Substrate modification of thin film composite (TFC) membranes by various crosslinkers is generally required for organic solvent nanofiltration (OSN) application, to enhance the membrane stability and solvent resistance, which however leads to the permeance decline. In this contribution, coordination-crosslinked polyimide substrate is developed for the first time, which is different with those covalently-crosslinked substrates, and achieves the enhanced solvent resistance, improved hydrophilicity and optimized porous microstructure simultaneously. The effects of the alkaline coagulation bath, subsequent ion exchange, and further solvent activation are investigated. The resultant TFC membrane breaks through the typical permeability-selectivity trade-off of OSN membranes successfully, exhibiting an astonishingly superior solvent permeance (1.5–2 times the highest data) (65.2 LMH/bar for methanol, 33.1 LMH/bar for ethanol and 59.1 LMH/bar for acetone) to previously reported polymeric-based TFC OSN membranes with a competitive solute rejection (>98% for Rose Bengal). This study is believed to provide a new orientation in the development of the desirable substrate for the high-performance OSN composite membrane and other separation applications.

有机溶剂纳滤 (OSN) 应用通常需要通过各种交联剂对薄膜复合 (TFC) 膜进行基材改性，以提高膜的稳定性和耐溶剂性，但这会导致渗透率下降。在此贡献中，首次开发了配位交联的聚酰亚胺基材，与那些共价交联的基材不同，同时实现了增强的耐溶剂性、改善的亲水性和优化的多孔微观结构。研究了碱性凝固浴、随后的离子交换和进一步溶剂活化的影响。由此产生的 TFC 膜成功地突破了 OSN 膜的典型渗透率-选择性权衡，表现出惊人的优异溶剂渗透性 (1. 最高数据的 5-2 倍）（甲醇为 65.2 LMH/bar，乙醇为 33.1 LMH/bar，丙酮为 59.1 LMH/bar）与先前报道的具有竞争性溶质截留率的基于聚合物的 TFC OSN 膜（Rose > 98%）孟加拉）。该研究被认为为高性能 OSN 复合膜和其他分离应用的理想基材的开发提供了新的方向。