Covalent organic frameworks (COFs) are attractive innovative crystalline porous materials that have immense potential for the production of high-performance nanofiltration membranes. Although the conventional water-organic interfacial polymerization process has been broadly applied to fabricate COFs composite membranes on polymeric substrates, it cannot be applicable for COFs constructed by poorly water-soluble aromatic amine monomers. Herein, we report the fabrication of triphenylamine-based COFs composite membranes via an oligomer-triggered interfacial polymerization (OT-IP) process on a hydrolyzed polyacrylonitrile (HPAN) substrate, in which the interfacial reaction occurred between an acetic acid aqueous solution and an organic solution of 1,3,5-triformylphloroglucinol (Tp) in n-hexane and tris(4-aminophenyl)amine (TAPA) in mesitylene premixed in a short time. The Tp-TAPA oligomers generated during the premixing were characterized in terms of morphology and molecular weight. The TpTAPA film formation during the OT-IP process was in situ observed through an optical contact angle measurement device. The TpTAPA/HPAN composite membranes displayed a water permeance of 68.1 L⋅m⁻²⋅h⁻¹·bar⁻¹, and the rejections of different dye (EBT, CR) and drug (DG, AG) molecules above 92.0%. In addition, the composite membrane showed excellent stability in acidic solution and continuous filtration for 75 h. The results indicated that the OT-IP approach is a feasible and efficient approach to fabricate triphenylamine-based COF composite membranes with water-insoluble monomers.

共价有机框架 (COF) 是极具吸引力的创新结晶多孔材料，在生产高性能纳滤膜方面具有巨大潜力。尽管传统的水-有机界面聚合工艺已广泛应用于在聚合物基底上制备 COFs 复合膜，但它不适用于由水溶性差的芳香胺单体构建的 COFs。在此，我们报告了基于三苯胺的 COFs 复合膜的制备在水解聚丙烯腈 (HPAN) 底物上进行低聚物引发的界面聚合 (OT-IP) 过程，其中界面反应发生在乙酸水溶液和 1,3,5-三甲酰基间苯三酚 (Tp) 在 n 中的有机溶液之间-己烷和三（4-氨基苯基）胺（TAPA）在均三甲苯中短时间预混合。在预混合过程中产生的 Tp-TAPA 低聚物的特征在于形态和分子量。通过光学接触角测量装置原位观察了 OT-IP 过程中 TpTAPA 膜的形成。TpTAPA/HPAN 复合膜的透水率为 68.1 L⋅m ^-2 ⋅h ^-1 ·bar ^-1, 不同染料 (EBT, CR) 和药物 (DG, AG) 分子的截留率在 92.0% 以上。此外，该复合膜在酸性溶液和连续过滤75小时后表现出优异的稳定性。结果表明，OT-IP 方法是用水不溶性单体制备三苯胺基 COF 复合膜的一种可行且有效的方法。