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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Chemical Effects of a Solvent-Limited Approach to HCl-Doped Polyaniline Nanopowder Synthesis
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Chemical Effects of a Solvent-Limited Approach to HCl-Doped Polyaniline Nanopowder Synthesis

机译：溶剂限制的HCl掺杂聚苯胺纳米粉合成方法的化学作用

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摘要

The unconventional solvent-limited synthesis approach for conductive polymer production is analyzed for the well-known system of HCl-doped polyaniline (PAN) to elucidate the impact of nearly solvent-free reactions on chemical and electronic structures including chain conformation, specifically, branching and cross-linking. Moreover, the dependence of PAN polymorphism on the synthesis approach was demonstrated. A careful comparison is established with conventionally solvent-rich syntheses for rapid and extremely slow oxidations. Detailed Raman and UV-vis spectroscopy analyses demonstrate that the "solvent-free" product has the lowest cross-linking density with enhanced charge delocalization as a result of more expanded-coil chains and achieves an optimal oxidation level for the highest conductivity. This is in contrast to conventional solvent-rich polymerization for more compact coils and cross-links producing lower conductivities. The importance of tuning synthesis conditions toward delocalized polaron electronic structure relative to bipolarons and/or localized polarons is exemplified. These findings further support previous results from electromagnetic shielding effectiveness using the three synthesis-varied HCl-PAN nanopowders in the microwave band as well as explain the apparent independence of the polymer conductivity and crystallinity from previous studies.
机译：针对众所周知的HCl掺杂聚苯胺（PAN）系统分析了用于导电聚合物生产的非常规溶剂受限合成方法，以阐明几乎无溶剂的反应对化学和电子结构的影响，包括链构象，特别是支链和交联。此外，证明了PAN多态性对合成方法的依赖性。与常规的富含溶剂的合成方法进行了仔细的比较，以进行快速和极慢的氧化。详细的拉曼光谱和紫外可见光谱分析表明，“无溶剂”产品具有最低的交联密度，由于更多的盘绕链增加了电荷的离域作用，并实现了最佳的氧化水平，从而获得了最高的电导率。这与用于更紧凑的线圈和交联的传统的富含溶剂的聚合反应产生较低的电导率相反。例示了相对于双极化子和/或局域极化子，朝着局域极化子电子结构调整合成条件的重要性。这些发现进一步支持了使用微波波段中三种合成变量的HCl-PAN纳米粉的电磁屏蔽效果的先前结果，并解释了聚合物电导率和结晶度与先前研究之间的明显独立性。

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