碳纳米管共价功能化

碳纳米管由于其独特的结构与优异的各项性能,在许多领域具有巨大的应用潜力,已引起了广泛的关注。由于碳纳米管不溶于水和有机溶剂,极大地制约了其性能应用,因此碳纳米管的功能化就成为目前研究的热点。本文侧重于碳纳米管的共价功能化,详细讨论了碳纳米管不同位置共价功能化的研究进展。     

自由基反应修饰碳纳米管

碳纳米管由于其特异的光电及力学性能受到广泛的关注,但其在溶剂中的分散性及与材料的相容性较差,应用受到一定的限制。为了解决这一技术问题,已报到了多种修饰碳纳米管的方法。本文综述了通过自由基反应修饰碳纳米管的各种途径与方法,大体分为小分子自由基反应改性碳纳米管与大分子自由基聚合反应改性碳纳米管。用于改性碳纳米管的小分子自由基包括芳香偶氮盐、过氧化物分解产生的自由基、卡宾与乃春自由基等;大分子自由基聚合反应包括ATRP、RAFT、NMP、铈离子引发聚合、原位聚合、溶液聚合、沉淀聚合、无皂乳液聚合、乳液聚合等。本文也简要地概述了通过其他途径产生的自由基修饰碳纳米管的方法。     

Noncovalent Functionalization of Single-Walled Carbon Nanotube by Porphyrin: Dispersion of Carbon Nanotubes in Water and Formation of Self-Assembly Donor-Acceptor Nanoensemble

A water-soluble nanoensemble of porphyrin and single-walled carbon nanotubes (SWNTs) was fabricated via electrostatic attraction. The formation of this supramolecular complex was monitored by UV-vis spectra and fluorescence spectra. The donor-acceptor properties of this nanoensemble were characterized by I–V performance of relative photovoltaic device fabricated by layer-by-layer (LBL) technique.     

碳纳米管的功能化及其电化学性能

超级电容器作为一种新型的储能元件,以其快速储存、释放能量等优点,近年来成为各国科研工作的研究重点和焦点[1￣3],并在数据记忆存储系统、便携式仪器设备、后备电源、通讯设备、计算机、燃料电池、电动车混合电源等许多领域都有广泛的应用前景[4]。目前,超级电容器用的电极材     

碳纳米管的共价修饰

碳纳米管(carbon nanotubes, CNTs)的溶解性和分散性较差是目前制约其广泛应用及在一些有特殊要求的领域(如生物技术)应用的主要原因之一. 对CNTs进行共价修饰是改善其溶解性和分散性的有效方法之一. 目前CNTs的共价修饰主要通过两类反应来实现: 羧基的衍生反应和直接加成反应. 介绍了基于这两种反应的几种共价修饰方法, 比较了各种修饰方法的优缺点及其对CNTs的溶解性和分散性的改善效果.     

Quantitative Non-Covalent Functionalization of Carbon Nanotubes

We report a convenient method for quantitative non-covalent functionalization of single-walled carbon nanotubes (SWNT) with phthalocyanine (Pc) compounds, in which a surface coverage of 49% was achieved. The effect of several process parameters on the functionalization process was elucidated. Firstly, as-produced SWNT gave the largest extent of functionalization compared with purified SWNT and as-produced multi-walled carbon nanotubes (MWNT). Secondly, the extent of functionalization was sensitive to the specific molecular structures of the Pc compounds. Finally, in terms of solvent selection, dimethylformamide (DMF) was found to give the largest extent of functionalization, which is then followed by chloroform (CHCl₃) and 1,2-dichlorobenzene (ODCB). The method reported in this paper provides new insights on the interactions between Pc molecules and carbon nanotubes and paves the way for rational control of the degree of functionalization, which is an important step from the perspective of carbon nanotube applications. Electronic supplementary material Supplementary material for this article is avilable at and is accessible for authorised users.     

Functionalization of Single‐Walled Carbon Nanotubes

Through chemical functionalization of single‐walled carbon nanotubes, the prerequisites for possible applications of such nanostructures are established. The derivatized tubes differ from the crude materials in their good solubility, which enables both a more extensive characterization and subsequent chemical reactivity. Current derivatization methods include defect and covalent sidewall functionalization, as well as noncovalent exo‐ and endohedral functionalization. In this way, for example, a range of nanotubes can be prepared: with sidewall substituents, wrapped with polymers, or with guest molecules included. The current state of the literature is presented in this Minireview.     

共价功能化碳纳米管的应用研究进展

本文跟踪碳纳米管的功能化研究进展,对共价功能化碳纳米管在材料领域,如复合材料、催化剂载体、电子器件、光学材料、及生物医学中的应用进行了综述.     

Double Functionalization of Carbon Nanotubes with Purine and Pyrimidine Derivatives

Herein, we have developed a synthetic strategy for the covalent double functionalization of single‐walled carbon nanotubes (SWCNTs) with a combination of purine–pyrimidine and purine–purine nucleobase systems. The nucleobases were introduced on the sidewall of oxidized SWCNTs through 1,3‐dipolar cycloaddition and by amidation of the carboxylic acids located at the tips and defect sites of the nanotubes. The new nanohybrids were characterized by transmission electron microscopy, thermogravimetric analysis, FTIR and Raman spectroscopy, magic‐angle spinning NMR spectroscopy, and Kaiser test. The nucleobase/SWCNT conjugates can be envisaged for the modulation of the interactions with nucleic acids by means of base pairing, thereby opening new possibilities in the development of DNA/CNT nanobioconjugates.     

A 1,3‐Phenylene‐Bridged Hexameric Porphyrin Wheel and Efficient Excitation Energy Transfer along the Wheel

A 1,3‐phenylene‐bridged hexameric Zn^II porphyrin wheel was synthesized by a Suzuki–Miyaura coupling reaction through a one‐pot or a stepwise route. The hexameric wheel structure was revealed by using X‐ray diffraction analysis. The porphyrin wheel exhibits a split Soret band due to effective exciton coupling and displays efficient excitation energy transfer along the wheel. Measurements of fluorescence anisotropy decay and pump‐power‐dependent decay reveal a rapid excitation energy hopping along the wheel with a rate of 1.4 ps.     

Surface functionalization of multiwalled carbon nanotubes by the photo‐responsive strategy of π‐π stacking and azide‐grafting

In this communication, we report a new, simple, and eco‐friendly method to develop highly dispersible multiwalled carbon nanotubes (MWCNTs) by π‐π stacking and azide‐grafting. MWCNTs were functionalized via standard physisorption, followed by nitrene addition using azido compounds upon ultraviolet activation. The functionalized MWCNTs show excellent dispersibility without raising distinct damage, which can bear comparison with that of MWCNTs oxidized with mixture acids. This method allows for the improvement of the chemical compatibility of MWCNTs with specific polymers for application in nanotube‐based composites and opens a potential pathway for surface protection.     

微波辅助有机过氧化物功能化修饰单壁碳纳米管

本文报道了微波辅助下,利用过氧化月桂酰分解得到的十一烷基,化学功能化修饰单壁碳纳米管。这种快速、高效的方法将反应时间缩短至10分钟,并得到了比传统回流方法具有更高接枝率的产物。利用傅立叶变换红外光谱(FT-IR),热失重分析(TGA),拉曼光谱,探究了不同的反应时间和微波功率对单壁碳纳米管的接枝率的影响。结果表明：过长的反应时间会导致部分的去功能化的发生,而过高的微波功率(大于900瓦),则会将单壁碳纳米管上起初键连上的十一烷基剥落下来。分散性照片和高分辨率透射电子显微镜(HRTEM)照片显示出,功能化后的单壁碳纳米管与原始的碳管相比,在有机溶剂中的分散性有了明显的提高。     

Multipurpose Nature of Rapid Covalent Functionalization on Carbon Nanotubes

In the vast field of functionalization routes to carbon nanoforms, the fulfillment of such critical requirements as quick and nonharsh methods, good dispersibility, introduction of reactive groups, short reaction time, and low cost can be quite challenging. Traditional thermally induced diazonium chemistry on single‐walled carbon nanotubes (SWCNTs) is revisited by using commercial anilines and providing useful insight into the versatility of this approach. Functionalized SWCNTs with multiple controllable features, such as degree (and ratio) of coverage, orthogonalization, doping, and high water dispersibility, are obtained by introducing benzenesulfonic acid and benzylamine moieties. The scenario opens up an avenue to address relevant applications in which most functionalization methods could not be applied in a straightforward way.     

Functionalization of Multi‐Walled Carbon Nanotubes by Thermo‐Grafting with α‐Methylstyrene‐Containing Copolymers

The present article reports on a strategy for the functionalization of multi‐walled carbon nanotubes (MWCNTs) by grafting with various polymer chains. Copolymers consisting of α‐methylstyrene (AMS) and a second monomer, that is glycidyl methacrylate (GMA) or styrene (St), were synthesized in advance. The copolymers were heated in the presence of MWCNTs in solution, decomposition of the AMS sequences occurred, providing macroradicals, which further attacked the double bonds on the MWCNT surfaces. Grafting of the copolymer chains onto the surface of the MWCNTs was thus achieved, as demonstrated by FT‐IR, XPS and Raman technologies. The resulting poly(AMS‐co‐GMA)‐g‐MWCNTs could be uniformly dispersed in N,N‐dimethylformamide (DMF) and acetone, and the poly(AMS‐co‐St)‐g‐MWCNTs also could be uniformly dispersed in DMF.

     

Functionalization of Carbon Nanotubes with Well‐Defined Functional Polymers via Thiol‐Coupling Reaction

Summary: Thiol‐reactive‐functionality decorated multi‐walled carbon nanotubes (MWNTs) have been obtained. Trithiocarbonate‐ended poly(N‐(2‐hydroxypropyl)methacrylamide) (PHPMA) is prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization of N‐(2‐hydroxypropyl)methacrylamide (HPMA) using S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate as chain transfer agent, subsequently, thiol‐terminated PHPMA (PHPMA‐SH) is obtained by treating trithiocarbonate‐ended PHPMA with hexylamine. The PHPMA‐S‐S‐MWNT conjugate is formed by simply stirring the mixture of thiol‐reactive‐functionality decorated MWNTs with PHPMA‐SH in phosphate buffered saline by a thiol‐coupling reaction. FT‐IR, HRTEM, ¹H NMR, and TGA results show that this thiol‐coupling reaction is effective to produce aqueous soluble polymer–MWNT conjugates under mild conditions.

Thiol‐reactive‐functionality decorated multi‐walled carbon nanotubes are modified with thiol end‐capped polymers by a thiol‐coupling reaction.     

Solid‐Phase Synthesis of Peptide Libraries Combining α‐Amino Acids with Inorganic and Organic Chromophores

The synthesis of two series of peptidic chains composed of bis(terpyridine)ruthenium(II) acceptor units and organic chromophores (coumarin, naphthalene, anthracene, fluorene) by stepwise solid‐phase peptide synthesis (SPPS) techniques is described. The first series of dyads comprises directly amide linked chromophores, while the second one possesses a glycine spacer between the two chromophores. All dyads were studied by UV/Vis and NMR spectroscopy, steady‐state luminescence, luminescence decay and electrochemistry, as well as by DFT calculations. The results of these studies indicate weak electronic coupling of the chromophores in the ground state. Absorpion spectra of all dyads are dominated by metal‐to‐ligand charge‐transfer (MLCT) bands around 500 nm. The bichromophoric systems, especially with coumarin as organic chromophore, display additional strong absorptions in the visible spectral region. All complexes are luminescent at room temperature (³MLCT). Efficient quenching of the fluorescence of the organic chromophore by the attached ruthenium complex is observed in all dyads. Excitation spectra indicate energy transfer from the organic dye to the ruthenium chromophore.     

β‐to‐β 2,5‐Pyrrolylene‐Linked Cyclic Porphyrin Oligomers

β‐to‐β 2,5‐Pyrrolylene linked cyclic porphyrin oligomers have been synthesized by Suzuki–Miyaura coupling of 2,5‐diborylpyrrole and 3,7‐dibromoporphyrin. The cyclic porphyrin oligomers exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO–LUMO gaps, and ultrafast excitation energy transfer between the neighboring porphyrins via the pyrrolylene bridge.