Atomic layer deposition on suspended single-walled carbon nanotubes via gas-phase noncovalent functionalization

Alternating exposures of nitrogen dioxide gas and trimethylaluminum vapor are shown to functionalize the surfaces of single-walled carbon nanotubes with a self-limited monolayer. Functionalized nanotube surfaces are susceptible to atomic layer deposition of continuous, radially isotropic material. This allows for the creation of coaxial nanotube structures of multiple materials with precisely controlled diameters. Functionalization involves only weak physical bonding, avoiding covalent modification, which should preserve the unique optical, electrical, and mechanical properties of the nanotubes.     

基于碳纳米管复合物的电化学生物传感器研究进展

新型碳纳米管复合物的开发及其在电化学生物传感器中的应用是近年来材料学和分析领域的研究热点.介绍了碳纳米管复合物在电化学生物传感领域的研究发展,重点对碳纳米管与纳米颗粒、聚合物及离子液体复合材料在电化学生物传感中的应用进行了论述.     

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.     

Chemical functionalization of carbon nanotubes

There are many reasons why one would want to form chemical attachments to the walls or ends of carbon nanotubes: these chemical bonds might be used to tailor the interaction of the nanotube with other entities, such as a solvent, a polymer matrix, or other nanotubes. The chemically functionalized nanotube might have mechanical or electrical properties that are different from those of the unfunctionalized nanotube and thus might be used as a chemical sensor or a nanometer-scale electronic device. The challenge is to find a way to reproducibly and reliably chemically alter carbon nanotubes that, like graphite, are fairly unreactive. The various methods used to date and the possible application of the resulting functionalized nanotubes is discussed in this review paper.     

The preparation of highly water-soluble multi-walled carbon nanotubes by irreversible noncovalent functionalization with a pyrene-carrying polymer

Multi-walled carbon nanotubes (MWNTs) have been solubilized in water via a noncovalent method of exfoliation and centrifugation cycles with the assistance of hydrolyzed poly(styrene-co-maleic anhydride) carrying pyrene (HPSMAP). After the obtained solution was micro-filtered and dried, a water-soluble complex of HPSMAP-MWNTs was obtained. The solubility of HPSMAP-MWNTs was measured to be 46.2?mg?ml(-1) with a net MWNT concentration of 7.4?mg?ml(-1) in water. Thermal gravimetric analyses showed that there was a large amount of polymer remaining on the surface of MWNTs irreversibly after thoroughly removing the free polymer. Other characterizations using transmission electron microscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence spectra, and fluorescence decay were conducted.     

碳纳米管溶解性及其化学修饰

详细评述了增加碳纳米管在水和有机溶剂中溶解性的途径，包括单一溶剂直接分散、电子供一受体电荷转移、可溶性聚合物或表面活性剂筒状胶束包裹等非共价键相互作用和顶端开口、化学衍生以及侧壁化学修饰等共价化学修饰。指出今后一段时期碳纳米管化学的主要任务为通过非共价的或共价的化学修饰，改善碳纳米管本身的性能和用途，并耦合其他如化学的、生物的或物理的功能扩展其应用范围。进一步深入理解碳纳米管化学(尤其是其溶液化学)反应理论。     

Raman spectra of double-wall carbon nanotubes under extreme uniaxial stress

We investigated the pressure dependence of the Raman frequencies and intensities of the D and G bands of double-wall carbon nanotubes under strong uniaxial conditions. Using moissanite anvils, we observed for the first time the evolution of the D band under extreme stress/pressure conditions. We find that the difference between D and G frequencies remains constant over the whole stress range. In addition, we observe that double-wall carbon nanotubes behave elastically up to the maximum uniaxial stress reached in our experiments, which is estimated to be about 12 GPa.     

Spectroscopy of single- and double-wall carbon nanotubes in different environments

Individual single-wall carbon nanotubes (SWNTs) and double-wall carbon nanotubes (DWNTs) were suspended in water for optical studies using sodium-cholate and other surfactants. We used time-resolved photoluminescence (PL) spectroscopy to study the influence of tube chirality and diameter as well as of the environment on nonradiative decay in small diameter tubes. The studies provide evidence for PL from small diameter core tubes in DWNTs and for a correlation of nonradiative decay with tube diameter and exciton red shift as induced by interaction with the environment.     

Layer-by-layer assemblies of chitosan/multi-wall carbon nanotubes and glucose oxidase for amperometric glucose biosensor applications

A novel amperometric glucose biosensor based on multilayer films containing chitosan, multi-wall carbon nanotubes (MWCNTs) and glucose oxidase (GOD) was developed. MWCNTs were solubilized in chitosan (Chit-MWCNTs) used to interact with GOD. Poly (allylamine) (PAA) and polyvinylsulfuric acid potassium salt (PVS) were alternately deposited on the cleaned Pt electrode surface ((PVS/PAA)₃/Pt). The (PVS/PAA)₃/Pt electrode was alternately immersed in Chit-MWCNTs and GOD to assemble different layers of multilayer films. PBS washing was applied at the end of each assembly deposition for dissociating the weak adsorption. Micrographs of MWCNTs were obtained by scanning electron microscope, and properties of the resulting biosensors were measured by electrochemical measurements. Among the resulting biosensors, the biosensor based on eight layers of multilayer films was best. The resulting biosensor was able to efficiently monitor glucose, with the response time within 8 s, a detection limit of 21 μM estimated at a signal-to-noise ratio of 3, a linear range of 1–10 mM, the sensitivity of 0.45 μA/mM, and well stability. The study can provide a feasible simple approach on developing a new immobilization matrix for biosensors and surface functionalization.     

Sidewall functionalization of carbon nanotubes through electrophilic substitution

We report a general strategy for functionalizing the sidewalls of carbon nanotubes (CNTs), which is based on electrophilic substitution reactions on phenylated CNTs. By using this strategy, four new functionalized CNTs were prepared, including diphenyl ketone, benzenesulfonyl chloride, benzyl chloride and thiophenol modified CNTs. The benzenesulfonyl chloride and benzyl chloride functinalized CNTs could serve as novel initiators for surface-initiated atom transfer radical polymerization. The thiophenol modified CNTs were used in immobilizing Pd nanoparticles on the CNT surface, and the CNT/Pd hybrid produced exhibits good catalytic efficiency for the electrochemical oxidation of methanol.     

碳纳米管共价修饰功能化研究进展

综述了近年来国内外碳纳米管共价修饰功能化的研究进展,功能化后的碳纳米管不仅保持了原有的特异性质,而且还表现出修饰基团参加反应的活性,为碳纳米管的分散、组装及表面反应提供可能。     

Microwave-assisted functionalization of single-wall carbon nanotubes through diazonium

Single-wall carbon nanotubes (SWNTs) have been functionalized by a diazonium method through both a classical thermal reaction and a microwave-assisted reaction. The functionalized SWNTs have been characterized by nIR-Vis-UV absorption spectroscopy, Raman spectroscopy, and thermal gravimetric analysis. The results show that SWNTs are covalently functionalized through both reactions and that the microwave-assisted reaction is more rapid. Moreover, optimal choice of the reaction time can prevent the microwave irradiation from the adverse effect of subsequently removing the functional groups on the SWNT surface.     

Structure determinations of double-wall carbon nanotubes grown by catalytic chemical vapor deposition

We report an application of nanoarea electron diffraction for structure determination of double-wall carbon nanotubes (DWNT) grown by catalytic chemical vapor deposition. The structures of 30 tubes were determined from experimental diffraction patterns. Among these tubes, the inner and outer wall structure of 18 tubes was precisely determined by comparison with kinematic electron diffraction simulations. For the structure of the DWNTs, our experiment revealed a mixture of semiconducting-metallic (S-M), S-S and M-M tubes. The spacing between the two walls ranges from 0.335 nm to 0.384 nm. Most DWNTs are incommensurate and chiral.     

Nitrogen plasma functionalization of carbon nanotubes for supercapacitor applications

Surface modification of carbon nanotubes with a simple and fast plasma treatment allows for the design of new nanomaterials with enhanced electrochemical properties. Both structural disorder and nitrogen concentration of the nanotubes increase after a nitrogen plasma treatment. The effect of plasma power and nitrogen pressure on the charge storage capability of the nanotubes has been investigated in detail. Depending on the plasma conditions, nitrogen functionalities such as quaternary nitrogen in the basal planes, and pyrrolic groups at the edges are introduced in the nanotubes structure. The potential difference between anodic and cathodic peaks of the Fe³⁺/Fe²⁺ redox couple decreases from 102 mV down to 75.7 mV after the nitrogen plasma treatment, which accounts for an increased reversibility of the electron transfer process between nanotubes and electrolyte. Moreover, the treated nanotubes show a significant increase in their specific capacitance from 22 up to 55 F g^?1 at a scan rate of 10 mV s^?1 in a 0.1 M Na₂SO₄ solution. Pyridinic and pyrrolic functionalities are found to play an important role in enhancing the reversibility and specific capacitance of the obtained electrodes.     

1.6-己二胺化学修饰多壁碳纳米管

为获得两端具有活性端胺基的碳纳米管,通过化学方法对多壁碳纳米管(MWCNTs)接枝改性,利用氯化亚砜将MWCNTs酸处理产生的羧基转化为酰氯,进一步与1.6-己二胺发生亲核取代反应,将1.6-己二胺接枝到碳纳米管端部.采用X射线光电子能谱(XPS)、透射电镜(TEM)及扫描电镜(SEM)对化学修饰过程中各反应产物进行表征.结果表明:酸的切割作用,使碳纳米管从端帽下及管壁缺陷处打开,碳管长度由十几微米变为500nm左右;1.6-己二胺成功地接枝到碳纳米管端部,能谱分析(EDS)结果表明N元素接枝率达3.29%,接枝后的碳纳米管可以均匀分散在丙酮溶液中,并含有活性端胺基.     

Highly conductive and mechanically robust multiwalled carbon nanotube-polyamide nanocomposites via noncovalent functionalization

Journal of Materials Science - Electrically conductive multiwalled carbon nanotube (MWNT)/polyamide 6 (PA 6) nanocomposite films with high mechanical strength were fabricated by blending modified...     

Rayleigh scattering studies on inter-layer interactions in structure-defined individual double-wall carbon nanotubes

Although the inter-layer coupling in layered materials has attracted considerable interest due to its importance in determining physical properties of two-dimensional systems, studies on the inter-layer coupling in one-dimensional systems have so far been limited. Double-wall carbon nanotubes (DWCNTs) are one of the most fundamental and ideal model systems to study the inter-layer coupling in one-dimensional systems. In this work, Rayleigh scattering spectroscopy and transmission electron microscopy are used to characterize the electronic transition between inner-and outer-nanotubes of the exactly same individual DWCNT. We find that the inter-layer coupling is strong, leading to downshifts in most of the optical transition energies (up to ～0.2 eV) compared to isolated CNTs. We also find that the presence of metallic tubes lead to stronger shifts. The inter-layer screening of Coulomb interactions is one of the key factors in explaining the observed results.      

Dispersion and functionalization of carbon nanotubes for polymer-based nanocomposites: A review

Carbon nanotubes (CNTs) hold the promise of delivering exceptional mechanical properties and multi-functional characteristics. Ever-increasing interest in applying CNTs in many different fields has led to continued efforts to develop dispersion and functionalization techniques. To employ CNTs as effective reinforcement in polymer nanocomposites, proper dispersion and appropriate interfacial adhesion between the CNTs and polymer matrix have to be guaranteed. This paper reviews the current understanding of CNTs and CNT/polymer nanocomposites with two particular topics: (i) the principles and techniques for CNT dispersion and functionalization and (ii) the effects of CNT dispersion and functionalization on the properties of CNT/polymer nanocomposites. The fabrication techniques and potential applications of CNT/polymer nanocomposites are also highlighted.     

Amperometric biosensor based on carbon nanotubes coated with polyaniline/dendrimer-encapsulated Pt nanoparticles for glucose detection

A novel amperometric glucose biosensor based on the nanocomposites of multi-wall carbon nanotubes (CNT) coated with polyaniline (PANI) and dendrimer-encapsulated Pt nanoparticles (Pt-DENs) is prepared. CNT coated with protonated PANI is in situ synthesized and Pt-DENs is absorbed on PANI/CNT composite surface by self-assembly method. Then Glucose oxidase (GOx) is crosslink-immobilizated onto Pt-DENs/PANI/CNT composite film. The results show that the fabricated GOx/Pt-DENs/PANI/CNT electrode exhibits excellent response performance to glucose, such as low detection limit (0.5 µM), wide linear range (1 µM–12 mM), short response time (about 5 s), high sensitivity (42.0 µA mM^? 1 cm^? 2) and stability (83% remains after 3 weeks).     

碳纳米管羧基化及其电化学性能研究

利用氧化剂对多壁碳纳米管(MWNTs)进行处理,成功的制备了羧基化的碳纳米管。分别通过TEM、XRD、全自动比表面及孔隙度分析仪及恒流充放电装置对它们的形貌、晶体结构、比表面积及电容性能进行了研究,电容性能结果显示羧基化的碳纳米管电容值明显增强,这应该归因于羧基化的碳纳米管拥有较大的比表面积和亲水性,有利于电解液离子的传输。