Bai Yichao, Liu Youxing, Liu Minghui, Wang Xinyu, Shang Shengcong, Gao Wenqiang, Du Changsheng, Qiao Yan, Chen Jianyi, Dong Jichen, Liu Yunqi
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Angew Chem Int Ed Engl. 2022 Jan 10;61(2):e202113067. doi: 10.1002/anie.202113067. Epub 2021 Nov 22.
Facile synthesis and post-processing of covalent organic frameworks (COFs) under mild synthetic conditions are highly sought after and important for widespread utilizations in catalysis and energy storage. Here we report the synthesis of the chemically stable aza-fused COFs BPT-COF and PT-COF by a liquid-phase method. The process involves the spontaneous polycondensation of vicinal diamines and vicinal diketones, and is driven by the near-equilibrium growth of COF domains at a very low monomer concentration. The method permits in situ assembly of COFs and COF-GO hybrid materials and leads to the formation of a uniform conducting film on arbitrary substrates on vacuum filtration. When used as electrocatalysts, the as-prepared membranes show a fast hydrogen evolution reaction (HER) with a low overpotential (45 mV at 10 mA cm ) and a small Tafel slope (53 mV dec ), which are the best among metal-free catalysts. Our results may open a new route towards the preparation of highly π-conjugated COFs for multifunctional applications.
在温和的合成条件下对共价有机框架（COF）进行简便合成和后处理，对于其在催化和能量存储中的广泛应用而言备受追捧且至关重要。在此，我们报告通过液相法合成化学稳定的氮杂稠合COF即BPT-COF和PT-COF。该过程涉及邻二胺和邻二酮的自发缩聚反应，并且由在极低单体浓度下COF域的近平衡生长驱动。该方法允许COF和COF-GO杂化材料的原位组装，并通过真空过滤在任意基底上形成均匀的导电膜。当用作电催化剂时，所制备的膜表现出快速的析氢反应（HER），过电位低（在10 mA cm时为45 mV）且塔菲尔斜率小（53 mV dec），这在无金属催化剂中是最佳的。我们的结果可能为制备用于多功能应用的高度π共轭COF开辟一条新途径。
