Tao Sun, Hong Bi, Kerong Zhu
Department of Chemistry, Anhui University, Hefei 230039, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2007 Apr;66(4-5):1364-8. doi: 10.1016/j.saa.2006.08.011. Epub 2006 Aug 12.
Polyanilines doped with (HCl+KCl) and (HCl+CoCl2) were prepared by co-doping method, respectively. For comparison, polyaniline emeraldine salt (ES) by doping with HCl and its emeraldine base (EB) form were also synthesized. The co-doped polyanilines, ES and EB samples were all characterized by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy aiming to understand the transformations in the different doping status. The results show that the doping degree of K+ ions is considerably higher than that of Co2+ ions under the same co-doping conditions possibly due to different pseudoprotonation constants of EB with K+ ions and Co2+ ions. Moreover, morphology difference of polyaniline co-doped with alkaline metal ions or transition meal ions may arise from different coordination geometry of metal ions. Nevertheless, there are similar chemical transformations of quinoid units to benzenoid ones on polyaniline backbones for the ES and both co-doped samples. And the polyaniline backbones co-doped with H+ and metal cations are found to attain weaker charge delocalization than the ES which is doped solely with H+.
分别采用共掺杂法制备了掺杂(HCl + KCl)和(HCl + CoCl₂)的聚苯胺。作为对比,还合成了掺杂HCl的聚苯胺翡翠盐(ES)及其翡翠碱(EB)形式。通过傅里叶变换红外光谱(FTIR)和拉曼光谱对共掺杂聚苯胺、ES和EB样品进行了表征,旨在了解不同掺杂状态下的转变情况。结果表明,在相同的共掺杂条件下,K⁺离子的掺杂程度明显高于Co²⁺离子,这可能是由于EB与K⁺离子和Co²⁺离子的假质子化常数不同所致。此外,掺杂碱金属离子或过渡金属离子的聚苯胺的形态差异可能源于金属离子不同的配位几何结构。然而,ES和两种共掺杂样品在聚苯胺主链上都存在类似的醌型单元向苯型单元的化学转变。并且发现,与仅掺杂H⁺的ES相比,共掺杂H⁺和金属阳离子的聚苯胺主链实现了较弱电荷离域。