Tannin-assisted interfacial polymerization towards COF membranes for efficient dye separation

Abstract

Membrane separation has been shown to have significant potential in addressing the global shortage of clean water. Covalent organic frameworks (COFs) have gained significant attention in the field of membrane separation due to their structural stability and controllable pore size. Here, a modification of polyethersulfone ultrafiltration membranes with TA-assisted COFs is prepared by interfacial polymerization and co-deposition. Intriguingly, in comparison to the conventional COF synthesis method, the interfacial polymerization reaction used n-butanol as the oil-phase monomer to prevent substrate corrosion. More importantly, the TA-assisted co-deposition not only introduces a large number of environmentally friendly hydrophilic groups to enhance the hydrophilicity of the membrane surface, but also the phenolic hydroxyl group contained in TA generates a quinone group upon oxidation. This group can undergo a Michael addition reaction with the amine group, followed by interfacial polymerization to regulate the COFs pore size. Consequently, the optimized membrane exhibited a high permeation flux of 122.03 L m⁻² h⁻¹ bar⁻¹ without altering the pore size structure of the original membranes and demonstrated separation performance for various dyes (Mw: 300–1300 g mol⁻¹), with a retention rate of over 98%. Despite multiple filtrations of methyl blue dye, the membrane prepared by simple rinsing still exhibited high retention rates (>98%) with exceptional stability and retention performance. The optimized membrane demonstrated good hydrophilicity and dye separation performance, indicated promising potential for dye separation applications.