Phenoxazine-Containing Polyaniline Derivatives with Improved Electrochemical Stability and Processability
Phenoxazine-Containing Polyaniline Derivatives with Improved Electrochemical Stability and Processability
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DOI：
10.1021/acsapm.1c00152
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发表时间：
2021-05-19
影响因子：
5
通讯作者：
Scott, Colleen N.
中科院分区：
文献类型：
--
作者：
Almtiri, Mohammed;Dowell, Timothy J.;Scott, Colleen N.
聚苯胺（PANI）是最容易获得的导电聚合物之一，以其部分氧化导电状态下的环境稳定性而闻名。然而，它很难加工，并且在部分氧化和完全氧化状态之间经历电化学降解。虽然已经有几种方法来解决聚苯胺的可加工性，但解决其电化学不稳定性的方法很少。我们制备了两种聚苯胺衍生物，它们含有苯恶嗪单元与2,5-二甲基-对苯二胺（P1）和对苯二胺（P2）共聚，并测定了它们的光电性能、可加工性、形貌和电化学稳定性。将樟脑磺酸（CSA）掺杂聚合物溶解在有机溶剂中，并浇铸成薄膜，通过吸收光谱、循环伏安法和电导率测量对其进行分析。重要的是，这些薄膜在多次氧化还原和光谱电化学循环中表现出出色的电化学稳定性，并且当暴露于间甲酚蒸汽时，在高半导体状态下（0.1至1 S/cm）表现出优异的导电性。此外，在没有间甲酚蒸汽的情况下，P1以聚集体的形式存在，但在间甲酚存在的情况下，通过SEM， TEM和AFM图像显示，P1以高导电性的片状结构存在。这些结果表明，P1和P2将是需要稳定氧化还原导电聚合物应用的杰出候选者。
Polyaniline (PANI) is one of the most accessible conducting polymers and is known for its environmental stability in its partially oxidized conductive state. However, it is difficult to process and undergoes electrochemical degradation between its partially and fully oxidized states. While there have been several approaches to address PANI's processability, little has been done to address its electrochemical instability. We have prepared two polyaniline derivatives that contain a phenoxazine unit copolymerized with 2,5-dimethyl-p-phenylenediamine (P1) and p-phenylenediamine (P2) and determined their optoelectronic properties, processability, morphology, and electrochemical stability. Camphor sulfonic acid (CSA) doped polymers were dissolved in organic solvents and cast into films, which were analyzed by absorption spectroscopy, cyclic voltammetry, and conductivity measurements. Importantly, the films exhibit outstanding electrochemical stability over multiple redox and spectroelectrochemical cycles and conductivity in the high semiconductive regime (0.1 to 1 S/cm) when exposed to m-cresol vapors. Additionally, P1 exists as aggregates in the absence of m-cresol vapors, but as highly conductive sheet-like structures in the presence of m-cresol as shown by SEM, TEM, and AFM images. These results show that P1 and P2 would be outstanding candidates for applications that required stable redox conductive polymers.