School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039, PR China.
Nanoscale. 2012 Jun 21;4(12):3729-33. doi: 10.1039/c2nr30743j. Epub 2012 May 21.
While the number of man-made nano superstructures realized by self-assembly is growing in recent years, assemblies of conductive polymer nanocrystals, especially for superlattices, are still a significant challenge, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we firstly report a facile and general route to a new generation of 3D layered superlattices of polyaniline doped with CSA (PANI-CSA) and show how PANI crystallize and self-assemble, in a suitable single solution environment. In cyclohexane, 1D amorphous nanofibers transformed to 1D nanorods as building blocks, and then to 2D single-crystal nanosheets with a hexagonal phase, and lastly to 3D ordered layered superlattices with the narrowest polydispersity value (M(w)/M(n) = 1.47). Remarkably, all the instructions for the hierarchical self-assembly are encoded in the layered shape in other non-polar solvents (hexane, octane) and their conductivity in the π-π stacking direction is improved to about 50 S cm(-1), which is even higher than that of the highest previously reported value (16 S cm(-1)). The method used in this study is greatly expected to be readily scalable to produce superlattices of conductive polymers with high quality and low cost.
近年来，通过自组装实现的人造纳米超结构的数量不断增加，但导电聚合物纳米晶体的组装，特别是超晶格的组装，仍然是一个重大挑战，这不仅是因为纳米晶体构建块的形状和它们的相互作用简单，还因为在更精细的纳米晶体制造中对这些参数的控制较差。在这里，我们首先报道了一种简便通用的方法，用于制备新一代聚掺杂 CSA 的 3D 层状超晶格（PANI-CSA），并展示了 PANI 如何在合适的单一溶液环境中结晶和自组装。在环己烷中，一维无定形纳米纤维转化为一维纳米棒作为构建块，然后转化为具有六方相的二维单晶纳米片，最后转化为具有最窄多分散性值（M(w)/M(n) = 1.47）的 3D 有序层状超晶格。值得注意的是，所有的分层自组装指令都编码在其他非极性溶剂（己烷、辛烷）中的层状形状中，其在π-π堆积方向上的电导率提高到约 50 S cm(-1)，甚至高于之前报道的最高值（16 S cm(-1)）。本研究中使用的方法有望很容易扩展到高质量、低成本的导电聚合物超晶格的生产。
