A Novel Recognition-Polymerization Coupling Strategy for Designing Molecularly Imprinted Functional Monomers with Enhanced Phloroglucinol Adsorption

Surface molecular-imprinting is an efficient and eco-friendly route to resource recovery. Yet most studies prioritize template–monomer affinity and seldom integrate radical-polymerization characteristics upfront, risking an affinity–performance gap. Using phloroglucinol (PG) as a model, a 3D “binding energy–SOMO/LUMO gap–steric hindrance” screening framework is established that identifies N-vinylimidazole (VIM) for matrix grafting and 2-(dimethylamino)ethyl methacrylate (DMAEMA) for imprinting. Surface radical polymerization on VIM-grafted chloromethylated polystyrene with DMAEMA (imprinting monomer) and PG (template) affords CMPS-VIM-MIP. The material exhibits an equilibrium adsorption capacity of 118.4 mg g −1 , 2.6 times that of the commercial resin NKA-II (45.5 mg g −1 ). In the fermentation system, the capacity decreases by 19.9% yet remains 4.0 times that of NKA-II. Mechanistic analysis reveals that imidazolium sites induce long-range electrostatic polarization, while multiple hydrogen bonds between the polymer's carbonyl/tertiary-amine groups and the hydroxyl groups of PG, act cooperatively to form high-affinity imprinting cavities. This multidimensional co-screening of functional monomers delivers concurrent gains in adsorption performance and offers a generalizable route for the green recovery of high-value phenolics.