采用密度泛函理论对吡咯(Py)和聚吡咯分子(PPy)进行全优化,并在b31yp/6-31g(d)水平上计算了Py和PPy分子中氮原子的电荷密度、最高占据分子轨道(HOMO)能量、最低空轨道(LUMO)能量和能带隙(ΔE)。从理论角度探究了Py和PPy分子结构与导电性的关系。在理论分析预测的基础上,选择合适的氧化剂和掺杂剂及其在实验中适宜的用量,采用化学氧化法制备不同反应温度下的PPy,探讨了反应温度对PPy聚合度及其导电性能的影响。结果表明:PPy的聚合度越大,其导电性就越好;低温有利于制备聚合度较高和电导率较好的PPy。
Density functional theory was used to fully optimize pyrrole (Py) and polypyrrole (PPy,C4nH3n+2Nn,n= 2,3,4,5,6,7,8) molecules.The charge density of nitrogen atoms,highest occupied molecular orbital (HOMO) energy,lowest unoccupied molecular orbital (LUMO) energy and energy band gap (ΔE) of Py and PPy molecules were calculated at the b31yp/6-31g(d) level.The relationship between molecular structure and electrical conductivity of Py and PPy was explored theoretically.Based on the theoretical analysis and prediction,PPy was prepared by chemical oxidation method at different reaction temperatures by selecting suitable oxidants and dopants and their appropriate dosages in the experiments.The influence of reaction temperature on the polymerization degree and conductivity of PPy was investigated.The results showed that the higher the degree of polymerization,the better the conductivity of PPy.Low temperature was conducive to the preparation of PPy with higher polymerization degree and better conductivity.
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基金资助
国家自然科学基金(62105179);浙江省公益技术应用研究计划项目(LGG22B060001);浙江大学衢州研究院科技计划项目(IZQ2019-KJ-027);衢州市科技攻关项目(2022K101)
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