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

Abstract 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.