多壁碳纳米管功能化及其在电化学葡萄糖传感器中的应用

利用硅烷偶联剂的表面修饰技术,将氨基丙基三乙氧基硅烷(APS)共价接枝到酸处理后的碳纳米管的表面.红外光谱数据证实了该反应的可行性.修饰后的碳纳米管在水中具有良好的分散性.利用西夫碱反应将氨基化的碳纳米管与醛基化的葡萄糖氧化酶共价层层自组装到电极表面,获得灵敏度可控的葡萄糖传感器.用电化学交流阻抗法和扫描电镜对成膜过程...     

超支化聚对氯甲基苯乙烯修饰碳纳米管表面的研究

用原子转移自由基聚合(ATRP)与自缩合乙烯基聚合(SCVP)相结合合成超支化聚合物聚对氯甲基苯乙烯(PCMS),该聚合物每个分枝均以卤素原子封端. 用叠氮化反应将卤素原子转换为—N3. 通过—N3与单壁或复壁碳纳米管反应将超支化聚合物接到碳纳米管的表面上, 实现了碳纳米管的化学修饰. 通过FTIR, XPS, TEM和Raman光谱等证明PCMS是以共价键形式结合到碳纳米管表面上的. 利用TGA估算出碳纳米管表面的修饰密度, 证明用超支化结构大量的端基可反应的官能团可以改善聚合物对碳纳米管的修饰效果.     

非共价键法改性碳纳米管的研究进展

阐述了非共价键改性在碳纳米管功能化方面的应用进展,详细介绍了表面活性剂修饰、小分子的π-π堆积相互作用、聚合物的缠绕和包覆、生物大分子的包裹和吸附、内嵌填充修饰等改性方式的研究现状,并提出了非共价键法修饰碳纳米管未来改进的方向,探讨了不同修饰物与碳纳米管之间的相互作用机制。其中,含有共轭基团或芳基基团的聚合物,可以通过其共轭或芳基基团与碳纳米管间的π-π相互作用和范德华作用,实现对碳纳米管的非共价物理包覆。经聚合物功能化的碳纳米管在电池、催化剂、生物传感器和电化学装置上有较好的应用前景。此外,生物大分子对碳纳米管的非共价修饰不仅可以改善其在生物体系中的水溶性,而且通过合理设计还可以避免蛋白质、核酸等生物分子的非特异性吸附,从而得到具有特异性的生物分子-碳纳米管复合体系。     

聚合物微相分离诱导聚合物功能化碳纳米管的自组装

利用自组装的方法实现碳纳米管的有序排列对制备碳纳米管基复合材料至关重要.将聚4-乙烯基吡啶修饰的碳纳米管与含有羧基的接枝共聚物聚丙烯酸-g-聚甲基丙烯酸甲酯(PAA-g-PMMA)相混合,由于吡啶基团与羧基之间的氢键作用,在聚合物微相分离的过程中,将诱导形成碳纳米管的有序排列,得到一种基于碳纳米管自组装的蜂窝状膜.     

银溶胶诱导多壁碳纳米管非共价表面修饰

利用银溶胶活化诱导淀粉螺旋结构实现了多壁碳纳米管非共价表面修饰. 实验结果表明, 淀粉非共价表面修饰的多壁碳纳米管在水中容易分散, 扫描电镜分析表明, 经银溶胶处理的多壁碳纳米管被单根分散在银溶胶溶液中. 酶解试验、IR和EDS分析表明, 碳纳米管表面修饰了一层淀粉.     

两亲性聚合物修饰碳纳米管研究进展

随着两亲性共聚物在越来越多的领域显示出其功能,它的重要理论和应用意义正为人们所认识。用它来修饰碳纳米管,将会赋予碳纳米管更加优异的性能,因此为碳纳米管的研究提供了一个方向。本文综述了两亲性聚合物修饰碳纳米管表面的研究进展,从化学修饰和物理吸附、包裹两种修饰手段入手,着重介绍了两亲性聚合物化学修饰碳纳米管的方法和研究状况。最后,对修饰后的两亲性聚合物碳纳米管的分散性和自组装行为进行了综述。     

聚乙烯基吡咯烷酮修饰多壁碳纳米管的研究

采用超声波辅助技术,研究了两亲性聚合物聚乙烯基吡咯烷酮(PVP)修饰多壁碳纳米管(MWNTs)的效果、作用机理及影响因素.研究结果表明在适合的条件下两亲性聚合物PVP可以被引入到多壁碳纳米管表面,修饰后的MWNTs在DMF、乙醇和水等溶剂中具有良好的分散性.通过红外光谱(FTIR)和拉曼光谱(Raman)分析表明,两亲性聚合物与MWNTs之间产生了化学接枝作用,高分辨透射电镜分析表明两亲性聚合物不均匀地存在于MWNTs的表面和端部.两亲性聚合物的浓度对接枝量的影响不大,但超声波作用时间对MWNTs表面两亲性聚合物PVP的接枝量有较大的影响,在超声时间为4h时接枝量最大.两亲性聚合物修饰效果不同于表面活性剂,采用表面活性剂十二烷基苯磺酸钠(SDBS)修饰的MWNTs经过洗涤过滤后,不能重新溶于水中,而两亲性聚合物PVP修饰的MWNTs可以重新溶解.     

聚氨酯接枝多壁碳纳米管的制备及表征

采用两步法成功地将聚氨酯分子链以共价键连接到碳纳米管表面. 首先将聚丙烯酰氯通过与强酸氧化后多壁碳纳米管表面产生的羟基及少量羧基之间的化学反应共价接枝到碳纳米管表面; 然后将接枝到碳纳米管表面的聚丙烯酰氯与端羟基聚氨酯发生酯化反应, 实现了聚氨酯对碳纳米管的表面共价接枝. 采用傅里叶变换红外光谱(FTIR)、透射电镜(TEM)、扫描电镜(SEM) 和热重分析(TGA)等对接枝后的产物进行了表征, 结果表明, 聚氨酯已共价接枝到碳纳米管表面, 被接枝的聚合物的含量接近90%.     

表面引发原子转移自由基聚合制备聚电解质修饰的碳纳米管

利用聚电解质对多壁碳纳米管(MWNT)的表面进行修饰,能有效改善碳纳米管在溶剂中的分散性.首先将经硝酸氧化的碳纳米管与二甲亚砜和乙二醇反应,得到羟基修饰的碳纳米管.然后利用羟基与α-溴异丁酰溴(或α-氯丙酰氯)的酯化反应,在碳纳米管的表面引入了原子转移自由基聚合(atom transfer radical polymerization,ATRP)引发基团,引发丙烯酸叔丁酯(tBA)或4-乙烯基吡啶(4VP)聚合,通过投料比的改变,得到接入量不同的聚合物修饰的碳纳米管.利用热重分析(TGA)和红外对聚合物修饰的碳纳米管进行表征.将聚合物修饰的碳纳米管进行水解(或季胺化),制备得到在水溶液中良好分散的聚电解质修饰的碳纳米管.     

碳纳米管的快速糖基化及用于糖-凝集素特异性识别作用的研究

将含糖基的简单两亲分子N-十八烷基麦芽糖酰胺(N-n-Octadecyl-D-maltonamide, NOMA)非共价修饰到单壁碳纳米管(SWNT)表面形成糖-碳纳米管复合体(NOMA-SWNT), 谱学和形态学结果表明, NOMA不仅能快速、高效地吸附到SWNT表面, 而且能有效地改善SWNT在水溶液中的分散性能. 以NOMA-SWNT管束为导通沟道构建了碳纳米管场效应管(CNTFET)器件, 检测了麦芽糖和伴刀豆凝集素蛋白(Con A)的特异性识别作用. 检测器件在每个修饰阶段的电学性能的变化证明了NOMA对SWNT的非共价糖基化修饰及用CNTFET来检测糖-凝集素特异性识别作用的可能性.     

碳纳米管/聚合物复合材料

本文简要介绍了碳纳米管的纯化和表面改性方法，着重对碳纳米管/聚合物复合材料的制备方法、微观结构表征及其力学、电学、光学等性能的研究进行了综述；简述了此类复合材料在电学、电磁屏蔽材料及吸波隐身材料、纤维材料以及航天工业等领域的应用，探讨了该研究领域所面临的一些问题及今后的发展方向。     

Dispersible Carbon Nanotubes

A method is proposed to produce nanoparticles dispersible and recyclable in any class of solvents, and the concept is illustrated with the carbon nanotubes. Classically, dispersions of CNTs can be achieved through steric stabilization induced by adsorbed or grafted polymer chains. Yet, the surface modification of CNTs surfaces is irreversible, and the chemical nature of the polymer chains imposes the range of solvents in which CNTs can be dispersed. To address this limitation, supramolecular bonds can be used to attach and to detach polymer chains from the surface of CNTs. The reversibility of supramolecular bonds offers an easy way to recycle CNTs as well as the possibility to disperse the same functional CNTs in any type of solvent, by simply adapting the chemical nature of the stabilizing chains to the dispersing medium. The concept of supramolecular functionalization can be applied to other particles, for example, silica or metal oxides, as well as to dispersing in polymer melts, films or coatings.     

A Review Featuring Fabrication,Properties and Applications of Carbon Nanotubes (CNTs) Reinforced Polymer and Epoxy Nanocomposites

Carbon nanotubes (CNTs) have long been recognized as the stiffest and strongest man-made material known to date.In addition,their high electrical conductivity has roused interest in the areas of electrical appliances and communication related applications.However,due to their miniature size,the excellent properties of these nanostructures can only be exploited if they are homogeneously embedded into light-weight matrices as those offered by a whole series of engineering polymers.In order to enhance their chemical affinity to engineering polymer matrices,chemical modification of the graphitic sidewalls and tips is necessary.The mechanical and electrical properties to date of a whole range of nanocomposites of various carbon nanotube contents are also reviewed in this attempt to facilitate progress in this emerging area.Recently,carbonaceous nano-fillers such as graphene and carbon nanotubes (CNTs) play a promising role due to their better structural and functional properties and broad range of applications in every field.Since CNTs usually form stabilized bundles due to van der Waals interactions,they are extremely difficult to disperse and align in a polymer matrix.The biggest issues in the preparation of CNTs reinforced composites reside in efficient dispersion of CNTs into a polymer matrix,the assessment of the dispersion,and the alignment and control of the CNTs in the matrix.An overview of various CNT functionalization methods is given.In particular,CNT functionalization using click chemistry and the preparation of CNT composites employing hyperbranched polymers are stressed as potential techniques to achieve good CNT dispersion.In addition,discussions on mechanical,thermal,electrical,electrochemical and applications ofpolymer/CNT composites are also included.     

Marrying mussel inspired chemistry with SET‐LRP: A novel strategy for surface functionalization of carbon nanotubes

Surface functionalization of carbon nanotubes (CNTs) with a thermo responsive polymer was achieved via combination of mussel inspired chemistry and surface initiated single electron transfer living radical polymerization (SET‐LRP). In this procedure, CNTs were first coated with polydopamine (PDA) through self polymerization under a rather mild condition. And then PDA functionalized CNTs bearing with amino and hydroxyl groups were further reacted with bromo isobutyryl bromide. Finally, a thermo responsive polymer poly(N‐isopropylacrylamide) (PNIPAM) was introduced on the CNTs via SET‐LRP. The successful surface modification of CNT‐PDA‐PNIPAM was evidenced by a series of characterization techniques. The resulting CNT‐PDA‐PNIPAM showed significant enhancement of dispersibility in both aqueous and organic solvents. More importantly, these CNT‐polymer nanocomposites showed obvious thermo responsive behavior due to the surface coating CNTs with PNIPAM. As compared with previous methods, this method is not required oxidation of CNTs to introduce funcitonal groups for immobilization of the polymerization initiators. More importantly, this method could also be utilized for fabricating many other polymer nanocomposites because of the strong and universal adhesive of PDA to various materials. It is therefore, the novel strategy via marrying mussel inspired chemistry with SET‐LRP should be a simple, general and effective method for surface functionalization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1872–1879     

Modifications of carbon nanotubes with polymers

The chemical functionalizations of carbon nanotubes (CNTs) could enhance their chemical compatibility and dissolution properties, which enable both a more extensive characterization and subsequent chemical reactivity. The modifications with polymers could not only improve CNTs’ solubility and dispersibility but also the interfacial interaction to polymeric matrices in its composites. The main methods for the modification of CNTs with polymers are noncovalent attachment (polymer wrapping and absorption) and covalent attachment (“grafting to”and “grafting from”). The current states of the literatures in the field are presented in this review.     

Cytotoxicity of carbon nanotubes

With large-scale production and application at large scale, carbon nanotubes (CNTs) may cause ad-verse response to the environment and human health. Thus, study on bio-effects and safety of CNTs has attracted great attention from scientists and governments worldwide. This report briefly summa-rizes the main results from the in vitro toxicity study of CNTs. The emphasis is placed on the descrip-tion of a variety of factors affecting CNTs cytotoxicity, including species of CNTs, impurities contained, lengths of CNTs, aspect ratios, chemical modification, and assaying methods of cytotoxicity. However, experimental information obtained thus far on CNTs' cytotoxicity is lacking in comparability, and some-times there is controversy about it. In order to assess more accurately the potential risks of CNTs to human health, we suggest that care should be taken for issues such as chemical modification and quantitative characterization of CNTs in cytotoxicity assessment. More importantly, studies on physical and chemical mechanisms of CNTs' cytotoxicity should be strengthened; assaying methods and evaluating criteria characterized by nanotoxicology should be gradually established.     

Effect of elongational flow on morphology and properties of polymer/CNTs nanocomposite fibers

Carbon nanotubes (CNTs) have been attracting increasing interest for the fabrication of polymer‐based nanocomposites because of their excellent properties. Traditional methods for the preparation of polymer/CNTs nanocomposites are in situ polymerization, solution blending, and melt mixing. The achievement of a good CNT dispersion and a percolation network is important in order to obtain better mechanical and electrical properties. However, the rheological behavior of polymer/CNTs systems, in particular regarding the extensional flow, has not been much investigated so far. In this work we present, for the first time, rheological data in non‐isothermal extensional flow and an investigation on the effect of the extensional flow upon the final properties of several polymer/CNTs systems was carried out as well. Extensional flow led to higher mechanical properties and higher melt strength, but only a slightly reduced breaking stretching ratio. This result could be particularly interesting in the view of potential industrial applications such as film blowing and spinning. Morphological analyses also showed higher degrees of dispersion and variation in the CNTs final dimensions. Copyright © 2010 John Wiley & Sons, Ltd.     

碳纳米管的修饰及其在超级电容器中的应用

碳纳米管以其窄孔径分布、高有效比表面积、良好导电性能、良好力学性能、优良化学稳定性和良好热稳定性以及较低成本等优点,被认为是超级电容器的理想电极材料之一.本文结合碳材料具有的双电层电容和金属氧化物、导电聚合物具有的准法拉第电容,综述了碳纳米管的修饰处理技术及碳纳米管/金属氧化物、碳纳米管/导电聚合物复合材料、碳纳米管原位再生长技术的研究进展,指出碳纳米管的修饰能更好地改善其电化学性质,因此碳纳米管复合材料是超级电容器电极材料研究的一个重要发展方向.     

水分散性碳纳米管的制备研究进展

采用化学修饰的方法制备水分散性碳纳米管(Carbon nanotubes,CNTs)是扩大CNTs在生物传感器、医药、功能材料和电子电器元件等领域应用的重要手段。化学修饰法主要包括非共价修饰和共价修饰两种,非共价修饰是采用表面活性剂、有共轭平面结构的分子以及聚合物或生物大分子对CNTs进行表面包覆;共价修饰包括"grafting to"和"grafting from"两种类型。本文从反应原理和实施方法上综述了化学修饰法制备水分散性CNTs的研究进展,并对水分散性CNTs的研究和应用前景进行了展望。     

Electrochemistry of polystyrene intercalated vertically aligned single- and double-walled carbon nanotubes on gold electrodes

Electrochemical electrodes incorporating double- and single-walled carbon nanotubes (CNTs) were fabricated on cysteamine modified flat gold substrates. Through covalent coupling of the amine end groups with carboxyl functionalized CNTs, a dense forest of vertically aligned CNTs was produced. To these a 30 nm thick insulating polystyrene layer was spin coated, resulting in exposure of the uppermost carbon nanotube ends. The electrochemical performance of each electrode was then determined using the redox probe ruthenium hexaamine. Once surrounded by polymer, the double-walled CNTs (DWCNTs) showed an improved electron transfer rate, compared to the single-walled electrode. This improvement was attributed to the protection of the electronic properties of the inner wall of the DWCNT during the chemical modification and suggests that DWCNTs may offer a useful alternative to SWCNTs in future electrochemical sensors and biosensors.