Ren Yuxin, Li Shuang, Wang Meidi, Wu Xue-Qian, Wu Ya-Pan, Sun Bojing, Zhao Jun, Kang Fangyuan, Zhang Qichun, Li Dong-Sheng
College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, Hubei, 443002, P. R. China.
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007, P. R. China.
Adv Sci (Weinh). 2025 May;12(18):e2501442. doi: 10.1002/advs.202501442. Epub 2025 Mar 19.
Developing diverse methods to approach highly crystalline covalent organic frameworks (COFs) for improvement of their electrocatalytic hydrogen evolution reaction (HER) activity is important but very challenging. Herein, for the first time, an electrochemically-driven reconstruction strategy is demonstrated to convert semi-polymerized low-crystalline COFs into highly crystalline, structurally ordered COFs with enhanced HER activity. In situ and ex situ characterizations reveal that cyclic voltammetry (CV) cycles can promote crystallinity, thereby leading to improved conductivity, increased active site density, and superior stability. As a result, the highly crystalline COF achieves low overpotentials of 103.6 and 219.4 mV at 10 and 50 mA cm, respectively, with excellent stability (1200 h at 50 mA cm). More importantly, this strategy is generalizable and effective for various imine-linked COFs with different bonding types, significantly improving their crystallinity and HER activity. This work not only establishes a novel method for constructing highly crystalline COFs but also demonstrates the versatility of electrochemically driven structural modulation in enhancing the catalytic performance of COFs.
开发多种方法来处理高度结晶的共价有机框架（COF）以提高其电催化析氢反应（HER）活性很重要，但极具挑战性。在此，首次展示了一种电化学驱动的重构策略，可将半聚合的低结晶度COF转化为具有增强HER活性的高度结晶、结构有序的COF。原位和非原位表征表明，循环伏安法（CV）循环可促进结晶度，从而提高导电性、增加活性位点密度并提升稳定性。结果，高度结晶的COF在10和50 mA cm时分别实现了103.6和219.4 mV的低过电位，具有出色的稳定性（在50 mA cm下1200小时）。更重要的是，该策略对于具有不同键合类型的各种亚胺连接的COF具有通用性和有效性，可显著提高其结晶度和HER活性。这项工作不仅建立了一种构建高度结晶COF的新方法，还展示了电化学驱动的结构调制在增强COF催化性能方面的多功能性。
