Surface-confinement strategy enabling ultrahigh filler loading in adsorptive membranes for selective TBBPA separation...

Adsorptive membranes (AMs) are promising for treating nontraditional water sources, yet their efficiencies are often limited by the poor accessibility of adsorption sites and a moderate binding affinity. Here, we combine a tandem delayed phase inversion method (DPIM) with molecularly imprinted technology (MIT) to create surface-confined imprinting sites for Tetrabromobisphenol A (TBBPA), resulting in TBBPA molecularly imprinted membranes (TB-MIMs). In detail, the functionalized mesoporous silicon nanoparticles (FMSNs) are dispersed as fillers into the coagulation bath, and the water/N, N‑dimethylacetamide (DMAc)/ethanol ratio is systematically varied to control and quantify the distribution of FMSNs across the substrate. This solvent composition strategy coordinates phase separation, indirectly positioning recognition cavities at the transport interface. The resulting TB‑MIMs reaches a TBBPA binding capacity of 415.00 mg g⁻¹ within 10 min and exhibits a high selectivity factor over structural analogues-bisphenol A (BPA), 4, 4'‑dihydroxybiphenyl (DDBP), and p‑tert‑butylphenol (BP), outperforming most reported materials. The synergy between the ultra-high accessible surface area and the development of well-matched TBBPA recognition sites supports the findings above. Furthermore, the structural integrity and reusability of the TB-MIMs were confirmed through extensive antifouling evaluations, repeated cycling, and testing in real water (Chao Lake). Overall, this work establishes a generalizable framework that couples membrane formation with filler placement, enabling coordinated control of membrane structure and advancing the development of high‑performance AMs for the selective capture and separation of target contaminants.