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有机压电材料具有高极化和非中心对称特性，在施加机械应力时产生能量，对自供电技术的发展至关重要。尽管部分聚合物已被证明显示出压电性，但聚合物链中偶极矩的随机分布和长程排列的缺乏限制了电极化过程中的畴演变和永久极化，导致较低的输出电压，严重限制它们的实际应用。故而亟需开发具有长程有序构象和稳健极化特性的高性能有机压电材料。 近日，香港城市大学的张其春教授、山东大学的秦伟教授、华南理工大学的韩宇教授和苏州大学的路建美教授合作，以典型的二维（2D）共价有机框架（COFs）为研究对象，从含氟聚合物的能量采集器的成功实施中汲取灵感，设计了一种全新的氟取代烷基链接枝到2D COFs实现周期性的非对称性、自发极化和压电性的功能化策略，构建了高性能的压电纳米发电机（PENG）有效地将机械应力转化为电能，并成功驱动了LED灯阵列和LED数显计时器
氟取代烷基极化链组装二维共价有机框架结构在压电纳米发电机的应用中具有独特优势。首先，在侧链引入氟烷基链增强了分子的极化性和不对称性，并赋予结构以高的疏水性、机械稳定性和空气稳定性。其次，构建的二维共价有机骨架为偶极矩的长程有序排列提供了通道，提高了材料整体的压电性质。 同时，DFT 理论模拟计算也表明该结构具有优异的偶极矩，有利于产生自发极化，并在机械应力刺激下发生电荷分离形成输出电压。通过压电力显微镜（PFM）、开尔文探针力显微镜（KPFM）和压电应变常数d33测试，氟烷基链组装二维共价有机框架具有优异的压电性质。 最终，该氟取代烷基链组装2D COFs在压电纳米发电机应用中表现出优异的输出电压、输出电流和良好的循环稳定性。在无极化条件下，压电COF纳米发电机的最大输出开路电压（Voc）可达60 V，短路电流（Isc）高达2.4μA，瞬时功率（P）高达3.3µW，并且具有长期稳定性（14天内输出电压依旧稳定）。该工作首次将氟化烷基链引入2D COFs用于压电纳米发电机，从而为功能化压电COFs的设计开发和有机压电纳米发电机的性能提升提供了一种新策略。 论文信息 High-Performance Piezoelectric Two-Dimensional Covalent Organic Frameworks Qianfeng Gu, Xiangqian Lu, Dr. Cailing Chen, Xiang Wang, Fangyuan Kang, Prof. Yang Yang Li Prof. Qingfeng Xu, Prof. Jianmei Lu, Prof. Yu Han, Prof. Wei Qin, Prof. Qichun Zhang. 文章的第一作者是香港城市大学的博士生顾钱锋和山东大学的博士生路向前。 Angewandte Chemie International Edition DOI: 10.1002/anie.202409708
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