氢等离子电弧法半连续制备单壁纳米碳管

用氢气到代拟气作为缓冲气体,适当改进电弧反应装置并掺加一种生长促进剂可以有效地提高单壁纳米碳管的产量和质量。氢电弧法制备出的单壁纳米碳管堆积成膜状或网状,电镜下可见产物主要由相互缠绕的单壁纳米碳管束构成,纯度较高;激光拉曼分析结果表明制得的单壁纳米碳管直径较大。单壁纳米碳管产物在形貌和结构上的上述特征与氢气和生长促进剂的作用密切相关。     

单壁纳米碳管的研究进展

综述了当前单壁纳米碳管的研制状况,对单纳米碳管的制备方法,结构特征,性能和应用前景进行了讨论,并且对单壁纳米碳管的新制备方法－本研究组独创的有机物气相催化热解法进行论述。     

高质量小直径单壁纳米碳管的CVD法制备

使用溶胶凝胶法制备了Fe/Mo/MgO催化剂,用化学气相沉积法在1000℃下催化裂解甲烷,制备了高质量的单壁纳米碳管.用SEM、TEM、HRTEM、TGA和Raman等方法对制备的纳米碳管粗产品进行了表征.结果表明:该产物确为单壁纳米碳管,单壁纳米碳管直径十分均一,在0.86～0.90nm之间,且其形态基本上都是以束状存在;本方法所制得粗产物中单壁碳管的含量在30%以上.     

硫促进剂对单壁纳米碳管生成的影响

研究了有机物催化热解法中硫生长促进剂对单壁纳米碳管生成的影响，结果表明，含硫生长促进剂能促进单壁纳米碳管的生成，提高产率，并改变其直径数值的分布；促进剂的添加量大，纳米碳管的直径也大。     

单壁纳米碳管制备方法的新进展

纳米碳管以其独特的结构、优异的物理化学性质以及超高的力学性能而具有巨大的应用前景．单壁纳米碳管作为纳米碳管结构的基础，在纳米电子器件、单电子器件、储能材料等方面表现出了良好的性能．基于对单壁纳米碳管的研究，综述了近年来在单壁纳米碳管制备技术方面取得的最新进展，其中包括电弧放电法、化学气相沉积法以及激光蒸发法等方法，并讨论了在不同方法中影响单壁纳米碳管生长的几个关键因素．     

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.     

以煤为碳源直流电弧法制备单壁纳米碳管绳

以太西无烟煤为碳源，以稀土氧化物La2O3和过渡金属Ni为催化剂制备复合的煤基炭棒，采用直流电弧放电技术，成功实现了单壁纳米碳管绳的批量制备。用TEM和Raman光谱技术对纳米碳管绳产品进行了分析表征。结果表明：太西煤是制备单壁纳米碳管的合适碳源；电弧放电得到的煤基单壁纳米碳管的直径分布在2．01nm-1．80nm之间；双金属催化剂Ni-La在单壁纳米碳管的形成过程中存在协同作用，其催化活性优于其中的单一组分。     

纳米碳管结构差异对树脂炭包覆硅/纳米碳管复合材料电化学性能的影响

采用聚乙烯醇（PVA）树脂炭化的方法，制备了PVA树脂炭包覆硅／不同纳米碳管复合材料，通过X-射线、高分辩电镜观察和电化学性能测试等手段比较研究了单壁、双壁和多壁纳米碳管作为弹性导电网络缓解硅在充放电过程中体积变化方面的效果。结果表明，单壁纳米碳管和双壁纳米碳管比多壁纳米碳管能够更好地缓解硅在循环过程中产生的结构和体积变化，这主要是因为其长径比大，缠裹效果更好。单壁纳米碳管和双壁纳米碳管具有相近的直径、长径比及宏观分布形式，但在循环过程中，双壁纳米碳管的结构稳定性好于单壁纳米碳管，进而其缓解硅结构变化的效果更好。     

多壁纳米碳管的制备与表面改性处理

以Co-MCM-41作催化剂,采用化学气相沉积(CVD)法催化热解无水乙醇制备纳米碳管(CNTs),然后将纳米碳管在120℃下用浓硝酸回流,进行纯化及表面酸氧化改性处理。通过XRD、FT-IR、TEM、N2吸附-脱附和Raman光谱等分析手段对酸处理前后的纳米碳管进行了表征。结果表明制备出品质较好、管径均匀、管壁较厚、顶端开口的多壁纳米碳管。浓硝酸氧化处理后在纳米碳管的表面存在羧基和羟基等官能团。     

CVD宏观量半连续制备纳米碳管的研究

研究了以乙炔为基本原料,用Ｎ_２做载流气体;以纳米钻颗粒为催化剂在７００～８００℃常压下纳米碳管的宏观量制备．粗产品中纳米碳管的含量接近５０％,而且纳米碳管缺陷很少,直而长,石墨化好．纳米碳管的形核过程是因为碳在催化剂表面分布不均匀造成的．纳米碳管的生长极限在１５ｍｉｎ左右,然后生长变得缓慢,纳米碳管的一般长度在５～３０μｍ．     

Polymeric nanocomposites of functionalized carbon nanotubes synthesized in supercritical CO2

A novel method to synthesize single-wall carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) nanocomposite by in-situ polymerization in supercritical CO2 is presented. The surfaces of the SWNT bundles were first functionalized with amino ethyl methacrylate (AEMA) followed by co-polymerization with methyl methacrylate. Supercritical fluid enhanced the diffusivity of monomer and facilitated the growth of tethered PMMA chains near the entanglement area and the interstitial space of the SWNT bundles. Partial debundling and disentanglement of the SWNT bundles and an enhanced dispersion in the polymer matrix were observed under SEM and TEM. After the removal of the polymer matrix physically attached to the nanotubes, it is found that the nanotubes were covered by tethered PMMA chains, which were a few nanometers in thickness. This work creates a route for improving impregnation and dispersion in SWNT composites; the same process can be extended to other vinyl polymers.     

Double-walled carbon nanotubes under hydrostatic pressure: Raman experiments and simulations

We have used Raman spectroscopy to study the behavior of double-walled carbon nanotubes (DWNT) under hydrostatic pressure. We find that the rate of change of the tangential mode frequency with pressure is higher for the sample with traces of polymer compared to the pristine sample. We have performed classical molecular dynamics simulations to study the collapse of single (SWNT) and double-walled carbon nanotube bundles under hydrostatic pressure. The collapse pressure (pc) was found to vary as 1/R3, where R is the SWNT radius or the DWNT effective radius. The bundles showed approximately 30% hysteresis and the hexagonally close packed lattice was completely restored on decompression. The pc of a DWNT bundle was found to be close to the sum of its values for the inner and the outer tubes considered separately as SWNT bundles, demonstrating that the inner tube supports the outer tube and that the effective bending stiffness of DWNT, D(DWNT) - 2D(SWNT).     

Enhanced cellular activation with single walled carbon nanotube bundles presenting antibody stimuli

Efficient immunotherapy can be accomplished by expanding T cells outside the body using single walled carbon nanotube (SWNT) bundles presenting antibody stimuli. Owing to the large surface area of these bundles, which can reach 1560 m (2)/g, T cell stimulating antibodies such as anti-CD3, can be presented at high local concentrations inducing potent activation of T cells. We show that anti-CD3 adsorbed onto SWNT bundles stimulate cells more effectively than equivalent concentrations of soluble anti-CD3. Stimulation by antibody adsorbed onto SWNT is significantly higher than other high surface area materials (activated carbon, polystyrene, and C60 nanoparticles), suggesting unique properties of SWNT bundles for stimuli presentation. We demonstrate the surface area tunability of these bundles by chemical treatment and its effect on antibody adsorption and subsequent T cell activation. In addition, the T cell response varied with the concentration of SWNT in a concentration dependent manner. Antibody stimuli adsorbed onto SWNT bundles represent a novel paradigm for efficient activation of lymphocytes, useful for basic science applications and clinical immunotherapy.     

Designing Catalysts for Chirality‐Selective Synthesis of Single‐Walled Carbon Nanotubes: Past Success and Future Opportunity

A major obstacle for the applications of single‐walled carbon nanotubes (SWNTs) in electronic devices is their structural diversity, ending in SWNTs with diverse electrical properties. Catalytic chemical vapor deposition has shown great promise in directly synthesizing high‐quality SWNTs with a high selectivity to specific chirality (n, m). During the growth process, the tube–catalyst interface plays crucial roles in regulating the SWNT nucleation thermodynamics and growth kinetics, ultimately governing the SWNT chirality distribution. Starting with the introduction of SWNT growth modes, this review seeks to extend the knowledge about chirality‐selective synthesis by clarifying the energetically favored SWNT cap nucleation and the threshold step for SWNT growth, which describes how the tube–catalyst interface affects both the nucleus energy and the new carbon atom incorporation. Such understandings are subsequently applied to interpret the (n, m) specific growth achieved on a variety of templates, such as SWNT segments or predefined molecular seeds, transition metal (Fe, Co and Ni)‐containing catalysts at low reaction temperatures, W‐based alloy catalysts, and metal carbides at relatively high reaction temperatures. The up to date achievements on chirality‐controlled synthesis of SWNTs is summarized and the remaining major challenges existing in the SWNT synthesis field are discussed.     

Diode-like properties of as-grown chemical vapor deposited single-walled carbon nanotubes

Current rectification property of as-grown single-walled carbon nanotubes (SWNTs) is investigated. The SWNTs are grown by chemical vapor deposition (CVD) process. The process allowed to grow long strands of SWNT bundles, which are then used to fabricate multiple arrays of switching devices with the channel length of 3, 5, 7 and 10 microm on a 15 mm x 15 mm SiO2 on Si substrate. Regardless of the channel length, a majority of the fabricated devices show current rectification characteristics, with high throughput of current (I) in the forward bias (V) giving the forward and reverse current ratio (Ifor/Irev) of approximately 10(6). Atomic force microscopic (AFM) analysis of the device structure and surface topology of SWNT suggest the observed rectification of current to possibly result from (a) cross-tube junctions, (b) a mixture of metallic and semiconducting tubes in the SWNT bundles, and/or (c) chirality change along a single tube. The exact mechanism underlying the observed rectification could not be conclusively established. However, the analyses of the experimental results strongly suggest the observed rectification to result from Schottky-type diode properties of SWNTs with mixed chirality along the tube.     

Towards a ‘catalyst activity map’ regarding the nucleation and growth of single walled carbon nanotubes

Quantification using scanning electron microscopy (SEM) of single walled carbon nanotubes (SWNTs) grown per unit area using a Co-Fe (50:50) catalyst system, prepared by the incorporation of the appropriate metal salts into a Spin-On Glass substrate, at 900°C. The effects of substrate, as well as catalyst precursor concentration, were investigated. SWNT growth density is maximised with a catalyst precursor concentration of ≥2.5 mM, associated with the formation of catalyst nanoparticles of a critical size for SWNT nucleation. Samples were subjected to secondary growth, using a range of H₂:CH₄ ratios to determine the optimum precursor composition. It was found that nucleation and growth stages are optimal under different conditions. Optimum conditions for nucleation resulted in >10× increase in SWNT density. Optimisation is dependent on temperature and the partial pressure of reagent gas species.     

A possible route to large-scale production of SWNTs through a combination of the substrate and floating catalyst methods

We describe a possible route for large-scale synthesis of single wall carbon nanotubes (SWNTs) by a combination of the substrate and floating methods. The template prohibits metal particle aggregation, resulting in high-purity SWNT growth, and the three-dimensional floating seeded state of the template induces improved yields of SWNTs in a semi-continuous system. The SWNTs obtained by this method exhibit large variations of texture (isolated tubes and bundles) and a wide range of diameters (0.4-4 nm).     

Mechanical Peeling of Free‐Standing Single‐Walled Carbon‐Nanotube Bundles

An in situ electron microscopy study is presented of adhesion interactions between single‐walled carbon nanotubes (SWNTs) by mechanically peeling thin free‐standing SWNT bundles using in situ nanomanipulation techniques inside a high‐resolution scanning electron microscope. The in situ measurements clearly reveal the process of delaminating one SWNT bundle from its originally bound SWNT bundle in a controlled‐displacement manner and capture the deformation curvature of the delaminated SWNT bundle during the peeling process. A theoretical model based on nonlinear elastica theory is employed to interpret the measured deformation curvatures of the SWNTs and to quantitatively evaluate the peeling force and the adhesion strength between bundled SWNTs. The estimated adhesion energy per unit length for each pair of neighboring tubes in the peeling interface based on our peeling experiments agrees reasonably well with the theoretical value. This in situ peeling technique provides a potential new method for separating bundled SWNTs without compromising their material properties. The combined peeling experiments and modeling presented in this paper will be very useful to the study of the adhesion interactions between SWNTs and their nonlinear mechanical behaviors in the large‐displacement regime.     

Separation of single-walled carbon nanotubes by use of ionic liquid-aided capillary electrophoresis

This paper presents a simple, highly efficient method for analyzing single-walled carbon nanotube (SWNT) bundles based on (1) ultrasound-assisted solubilization/dispersion of SWNTs in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, (2) encapsulation of the nanotubes in sodium dodecyl sulfate micelles, and (3) analysis by capillary electrophoresis. The process by which SWNTs disperse in the ionic liquid was studied by Raman spectroscopy. No degradation of SWNTs was observed under mild sonication conditions. The shape and position changes observed in the Raman spectral bands for the nanotubes are ascribed to debundling and interaction with the ionic liquid. Separation of solubilized SWNTs was accomplished by using a 50 mM formic acid solution at pH 2.0 as background electrolyte and a potential of -10 kV. Under these conditions, separation was completed within only 4 min. Eighteen peaks for SWNTs were identified in the analysis of commercial SWNT bundles. The two types of bundles studied exhibited distinct, highly characteristic electrophoretic profiles which could be used to control SWNTs purity.     

Single‐Walled Carbon‐Nanotube Networks on Large‐Area Glass Substrate by the Dip‐Coating Method

Highly uniform and large‐area single‐walled carbon‐nanotube (SWNT) networks are realized by the dip‐coating method, which is based on fundamental fluid‐dynamic phenomena such as capillary condensation and surface tension. The changes in the polarity and hydration properties of the substrate affect the morphology of the SWNT networks and result in nonlinear growth of the networks in the repetitive dip‐coating process. The density and the thickness of the SWNT networks are controlled by processing variables including number of dip coatings, concentration of SWNT colloidal solution, and withdrawal velocity. The networks have uniform sheet resistances and high optical transmittance in the visible wavelength range.