Supported Pt-particles on multi-walled carbon nanotubes with controlled surface chemistry

Multi-walled carbon nanotubes (MWCNTs) were functionalized by HNO₃ hydrothermal oxidation at 200 °C. The degree of surface functionalization was described by an exponential function in terms of HNO₃ concentration. Very small Pt particles, with mean particle size of 1.7 ± 0.3 nm, could be supported on the surface of pristine MWCNTs and also on MWCNTs treated with HNO₃ concentrations up to 0.20 mol L^− 1, while a broader range of particle sizes, and larger Pt particles (3.4 ± 1.3 nm) were obtained on the MWCNTs treated with a higher HNO₃ concentration (0.30 mol L^− 1). Therefore, the amounts of surface groups and Pt particle sizes can be selected by tuning the HNO₃ concentration used in the hydrothermal treatment.     

多壁碳纳米管吸附异甘草苷的热力学研究

多壁碳纳米管可选择性地吸附结构相似的两种黄酮类化合物甘草苷和异甘草苷,研究了异甘草苷被多壁碳纳米管吸附的吸附热力学特征。结果表明:多壁碳纳米管吸附异甘草苷的量随着异甘草苷浓度的增加而增加,随着温度升高而降低。异甘草苷的吸附过程符合Freundlich方程。其ΔH0和ΔG0值表明该吸附反应是自发进行的放热反应。     

Bed collapse dynamics of fluidized beds of nano-powder

Bed collapse experiments have been carried out in fluidized beds of agglomerated nano-powders possessing high void fractions. Transient responses for the local pressure-drop as well as the gas velocity during the collapse were recorded. From the local pressure transient data, occurrences of key events of the collapse dynamics were identified. The first event is the zero pressure-drop condition soon after the flow interruption while the second is the global minimum on the pressure-drop profile that marks the end of the first stage of the bed collapse characterized by fast bed transients. The second stage is a relatively slow process, which ends with the onset of the zero pressure-drop condition again (third event) that reflects particles becoming stationary, thus signaling the completion of the collapse dynamics. The time of the first stage of the collapse is found to vary linearly with the initial fluidization velocity at which the collapse experiment was initiated whereas the total collapse time shows a rather weak dependence on the fluidization velocity. On the other hand, the velocity transients during the collapse follow first-order time lag that can be accurately modeled using a single time constant irrespective of the initial fluidization velocity.     

Solvent-free microwave-assisted synthesis of tenorite nanoparticle-decorated multi-walled carbon nanotubes

Copper-decorated carbon nanotubes (CNTs) have important applications as precursors for ultra-conductive copper wires. Tenorite-decorated CNTs (CuO-CNTs) are ideal candidates and are currently developed using laborious processes. For this reason, we have developed a facile and scalable method for the synthesis of CuO-CNTs from copper acetate. It was found that the optimal loading of copper acetate onto the CNTs was 23.1 wt% and that three 1-minute microwave treatments were sufficient for the decomposition of copper acetate to copper oxide. The loading of copper oxide onto the nanotubes was confirmed using X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. The materials were characterised using X-ray diffraction and scanning electron microscopy.     

Direct evidence for lip-lip interactions in multi-walled carbon nanotubes

The stability of open edged multi-walled carbon nanotubes has been investigated by using in situ high resolution transmission electron microscopy at elevated temperatures. Formation of inter-shell structures was experimentally observed for the first time and attributed to a robust interaction between adjacent concentric shells (so-called lip-lip interaction). The fl uctuating behavior of the inter-shell structures suggests a mechanism by which the carbon atoms can pass in or out through the inter-shell edges during carbon nanotube growth or shrinkage processes. This article is published with open access at Springerlink.com     

Removal of vanadium from wastewater by multi-walled carbon nanotubes

Nitric acid heating reflux modified multi-walled carbon nanotubes (HMWCNTs) were used for the removal of vanadium(V) in aqueous solution. The removal rate of vanadium(V) decreased with the increase of the initial vanadium(V) concentration and the solution pH, and increased with the increase of reaction time, HMWCNTs amount and solution temperature. The adsorption equilibrium and dynamic kinetics fitted the Langmuir adsorption isotherm and pseudo-second order models. The results obtained by scanning electron micrography and Fourier transform infrared spectroscopy analysis revealed that the hydroxyl and carboxyl functional groups are mainly responsible for the vanadium adsorption. This study showed that the HMWCNTs proved to be a considerable adsorbent for the removal of vanadium from wastewater.     

Adsorption of ionizable organic contaminants on multi-walled carbon nanotubes with different oxygen contents

Multi-walled carbon nanotubes (MWNTs), which are considered to be promising candidates for the adsorption of toxic organics, are released into aqueous environment with their increasing production and application. In this study, the adsorption behaviors of five structurally related ionizable organic contaminants namely perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonamide (PFOSA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-n-nonylphenol (4-NP) onto MWNTs with different oxygen contents (3.84-22.85%) were investigated. The adsorption kinetics was investigated and simulated with pseudo-second-order model. The adsorption isotherms were found to be fitted with Freundlich model and influenced by both the properties of organic chemicals and the oxygen contents of MWNTs. As adsorption capacity decreases dramatically with the increasing of oxygen contents, the MWNTs with the lowest oxygen contents possess the highest adsorption capacity among four MWNTs. For the MWNTs with the oxygen contents of 3.84%, the adsorption affinity related with hydrophobic interaction and π-electron polarizability decreased in the order of 4-NP>PFOSA>PFOS>2,4-D>PFOA. Furthermore, the adsorption characters of five contaminants were affected by solution pH and solute pK(a) considering electrostatic repulse force and hydrogen bonding, which showed the adsorption of MWNTs with lower oxygen content is much sensitive to solution chemistry.     

己烷低耗喷雾热解法大规模制备多壁碳纳米管

以己烷为碳源,二茂铁为催化剂前躯体,应用喷雾热解法,制备了多壁碳纳米管(MWCNTs).采用酸沥滤和空气氧化对MWCNTs进行纯化.利用SEM、TEM、XRD、EDS、TGA及Raman光谱分析等方法分别对原生和纯化MWCNTs进行表征.为制得优质、高产MWCNTs,对制备工艺参数作了优选,分别研讨了最佳制备参数,包括:二茂铁升华温度、己烷中二茂铁浓度、热解温度和时间,己烷与H2的流量比.MWCNTs具有典型的腊肠状(Sawsage-like)构型,长度大于数十微米,内、外管径分别为15nm～45nm及25nm～70nm,MWCNTs的纯度和产率的质量分数分别高于95%和70%.     

Effect of a pulsed Nd:YAG laser irradiation on multi-walled carbon nanotubes film

Multi-walled carbon nanotubes (MWCNTs) film have been analyzed by Raman spectroscopy to clarify the effect of a pulsed Nd:YAG laser heating. The MWCNTs film surface was flashed with the fundamental harmonic (λ = 1064 nm) or the second harmonic (λ = 532 nm) of a single pulse of Nd:YAG laser in the air. The dynamics of pulsed nanosecond laser heating process was simulated by the solution of the one-dimensional heat conduction equation. At the laser fluence of 500 mJ/cm² with Nd:YAG laser (λ = 1064 nm), the surface reached the maximum temperature 1395 °C at 12 ns. Moreover, the Raman spectroscopy of MWCNTs films before and after irradiation were measured. The intensity of the two characteristic Raman shifts I_D (defect-mode) and I_G (graphite-mode) was measured by the Raman spectroscopy. The maximum surface temperature was calculated and compared with the I_G/I_D ratio of MWCNTs film. The graphitization occurred on the sample after irradiation.     

Studies on preparation and properties of the multi-walled carbon nanotubes (MWNTs)/epoxy nanocomposites

The MWNTs were coated with polyaniline (PANI) by in situ chemical oxidation polymerization method. FTIR spectroscopy, scanning electron microscope (SEM) and X-ray diffraction (XRD) indicated that the MWNTs were coated with PANI. The MWNTs/epoxy nanocomposites were fabricated by using the solution blending method. Differential scanning calorimetry (DSC), tensile testing, HP 4294A impedance analyzer and SEM were used to investigate the properties of the nanocomposites. The results showed that the modified carbon nanotubes were well dispersed in the polymer matrix. The nanocomposites have enhancements in mechanical, thermal and dielectric properties compare with the neat epoxy resin. The nanocomposites were proven to be a good polymer dielectric material.     

Solvent-free derivatization of pristine multi-walled carbon nanotubes with dithiols

We report on direct solvent-free derivatization of pristine multi-walled carbon nanotubes (MWNTs) with aliphatic dithiols (1,4-butanedithiol, 1,6-hexanedithiol and 1,8-octanedithiol), by means of heating at 130–150 °C under reduced pressure. This method requires no additional chemical activation and about 2 h only for completion. Studies by high-resolution transmission electron microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy showed that dithiol-derivatized MWNTs have a high affinity to ZnCl₂ in solution, which covers the nanotubes with a dense amorphous layer. According to PM3 semi-empirical calculations, employing a closed-cap zigzag (10,0) single-walled carbon nanotube (SWNT) model incorporating a Stone-Wales defect, site-specificity of the addition depends on the mutual position of pentagons. If the nanotube contains pyracylene units or Stone-Wales defect, the addition takes place on their 6,6 or 7,7 bonds, respectively, whereas for isolated pentagons, preferential reaction sites are their C–C bonds. Ideal graphene sheet sidewalls with cylindrical curvature are relatively inert (although one cannot discard the possibility to activate the reaction by heating). Dithiol groups introduced in the way proposed can be used as chemical linkers for anchoring metal complexes and nanoparticles to carbon nanotubes, attaching SWNTs to gold tips for atomic force and scanning tunneling microscopy, and potentially for adsorption and concentration of trace metal ions.     

嵌段共聚物修饰多壁碳纳米管

为了改善多壁碳纳米管的分散性,通过丙烯酸和羟基化多壁碳纳米管的酯化反应将双键引入到碳纳米管的表面,同时利用原子转移自由基聚合合成端基为卤素的苯乙烯-b-甲基丙烯酸羟乙酯嵌段共聚物,并通过对双键的加成反应,将嵌段共聚物引入到多壁碳纳米管的表面,实现了碳纳米管的化学修饰。通过FTIR、TGA和TEM技术对产物进行了表征,结果表明:嵌段共聚物通过共价键接枝到碳纳米管表面,其含量为42.9%,平均约277个碳原子接枝一条聚合物链;修饰后的MW CNTs在乙醇中分散良好。     

Mechanical and thermal properties of epoxy nanocomposites reinforced with amino-functionalized multi-walled carbon nanotubes

The functionalized multi-walled carbon nanotubes (MWNTs) with amino groups were prepared after such steps as oxidation, the addition of carboxyalkyl radicals, acylation and amidation. Besides oxidated-MWNTs/epoxy nanocomposites, amino-functionalized MWNTs/epoxy nanocomposites, in which MWNTs with amino groups acted as a curing agent and covalently attached into the epoxy matrix, were fabricated. Subsequently, the effects of MWNT content on the mechanical and thermal properties for the two systems were investigated. It is found that both the tensile strength and impact strength enhance with the increase of MWNT addition, and the most significant improvement of the tensile strength (+51%) and especially impact strength (+93%) is obtained with amine-treated MWNTs at an 1.5 wt.% content. Moreover, the thermal stability of the nanocomposites also distinctly improves. The improvement of the properties of the amine-treated MWNTs system is more remarkable than those of o-MWNTs system. The reasons for these changes were discussed.     

Vibration analysis of multi-walled carbon nanotubes using a spring–mass based finite element model

We report a study of the vibrational characteristics of multi-walled carbon nanotubes modeled exclusively using springs and lumped masses. Based on the atomic microstructure of the nanotube, three-dimensional nanoscale spring elements are utilized to simulate the dynamic behavior of each layer of the multi-walled carbon nanotubes. Appropriate spring elements are also developed to model the interlayer interactions and describe the van der Waals potentials between carbon atoms on different layers. Direct application of the physical variables of molecular mechanics theory to the springs is used to simulate the relative translations and rotations between atoms as well as the masses of the carbon atoms. The stiffness and mass matrices of the problem are used to construct the dynamic equilibrium equation. The natural modes of vibration and the corresponding natural frequencies are derived by solving the eigenvalue problem for different support conditions. The present method suggests novel basic modes of vibration, beyond those reported in the literature pertaining to multi-walled carbon nanotubes. The effects on the basic modes and natural frequencies created by van der Waals interactions and geometric parameters such as number of layers and aspect ratio are investigated in the context of elastic support conditions. Comparisons with other theoretical studies reveal very good correlations in terms of fundamental modes and frequencies.     

Cyclodextrin polyurethanes polymerized with multi-walled carbon nanotubes: Synthesis and characterization

Insoluble cyclodextrin polymers co-polymerized with multi-walled carbon nanotubes were synthesized by polymerizing β-cyclodextrin with acid-functionalized multi-walled carbon nanotubes and diisocyanate linkers; hexamethylene- and toluene-2,4-diisocyanate. The polymers are useful in removing some organic pollutants from water, and we now report the full characterization of these polymers using infrared spectroscopy (IR), Raman spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and thermal techniques such as thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).The polymers could be synthesized as either powders or amorphous solids. Results of the IR analysis showed the presence of functional groups such as CO, CC, CH and CO, indicating that polymerization indeed took place. Characterization of the polymers by scanning electron microscopy and BET analysis showed that these polymers had a spongy appearance indicating a hierarchical pore structure. Incorporation of small amounts (<5%) of multi-walled nanotubes (MWNTs) improved the thermal stability of the polymers. This observation was further confirmed by differential scanning calorimetry (DSC) measurements.     

Lyocell/多壁碳纳米管复合纤维的制备及性能

将多壁碳纳米管(MWCNTs)水悬浮液、N-甲基吗啉-N-氧化物(NMMO)溶液及纤维素共混得到纺丝液,通过干湿法制备了Lyocell/MWCNT复合纤维。采用X-衍射仪(WAXD)、扫描电镜(SEM)、透射电镜(TEM)、强度仪等分析了所得纤维的结构和性能。WAXD图谱显示复合纤维仍然具有纤维素II晶型的结构,同时还保留了MWCNTs的特征衍射峰;二维X衍射结果表明:MWCNTs质量分数为5%的复合纤维中,MWCNTs与纤维轴的取向角为±15.2°,说明复合纤维中MWCNTs基本沿着纤维轴取向。SEM结果显示复合纤维中MWCNTs在Lyocell基体中分布均匀。对纤维的力学性能分析进一步表明:添加适量的MWCNTs可使复合纤维的力学性能提高,MWCNTs质量分数为1%的复合纤维的初始模量和强度分别比Lyocell纤维增加49.4%和15.7%。     

Enhanced thermoelectric performance of CuAlS2 by adding multi-walled carbon nanotubes

In this paper, we report the first-ever study on a relatively uniform dispersion of multi-walled carbon nanotubes (MWCNTs) in CuAlS₂ nanoparticles, synthesized by high-energy ball-milling, and study the thermoelectric properties of the bulk materials. A vortex mixer and bath sonicator are used to achieve well dispersion of nanotubes in the matrix, and then the powder is hot-pressed. Carbon nanotubes dispersed in the matrix improve electrical conductivity and Seebeck coefficient. The addition of MWCNT causes an increase in the grain boundary and facilitates phonon scattering, resulting in a reduction in the lattice thermal conductivity and finally total thermal conductivity. The optimum amount of carbon nanotubes is effective for reducing thermal conductivity and increasing electrical conductivity, thereby elevating the figure-of-merit of the nanocomposites. Finally, the figure-of-merit is highly influenced by total thermal conductivity, and the maximum figure-of-merit was obtained for CuAlS₂/0.5 wt% MWCNT composite, which indicated about 20% improvement.     

Fabrication of humidity sensors by multi-walled carbon nanotubes

Humidity sensors have multi-walled carbon nanotubes (MWNTs) as the sensing material is demonstrated. The sensor was fabricated on a silicon dioxide coated silicon wafer with metal electrodes. MWNTs were deposited and interlinked with the electrodes by means of the dielectrophoresis technique. The sensing device has the function of a hygrometer when measuring resistance variations to the local relative humidity percentage (RH%) through MWNTs. By measuring the MWNT resistances, we find that higher RH% results in a decrease of conductivity. The results indicate that electron transports in MWNTs are affected by water molecules adsorption on the outermost nanotube surface. A miniature thermocouple sensor was also fabricated and integrated with the humidity sensor. This allowed us to simultaneously sense environmental humidity and temperature. Hence, accurate humidity measurements were achieved with this prototype by calibrating the electrical resistance and temperature levels to carry out the tests with the humidity percentages.     

Dispersion of functionalized multi-walled carbon nanotubes in multi-walled carbon nanotubes/liquid crystal nanocomposites and their thermal properties

A novel liquid crystal functionalized multi-walled carbon nanotubes (LC-MWNTs)/2-methyl-N,N′-bis(4′-methoxy benzoyloxy)-terephthalamide liquid crystal (LC) nanocomposite (LC-MWNTs/LC) was prepared via solution blend. The dispersion and thermal property of the nanocomposites with different loadings of LC-MWNTs (0.1-1 wt.%) were investigated using SEM, TGA and DSC. The results show that the dispersion of LC-MWNTs in LC matrix is more homogeneous than purified MWNTs. The decomposition temperature of nanocomposites exhibits obvious decrease at first and then increase with increasing concentration of LC-MWNTs, which is lower than that of LC for 0.1-0.4 wt.% LC-MWNT loadings and higher than that of LC for 0.5-1 wt.% LC-MWNT loadings. The addition of LC-MWNTs has little effects on the texture of smectic mesophase. These results illustrate the LC-MWNTs/LC nanocomposites, which have lower melting point and higher decomposition temperature than those of LC by adding adequate amount of LC-MWNTs, show a wide temperature range of mesophase and high thermostability. The increased mesophase temperature region of LC materials will be beneficial to their practical applications.     

Dynamic stability analysis of multi-walled carbon nanotubes with arbitrary boundary conditions based on the nonlocal elasticity theory

Dynamic stability of embedded multi-walled carbon nanotubes (MWCNTs) in an elastic medium and thermal environment and subjected to an axial compressive force is studied based on the nonlocal elasticity and Timoshenko beam theory. The developed nonlocal beam model has the capability to consider the small scale effects. The generalized differential quadrature method is employed to discretize the dynamic governing differential equations of MWCNTs with various end supports. A parametric study is conducted to investigate the influences of static load factor, temperature change, nonlocal parameter, slenderness ratio, and spring constant of elastic medium on the dynamic stability characteristics of MWCNTs.