with monocrystalline Zn(BO2)2 and the mechanism of straightening the tubes

We overgrew single-crystalline Zn(BO2)2 coatings on carbon nanotubes (CNTs) for the first time. Scanning electron microscopy and transmission electron microscopy analyses revealed that the carbon nanotube-zinc borate composite rods are from tens to hundreds of nm in diameter. It is notable that the original curly tubes were straightened by the monocrystalline coatings. In addition, the crystal nucleation and growth on the surface of CNT were explained. We set a two-dimensional model, which is based on our experimental result, to qualitatively explain the mechanism of straightening the curly tubes by coating them with single-crystals.