Amphiphilic resorcinarenes-regulated monomer diffusion enables crater-like polyesteramide membranes for high-performance nanofiltration

Developing nanofiltration (NF) membranes that simultaneously achieve high water permeance and selectivity remains a fundamental challenge due to their inherent permeability-selectivity trade-off. Herein, we report a monomer diffusion regulation strategy using amphiphilic sulfonated resorcinarenes (SRA) to fabricate high-performance polyesteramide NF membranes. Incorporated SRAs lower interfacial tension, facilitate PIP diffusion, and self-assemble into physical template aggregates. Driven by the kinetic competition between SRA hydroxyl groups and PIP amines for TMC stemming from their reactivity difference, SRAs temporarily retard crosslinking at SRA-rich sites while their amphiphilicity directs PIP toward adjacent regions to resume polymerization. This kinetic competition, combined with post-encapsulation collapse of SRA assemblies, yields polyesteramide membranes with characteristic crater-like structures and abundant nanovoids within the selective layer. These features increase the effective permeable area and reduce mass transfer resistance. The optimized membrane delivers a water permeance of 26.3 L m −2  h −1 bar −1 , with Na 2 SO 4 rejection of 98.87%, and a Cl − /SO 4 2− selectivity factor of 409.4 in mixed salt feed (1000 ppm Na 2 SO 4 +1000 ppm NaCl). SRA-PIP/TMC membranes achieve improved rejection toward organic micropollutants (OMPs), especially negatively charged hydrophobic species such as ofloxacin and chloroquine phosphate, through the synergistic effects of size sieving, Donnan repulsion, and host-guest inclusion within resorcinarene cavities. Benefiting from ester linkages, the membranes possess good chlorine resistance. This work demonstrates the potential of amphiphilic macrocycle co-monomers for regulating polymerization toward the preparation of high-performance NF membranes for water purification and precise molecular separation.