卟啉修饰碳纳米管研究进展

碳纳米管作为一类新型纳米材料具有许多独特的物理、化学性质,卟啉在可见光区具有广泛吸收.并可作为构筑分子体系的光捕捉单元.卟啉修饰的碳纳米管有望在生命、信息、材料科学等许多相关学科得到应用.本文综述了卟啉修饰碳纳米管的方法、影响因素,展望了其在光电领域的应用前景.     

水溶性磺酸钠苯基卟啉及其金属配合物共价与非共价修饰多壁碳纳米管的研究

合成了meso-四(4-磺酸钠苯基)卟啉及其Zn, Cu, Mn配合物, 通过共价与非共价的方法将其分别修饰到多壁碳纳米管上. 采用红外光谱对产物结构进行表征|通过透射电镜(TEM)考察了卟啉-多壁碳纳米管复合物的形貌特征|通过紫外光谱、荧光光谱对比分析了两类复合物, 发现在卟啉与多壁碳纳米管之间存在较强的电子效应, 同时发现非共价修饰的卟啉-碳纳米管复合物的荧光淬灭率更高|热重分析(TGA)表明非共价的卟啉-碳纳米管复合物中卟啉的含量比较高. 对修饰后的复合物进行了溶解性测试, 结果表明共价修饰的复合物在水中有较好的溶解性和分散性.     

卟啉-碳纳米管复合物研究进展

碳纳米管是具有一维纳米结构的新型纳米材料,具有许多独特的物理、化学性质.卟啉对可见光具有强烈吸收,其大π共轭体系使其具有良好的电子给予能力,可作为人工光合作用体系的光捕捉单元.将具有电子接受能力的碳纳米管与卟啉结合起来,通过卟啉对碳纳米管进行共价和非共价修饰,可以改善碳纳米管在溶剂中的溶解分散性能,同时实现卟啉和碳纳米管之间有效的电子传递,形成具有独特光电和光学性质卟啉-碳纳米管复合物.该类物质具备良好的应用前景,是碳纳米管和卟啉研究中的热点.就近年来该类复合物的构筑方法及性质研究等方面的进展进行了综述.     

卟啉和酞菁修饰的单壁碳纳米管的合成及光谱性质

利用5-(4-氨基苯基)-10,15,20-三(3,5-二辛氧基苯基)卟啉和2,9,16-三叔丁基-23-氨基锌(Ⅱ)酞菁通过酰胺键连接方式同时对单壁碳纳米管进行共价修饰, 通过红外光谱、拉曼光谱、X射线光电子能谱和透射电镜对所得碳纳米管复合物进行了表征, 证实了其结构. 紫外-可见吸收光谱和荧光光谱分析表明, 光活性分子卟啉和酞菁均与单壁碳纳米管之间存在较强的电子效应. 经卟啉和酞菁共同修饰的单壁碳纳米管复合物比卟啉和酞菁单独修饰的碳纳米管复合物的吸光范围更宽, 而且分散性较好(309 mg/L), 是潜在的光电转换材料.     

meso-四(4-酰肼基苯基)卟啉及其金属配合物共价和非共价修饰多壁碳纳米管

采用新方法合成了meso-四(4-酰肼基苯基)卟啉及其金属配合物, 通过化学键将酰肼卟啉上的酰肼基与活化的多壁碳纳米管(MWNTs)发生酰胺化反应, 从而得到卟啉共价化学修饰的多壁碳纳米管复合物; 利用卟啉环上的π电子与多壁碳纳米管管壁上的π电子通过π-π堆积效应, 得到卟啉非共价化学修饰的碳纳米管复合物. 通过红外光谱、紫外和荧光光谱对比分析, 发现在卟啉与碳纳米管间存在强烈的电子效应, 且非共价修饰的卟啉-碳纳米管复合物的荧光猝灭率更高.     

卟啉修饰碳纳米管研究进展

碳纳米管(Carbon Nanotubes,简称CNTs)独特的一维管状分子结构赋予其许多优良的物化性能。具有平面π共轭结构的卟啉分子与CNTs之间存在强烈的相互作用,利用卟啉修饰CNTs,可以通过共价和非共价两条途径实现。卟啉修饰CNTs不仅可以改善CNTs的溶解性能,而且还可以赋予其许多卟啉固有的优良性能。由此构筑的复合物体系在光电、催化、生物医用领域均显示出广阔的应用前景。本文系统总结了目前国内外利用卟啉修饰CNTs的相关研究成果,并对未来的研究进行了展望。     

金属卟啉有机共价和非共价修饰多壁碳纳米管

合成了5-(4-羟基苯基)-10,15,20-三苯基卟啉锌配合物, 与活化的多壁碳纳米管(MWNT)发生酯化反应, 从而得到金属卟啉有机共价化学修饰的多壁碳纳米管复合物; 利用金属卟啉环上的π电子与多壁碳纳米管管壁上的π电子通过π-π堆积效应, 得到金属卟啉有机非共价修饰的多壁碳纳米管复合物. 通过透射电镜(TEM)考察了金属卟啉-多壁碳纳米管复合物的形貌特征; 通过红外光谱对产物的化学结构进行了表征; 通过紫外光谱、荧光光谱和热失重分析(TGA)对比分析了两类复合物, 发现非共价修饰的金属卟啉-碳纳米管复合物的荧光淬灭率更高, 非共价修饰的金属卟啉-碳纳米管复合物中卟啉的含量比较高.     

金属卟啉化学共价和非共价修饰多壁碳纳米管

合成了5-(4-羟基苯基)-10,15,20-三苯基卟啉锌配合物,与活化的多壁碳纳米管(MWNT)发生酯化反应,从而得到金属卟啉有机共价化学修饰的多壁碳纳米管复合物;利用金属卟啉环上的π电子与多壁碳纳米管管壁上的π电子通过π-π堆积效应,得到金属卟啉有机非共价修饰的多壁碳纳米管复合物.通过透射电镜(TEM)考察了金属卟啉-多壁碳纳米管复合物的形貌特征;通过红外光谱对产物的化学结构进行了表征;通过紫外光谱、荧光光谱和热失重分析(TGA)对比分析了两类复合物,发现非共价修饰的金属卟啉-碳纳米管复合物的荧光淬灭率更高,非共价修饰的金属卟啉-碳纳米管复合物中卟啉的含量比较高.     

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。     

单壁碳纳米管的结构修饰

由于单壁碳纳米管具有独特的结构、电学及机械等性能，可望在许多新领域得 到应用，已引起广泛的关注。但由于单壁碳纳米管不溶于水和常见的有机溶剂，极 大地制约了其应用性能的研究。随着单壁碳纳米管制备技术的不断完善，其研究方 向已开始转向结构修饰及应用性能的研究。主要介绍近年来单壁碳纳米管结构修饰 方面的最新发展状况，重点讨论化学功能化及物理吸附。     

碳纳米管微结构的改变对其容量性能的影响

以KOH为活性剂，通过在高温下将碳纳米管进行活化处理来实现对碳纳米管管壁结构的改变，得到了比表面积和孔容分别是活化处理前约3倍和1.5倍的活性碳纳米管.将活化处理前后两种碳纳米管分别制作成电化学超级电容器电极，在充满氩气的无水手套箱组装成模拟电化学超级电容器，在恒流充放电模式下进行电化学可逆容量的测试，发现活性碳纳米管的电化学容量远高于活化前碳纳米管，是它的2倍.从而发现碳纳米管被打断，管壁变粗糙的活性碳纳米管比一般碳纳米管更适合用于电化学超级电容器电极材料.     

取向碳纳米管制备方法及其应用进展*

碳纳米管有广阔的应用前景,但很多应用是以碳纳米管定向的取向排列为前提.本文全面介绍了制备取向碳纳米管的各种方法和研究进展,综合阐述了各种制备方法的特点,并初步讨论了制备取向生长碳纳米管各种方法的机理.最后,对取向碳纳米管的应用进行了展望,提出了碳纳米管应用的新思路.     

Synthesis of carbon nanotubes by catalytic pyrolysis method with Feitknecht compound as precursor of NiZnAl catalyst

Carbon nanotubes are synthesized by catalytic pyrolysis method with a kind of new type catalyst--nickel-zinc-alumina catalyst prepared from Feitknecht compound. Tubular carbon nanotubes, bamboo-shaped carbon naotubes, herringbone carbon nanotubues and branched carbon nanotubes are all found formed at moderate temperature. It is important for the formation of quasi-liquid state of the metal nanoparticles at the tip of carbon naotubes during the growth of carbon nanotubes to lead to different kinds of carbon nanotubes. It is likely that the addition of zinc make the activity of nickel catalyst after calcinations and reduction changed strangely.     

Influence of Electric Field on Dispersion of Carbon Nanotubes in Liquids

Production processes for carbon nanotubes commonly produce mixtures of solid morphologies that are mechanically entangled or that self‐associate into aggregates. The entangled or aggregated carbon nanotubes often need to be dispersed in corresponding material matrices in order to develop materials that have unique mechanical characteristics or transport properties. The most effective method for dispersion of carbon nanotubes is to prepare fluid suspensions of them in liquid media with applications of surfactant or/and ultrasonication. The authors propose an innovative dispersion method for carbon nanotubes by which an electric field is applied to suspensions of carbon nanotubes in liquids treated by surfactant and ultrasonication. Compared to dispersion without the electric field, the dispersion status of carbon nanotubes in liquid media is evidently improved with the electric field. The results indicate that the electric field conditions are effective for dispersion of carbon nanotubes in liquids and that complex effects of electric field, surfactant, and ultrasonication are beneficial for improvement of dispersion of carbon nanotubes.     

纳米碳管表面羧基化及其电还原性能

应用红外吸收光谱、扫描电子显微镜分别对纳米碳管和硝化后的纳米碳管进行表征,将其制备成粉末微电极,并在碱性溶液中测试它对对硝基苯酚的电还原性能.实验表明:经硝化处理后,碳管表面修饰了羰基,其电还原性能明显提高.依据实验结果探讨了硝化后纳米碳管于对硝基苯酚电还原过程中的反应机理.     

Present and future applications of carbon nanotubes to analytical science

This article reviews the impact of carbon nanotubes on analytical science, and the main current and future applications of carbon nanotubes in this field. Given that it is necessary to solubilize carbon nanotubes for many applications, we consider the procedures developed to achieve this. The use of carbon nanotubes in analytical chemistry as a target analyte and as an analytical tool is also discussed. Chromatographic and electrophoretic methods used to separate and characterize carbon nanotubes are presented. The use of carbon nanotubes as an analytical tool in filters and membranes, as sorbent material for solid phase extraction, in electrochemical (bio)sensors, and in separation methods is discussed. It is clear that while nanotubes are being tested for use in many different fields, their truly enormous potential has yet to be realized in analytical chemistry.Dedicated to the memory of Wilhelm Fresenius     

Electrochemical Sensors Based on Carbon Nanotubes

Carbon nanotubes are attractive new materials. It has been about a decade since carbon nanotubes were discovered. Carbon nanotubes have many outstanding properties and have many practical or potential applications. In this short review we introduce recent advances in carbon nanotubes as potential material for electrochemical sensors. The advantages of carbon nanotubes as sensors are discussed along with future prospects.     

Preparation and Characterization of Poly(methyl methacrylate)-functionalized Carboxyl Multi-wall Carbon Nanotubes

"An in situ polymerization process was used to prepare poly (methyl methacrylate) (PMMA)-functionalized carboxyl multi-walled carbon nanotubes using carboxylate carbon nanotubes and methyl methacrylate as reactants and benzoyl peroxide as an initiator agent. The functionalized multi-walled carbon nanotubes were characterized using transmission electron microscope, scanning electron microscope, nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis and Raman. The results indicate that the PMMA chains are covalently linked with the surface of carboxylate carbon nanotubes. The surface morphology is controlled by the content of carboxylate carbon nanotubes in the reactants. The PMMA functionalized multi-walled carbon nanotubes are soluble in deuterated chloroform. The storage modulus and tanffi magnitude increase as the content of CCNTs increases up to 0.3%."     

聚乙烯醇用于碳纳米管的开口及修饰研究

在低温(250 ℃)下,用聚乙烯醇(polyvinyl alcohol, PVA)和提纯后的碳纳米管(carbon nanotubes, CNTs)的混合物在空气中加热,以研究聚乙烯醇对碳纳米管的修饰作用,并采用TEM对不同条件下所得的产物进行了形态分析.结果发现,碳纳米管的顶端被打开,随着时间的增加,弯曲的碳纳米管断裂成较短的碳纳米管.聚乙烯醇对碳纳米管的氧化及修饰在实验中得到证实.讨论分析了氧化和修饰机理,认为可能是聚乙烯醇在空气中分解所得的产物的一种或几种在氧化和修饰过程中起主要作用.     

Phenol adsorption on different nano-sized carbon materials: first comparative study

Carbon nanofibres and multi-branched carbon nanotubes are synthesized by using a new, proposed in this study method. The acid–base, adsorption and geometric properties of nanomaterials are characterised. Next we present first comparative adsorption and calorimetric studies of phenol uptake from aqueous solutions on mentioned nano-sized carbon materials and on nanotubes having similar diameter. The comparison of carbon nanofibres, multi-branched carbon nanotubes, and multi walled carbon nanotubes shows that for non-porous carbon nanomaterials the concentration of basic surface functionalities determines the mechanism of phenol adsorption. In consequence, larger phenol adsorption is recorded for the most basic nanomaterials (nanofibres and multi walled nanotubes) and smaller for multi branched nanotubes having the smallest surface concentration of basic groups. Possible explanation of differences between enthalpy of phenol displacement on graphite and on studied carbon adsorbents is also given.