关于两种因米因基共价有机框架的对比研究对质子导电性和机制分析
Shuai-Long Zhang1, Zhong-Cheng Guo1, An-Ran Su1
1College of Chemistry and Green Catalysis Center, Zhengzhou University, Zhengzhou, 450001, Henan, P.R. China.
Chemistry (Weinheim an der Bergstrasse, Germany)
|July 14, 2023
概括
在共价有机框架 (COF) 中的分子内H键阻碍了质子导电性. 引入伊米达会破坏这些键,形成分子间H键,并显著促进COF中的质子运输.
科学领域:
- 材料科学 材料科学 材料科学
- 化学 化学 化学
- 电化学 电化学 电化学
背景情况:
- 在多孔材料中的质子导电性对于能源应用至关重要.
- 共价有机框架 (COF) 提供可调节的结构,但往往表现出有限的质子传输.
- 在COF孔壁内的分子内键可以阻碍质子运动.
研究的目的:
- 研究分子内键对COF中质子导电性的影响.
- 探索伊米达功能化的潜力,以增强COF中的质子运输.
- 阐明伊米达加入改变结网络和质子导电性的机制.
主要方法:
- 合成和描述DaTta和TaTta的COFs.
- 将伊米达装入COF毛孔,从而产生Im@DaTta和Im@TaTta.
- 在不同温度和湿度下测量质子导电性.
- 气体吸附分析,激活能计算和密度函数理论 (DFT) 建模.
主要成果:
- 没有修改的DaTta和TaTtaCOF显示出较低的质子导电性,其中σ(DaTta) <σ(TaTta).
- 带有伊米达的COF (Im@DaTta和Im@TaTta) 显示出显著增强的质子导电性.
- 与Im@TaTta (3.73×10−3 S cm−1) 相比,Im@DaTta在100°C和98%RH时显示出更高的质子导电性 (0.91×10−2 S cm−1).
- 结构和计算分析表明,在含有伊米达时,分子内H键的破坏和分子间H键的形成.
结论:
- 在COF孔壁内的分子内键显著限制了质子导电性.
- 伊米达的功能化有效地破坏分子内H键,促进分子间H键的形成.
- 这种对结网的修改导致COF中的质子导电率大幅增加,使它们成为质子导电应用的有希望的应用.
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