Molecular Manipulation of Polyamide Nanostructures Reconciles the Permeance–Selectivity Threshold for Precise Ion Separation

Abstract Membrane nanofiltration (NF) has emerged as a prominent energy-efficient separation technology for widespread applications related to the water‒energy nexus. However, state-of-the-art polyamide (PA) NF membranes are markedly constrained by a ubiquitous, pernicious tradeoff between water permeance and selectivity. Leveraging the prestigious structure-determining performance rationale, this work conceives a facile and robust molecular engineering approach that enables simultaneous improvements in water permeance and co-cation selectivity through synthetic molecular construction of a PA nanofilm with unique cationic triazolyl heterocyclic polyamide (CTHP) structures during scalable interfacial polymerization. Experimental data in conjunction with molecular simulations reveal that the CTHP structures instigate exquisite regulation of the PA subnanometer pore architecture and the specific binding affinity with water and ions, which not only affords precise ion sieving ability and advanced Donnan exclusion selectivity but also energetically facilitates the partitioning and transport of water molecules. The exemplified PA membrane exhibits unparalleled divalent cation rejections of over 99%, accompanied by a 9-fold increase in monovalent/divalent cation sieving selectivity, which is substantially greater than that of the pristine benchmark, a superior water permeation rate, and excellent chemical and operational stability, circumventing the permeance/selectivity threshold. We believe that the molecular engineering strategy implemented in this work holds broad prospects for the rational design and fabrication of semipermeable polymeric NF membranes for sustainable and precision separations.