基于多酸团簇的单壁碳纳米管组装与结构分离

单壁碳纳米管因其独特结构和优异性质而受到广泛关注。然而商业化碳纳米管粉末样品是由各种不同手性的碳纳米管组合形成的管束状混合物，难以将其运用于高端碳纳米管应用当中。因此，纯半导体性或单一手性碳纳米管的制备具有重要意义。当前实现该目标的主要方法分别为在基底上生长单壁碳纳米管的化学气相沉积法和在溶液相中进行的选择性分离。相比较而言，溶液相中分离获得的碳纳米管量更多，可以实现分离的手性种类也更多。
本文主要以实现碳纳米管的选择性分离为目标，使用多金属氧酸盐团簇作为客体分子调控碳纳米管电子性质，基于共轭聚合物的分散作用进行选择性分离。主要研究内容及结论如下：

选择了一种尺寸约为1 nm的多金属氧酸盐团簇作为客体分子来封装到单壁碳纳米管的内腔中，以改变单壁碳纳米管的电子密度。通过这种策略，我们利用聚芴类化合物，实现了直径约3 nm、纯度约98%的半导体性单壁碳纳米管的选择性分离；在水相中，利用表面活性剂成功实现了直径的选择性分离。通过吸收光谱和拉曼光谱以及电学测量结果进行验证，并利用拉曼光谱、X射线光电子能谱、循环伏安法、原位透射电子显微镜和理论计算对实验机理进行研究。
选择多金属氧酸盐团簇作为空间位阻吸附在亚纳米级的单壁碳纳米管上，在超声处理过程中，团簇从某些仅与其具有弱相互作用的单壁碳纳米管分离，从而使聚合物能够选择性地包裹和分离该种单壁碳纳米管，而与团簇有着强相互作用的其他单壁碳纳米管管束则难以被聚合物包裹。通过这种策略，实现了亚纳米级(6,5)手性单壁碳纳米管的选择性分离，并利用吸收光谱和荧光光谱进行表征。通过理论计算、光谱学、透射电镜和X射线光电子能谱揭示碳纳米管和团簇之间的相互作用与纳米管直径相关。并且进一步证明这种分离策略在一系列具有合适氧化能力的多金属氧酸盐团簇中被是有效的。

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