Modular Functionalization of Carbon Nanotubes and Fullerenes
Modular Functionalization of Carbon Nanotubes and Fullerenes
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DOI：
10.1021/ja810049z
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发表时间：
2009-06-24
影响因子：
15
通讯作者：
Swager, Timothy M.
中科院分区：
文献类型：
--
作者：
Zhang, Wei;Sprafke, Johannes K.;Swager, Timothy M.
人们已经开发了一系列高效的、模块化的两性离子介导的转化方法，使碳纳米管(碳纳米管，单壁和多壁)和富勒烯具有不同的官能化。展示了三种功能化策略。(1)用添加的亲核剂捕获带电的两性离子中间体，允许在富勒烯和碳纳米管上一锅反应中安装各种官能团。(2)通过改变电泳液中乙酰二甲酸二甲酯和其他双取代酯的亲和力，可以得到带有氯乙基、烯丙基和炔丙基的碳纳米管，这些碳纳米管还可以进行S(N)2取代、硫醇加成或1，3-偶极环加成反应。(3)碳纳米管的环戊酮官能化后的转变(如脱甲基化和皂化)导致脱甲基化或水解产物，在水中具有很高的溶解度(对于MWCNTs为1.2 mg/mL)。后一类衍生物的碳纳米管水分散体稳定数月，已成功用于静电纺丝法制备碳纳米管-聚环氧乙烷纳米复合材料。大规模的MWCNT(10g)官能化也证明了两性离子反应的可扩展性。总而言之，我们详细介绍了在温和的条件下(60℃，没有强酸/碱或高压)和高效率(SWCNTs的碳原子中每10个碳原子中有1个官能团)的各种碳纳米管功能化，这扩大了这些材料的用途。
A series of highly efficient, modular zwitterion-mediated transformations have been developed which enable diverse functionalization of carbon nanotubes (CNTs, both single-walled and multi-walled) and fullerenes. Three functionalization strategies are demonstrated. (1) Trapping the charged zwitterion intermediate with added nucleophiles allows a variety of functional groups to be installed on the fullerenes and carbon nanotubes in a one-pot reaction. (2) Varying the electrophile from dimethyl acetylenedicarboxylate to other disubstituted esters provides CNTs functionalized with chloroethyl, allyl, and propargyl groups, which can further undergo S(N)2 substitution, thiol addition, or 1,3-dipolar cycloaddition reactions. (3) Postfunctionalization transformations on the cyclopentenones (e.g., demethylation and saponification) of the CNTs lead to demethylated or hydrolyzed products, with high solubility in water (1.2 mg/mL for MWCNTs). CNT aqueous dispersions of the latter derivatives are stable for months and have been successfully utilized in preparation of CNT-poly (ethylene oxide) nanocomposite via electrospinning. Large-scale MWCNT (10 g) functionalization has also been demonstrated to show the scalability of the zwitterion reaction. In total we present a detailed account of diverse CNT functionalization under mild conditions (60 degrees C, no strong acids/bases, or high pressure) and with high efficiency (1 functional group per 10 carbon atoms for SWCNTs), which expand the utility of these materials.