石墨烯非共价键功能化及应用研究进展

为了扩展石墨烯的应用范围，克服石墨烯在溶液中难于溶解和难以分散等缺陷，石墨烯的表面功能化处理势在必行。而非共价键功能化由于对石墨烯结构的非破坏性可以更好地保持发挥石墨烯本身的优异性能而备受研究者的重视。本文重点综述了近年来石墨烯在非共价键功能化研究方面的进展，包括π-π相互作用、表面活性剂与石墨烯之间的疏水作用和氢键作...     

石墨烯的功能化研究进展

目前石墨烯的功能化研究成为了国内外的研究热点,综述了石墨烯的共价键功能化和非共价键功能化研究的最新进展和重要研究结果,并对石墨烯功能化的发展做了展望和预测。     

碳纳米管的表面修饰及其在聚合物中的应用

介绍了碳纳米管的有机共价键化和有机非共价键化修饰,以及碳纳米管在聚合物中应用的情况。通过碳纳米管表面修饰技术制备可溶性碳纳米管,可以解决碳纳米管的纯化和分散问题：碳纳米管具有特殊的结构,独特的电学、力学性能和化学稳定性,在场发射器件、电子晶体管、储氢、太阳能利用、高效催化剂等方面具有诱人的应用前景。     

多壁碳纳米管的功能化及其应用研究

首先用混合酸纯化了原料碳纳米管,然后使用有机胺对碳纳米管进行了共价功能化。拉曼光谱和元素分析结果表明,烷基胺通过共价键接合于碳纳米管表面。从热重分析结果可知,碳纳米管表面附着有质量分数为6.9%～16.4%的有机物。透射电镜照片显示,在碳纳米管的外壳上覆盖有厚度为几纳米的无定形的材料,形成核—壳结构。力学性能结果表明,加入质量分数为1%的功能化纳米碳管可使环氧树脂的断裂韧性提高35%。     

非共价键修饰碳纳米管及其在电化学中的应用进展

本文跟踪碳纳米管非共价键功能化修饰的研究进展,对功能化碳纳米管在传感器领域中的应用进行了综述。     

碳纳米管功能化表面修饰研究进展

由于碳纳米管表面缺陷少、缺乏活性基团,并且具有很强的范德华力和很高的长径比,严重的影响了它的应用。本文从共价修饰和非共价修饰两方面,介绍了目前碳纳米管功能化修饰的方法和研究状况。从催化、医疗、材料等方面着重介绍了功能化修饰后的碳纳米管一些最新应用进展,并展望了碳纳米管的发展与应用前景。     

功能化碳纳米管/炭黑复合橡胶性能研究

表面活性剂十二烷基苯磺酸钠对碳纳米管进行非共价键改性包覆,研究功能化碳纳米管与炭黑复合材料性能。结果表明,十二烷基苯磺酸钠与碳纳米管的石墨表面形成π-π堆叠,可有效阻止碳纳米管间的团聚。功能化碳纳米管/炭黑复合材料硫化时间缩短,加工性能得到改善,断裂伸长率提高66.1%,导热率提高8.4%。Payne效应和TEM表明,十二烷基苯磺酸钠包覆碳纳米管可有效改善碳纳米管在橡胶基体中分散,也改善了炭黑在复合材料中的分散。混合填料在橡胶基体均匀分散,加强了填料与基体的界面作用,建立良好的三维空间网络结构,使复合材料性能得到改善。     

碳纳米管的分散及其在防腐涂料中的研究进展

在纳米填料中,碳纳米管具有出色的耐化学性、机械稳定性及导电性等特性,在增强有机涂层的机械性能和耐腐蚀性能方面发挥着重要作用。但是碳纳米管与聚合物基体的界面相互作用较弱,难以分散在聚合物中。本文综述了碳纳米管的分散方法,包括机械分散、共价功能化和非共价功能化处理,并概述了不同分散方法的优缺点,相继评述了碳纳米管在有机防腐涂料中的防腐机理及研究进展,包括溶剂型、水性及粉末防腐涂料,最后对碳纳米管防腐涂料的未来发展方向进行了展望。     

使用碱式溴甲酚绿功能化多壁碳纳米管

使用碱式溴甲酚绿对多壁碳纳米管进行非共价键功能化处理,使其分散在水溶液中。染料分子的化学结构通过1H核磁共振谱,二维1H-1H相关谱以及质谱分析得以确定。原子力显微镜照片说明染料分子被吸附在碳纳米管上;拉曼光谱分析表明碳纳米管被分散在水溶液中。     

碳纳米管的非共价功能化研究进展

综述了碳纳米管非共价功能化的一些新的研究进展情况,介绍了碳纳米管非共价功化的种类、方法和意义,并对功能化后的碳纳米管的性能表征方法及应用前景进行了介绍。针对碳纳米管非共价功能化后虽可同时保持原有的物化性质和引入的物化性质,但表征非常困难这一矛盾进行了评述,并对今后的发展进行了展望。     

The Prato reaction on nanodiamond: Surface functionalization by formation of pyrrolidine rings

The Prato reaction is a highly valued reaction for the functionalization of fullerenes and carbon nanotubes. It uses the generation of pyrrolidine rings from azomethine ylides in the formation of a covalent grafting of functional moieties. Here we present the first application of this reaction on thermally annealed nanodiamond as a way for the grafting of a multitude of functional moieties. We used two types of azomethine ylides (aliphatic and pyridine derived) to show the broad applicability of the reaction for the surface modification of nanodiamond. The possibility to attach glycol units or alkyl chains, both with or without reactive terminal groups opens the way to tune the surface properties of such “Prato-functionalized” diamond in a very flexible way.     

Grafting polyamide 6 onto multi‐walled carbon nanotubes using microwave irradiation

Chemical reactions under microwave irradiation can be very efficient, with a significant shortening of reaction time. Few studies have reported the use of microwaves to functionalize carbon nanotubes. In the work reported, a new method of formulating functionalized multi‐walled carbon nanotubes (MWNTs) was developed by covalent grafting of polyamide 6 (PA6) chains onto the carbon nanotubes assisted by microwave irradiation. PA6 chains were grafted onto acidified MWNTs through condensation reaction between the carboxylic groups of the MWNTs and the terminal amine groups of PA6 using microwave radiation heating. The functionalized carbon nanotubes (MWNT‐g‐PA6) were characterized systematically using infrared and Raman spectroscopy, transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). TEM showed that the surface of the MWNTs was covered with a layer of PA6. TGA results indicated that the MWNT‐g‐PA6 contained about 47 wt% of polymer. A novel, convenient and efficient functionalization approach is reported, involving covalently grafting PA6 chains onto MWNTs assisted by microwave irradiation. Copyright © 2010 Society of Chemical Industry     

Synthesizing polystyrene/carbon nanotube composites by emulsion polymerization with non-covalent and covalent functionalization

Polymer/carbon nanotube (CNT) composites were synthesized by first attaching functional groups onto CNT to make them reactive. For this purpose, we developed a combined approach of non-covalent and covalent functionalization process. Covalent functionalization was accomplished through refluxing of CNT with mineral acid (HNO₃) and with oleic acid. The FTIR spectra and zeta-potential data confirmed the effectiveness of functionalization and the improved dispersibility of the functionalized CNT. Styrene was used to synthesize polystyrene (PS)/CNT composites in conjunction with emulsion polymerization, a versatile and industrially important method that is seldom reported for composite synthesis. Our PS/CNT composites had high monomer conversion and the measured thermal and mechanical properties showed significant improvements over pure PS even with modest CNT content.     

Ionomer covalent functionalization of single‐walled carbon nanotubes by radical polymerization of zirconium acrylate

A facile and efficient covalent functionalization of single‐walled carbon nanotubes (SWCNTs) via peroxide‐mediated free radical covalent attachment and polymerization of zirconium acrylate is reported. The resulting covalently functionalized SWCNTs exhibit improved solubility in organic solvents. The covalently functionalized SWCNTs are characterized by cross polarization magic angle spinning ¹³C NMR, differential scanning calorimetry, thermogravimetric analysis, x‐ray diffraction, Raman, and infrared spectroscopy. Infrared spectroscopy reveals that carboxylate groups of covalently attached ionomers chelate with zirconium ions and the participating carboxylate groups may be from different ionomer chains leading to cross‐linking the chains. The SWCNT topology, ionic clustering, and π‐electron clouds were explored by transmission electron microscopy. © 2014 American Institute of Chemical Engineers AIChE J, 60: 820–828, 2014     

Design of carbon nanotube-polymer frameworks by electropolymerization of SWCNT-pyrrole derivatives

Single-walled carbon nanotubes (SWCNTs) have been functionalized by electropolymerizable pyrrole groups following covalent and non-covalent strategies. The covalent pyrrole grafting was carried out by ester formation between pyrrole alcohol and chemically oxidized SWCNT. The strong π-interactions between pyrene and SWCNT were exploited for the non-covalent adsorption of a new pyrene-pyrrole derivative on the pristine nanotube surface. The pyrrole-ester-SWCNT was solubilized in THF and electropolymerized by controlled potential electrolysis at 0.95 V. The pyrene-pyrrole SWCNT was spread on an electrode surface and electropolymerized in its adsorbed state at 0.95 V in CH₃CN. The reinforced nanostructured polypyrrole SWCNT-framework was investigated with scanning electron microscopy.     

Pyrene-POSS nanohybrid as a dispersant for carbon nanotubes in solvents of various polarities: its synthesis and application in the preparation of a composite membrane

ABSTRACT: In this study we report the preparation of nanohybrid dispersant molecules based on pyrene and polyhedral oligomeric silsesquioxanes for non-covalent functionalization of multi-walled carbon nanotubes (MWCNTs). The prepared dispersant improves the dispersion of MWCNTs in organic solvents with very different polarities such as tetrahydrofuran, toluene, and n-hexane. The functionalized MWCNTs were used to introduce conductivity into polydimethylsiloxane membranes which can be used for electrostatic discharge applications.     

Dispersion, interfacial interaction and re-agglomeration of functionalized carbon nanotubes in epoxy composites

The surface, interfacial and dispersion properties of carbon nanotubes (CNTs), and the mechanical properties of the CNT/epoxy composites affected by CNT functionalization are investigated. It is demonstrated that there exists strong correlations between amino-functionalization, dispersion, wettability, interfacial interaction and re-agglomeration behaviour of CNTs and the corresponding mechanical and thermo-mechanical properties of CNT/epoxy composites. The amino-functionalized CNTs exhibit higher surface energy and much better wettability with epoxy resin than the pristine CNTs, and the attached amine molecules arising from the functionalization effectively inhibit the re-agglomeration of CNTs during the curing of resin. These ameliorating effects along with improved interfacial adhesion between the matrix and functionalized CNTs through covalent bonds result in improved flexural and thermo-mechanical properties compared with those without functionalization.     

表面活性剂非共价功能化处理制备碳纳米管悬浊液

分别以十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、十二烷基聚氧乙烯(23)醚、十六烷基三甲基溴化铵等表面活性剂为分散剂,水为溶剂,超声波作用下对硝酸纯化的碳纳米管进行非共价功能化处理,制备了初始浓度为2 g/L的碳纳米管悬浊液,并对处理后的碳纳米管进行定性分析. 结果表明,功能化处理后,表面活性剂吸附到碳纳米管表面,促进碳纳米管的分散. 定量分析了碳纳米管悬浊液的浓度,并根据碳管浓度随时间的变化研究悬浊液的稳定性. 结果表明,表面活性剂功能化处理所制碳纳米管悬浊液存放240 h后趋于稳定,碳纳米管浓度不再下降,最终碳纳米管悬浊液浓度因所用表面活性剂不同而在1.68~1.84 g/L范围内略有差异.     

碳纳米管在聚合物基体中的分散方法

综述了碳纳米管（CNTs）在聚合物基体中的分散方法，包括直接分散法和表面修饰法，其中表面修饰又根据是否形成共价键分为两类，重点叙述了近几年成为研究热点的非共价键修饰法。直接分散法简单、快捷，保证了CNTs的结构完整性，但分散效果较差；表面修饰法通过共价键或非共价键的方式对CNTs的表面进行改性，克服了直接分散法的缺点，但共价键的形成会破坏CNTs的结构完整性，造成CNTs其他性能的下降，而非共价键修饰又存在结合不牢固的问题。因此，CNTs在聚合物基体中的分散方法仍是今后聚合物／CNTs复合材料应用中需要解决的一个重点问题。     

改善无机填料混合基质膜气体分离性能的研究进展

混合基质膜（MMMs）是结合了无机填料和有机基质特点的一类膜材料,因其在气体分离应用上具有良好的渗透通量和分离性能被广泛关注。无机填料诸如二氧化硅纳米颗粒球、沸石分子筛、金属有机框架（MOF）、氧化石墨烯（GO）、碳纳米管（CNT）均被广泛应用于混合基质膜的制备,但是碍于无机填料在有机相中的分散性问题、两相相容性问题和界面缺陷问题,常会导致较差的气体分离性能。针对近年通过对无机填料进行表面官能化修饰、共价交联、多元填充、调控形貌等来改善混合基质膜气体分离性能的研究进行总结和阐述,并对其未来的发展趋势进行了展望。