Evolution of morphology, structure, and performance of the COF membranes with monomer concentrations: Enabling effective desalination and kinetics analysis

Fabricating crystalline covalent organic framework (COF) membrane with sub-nanopores for desalination remains challenging. Monomer (p-phenylenediamine (Pa) and 1,3,5-triformylphloroglucinol (Tp)) concentration) was crucial to tailor the diffusion-reaction of monomers in the p-toluenesulfonic acid (PTSA)-mediated interfacial catalytic polymerization process for crystalline TpPa-COF membrane fabrication. By increasing monomer concentration, membrane surface color evolved from light yellow to dark orange. TpPa-COF layers with adjustable thickness (90.47–436 nm) transformed from amorphous to crystalline with crystalline and cross-linking degree increasing from 16.47 % to 73.90 %, and 66.40 % to 87.60 %, respectively. Pore size decreased from 1.69 to 0.17 nm, while Na2SO4 rejection significantly increased from 26.7 % to 90.4 %. A 3-day filtration test for RO concentrate demonstrated the stability and robust desalination performance with SO42− and Mg2+ rejection ratio of 74.3 ± 1.08 % and 65.6 ± 1.33 %, respectively. Diffusion behavior experiments demonstrated that diffusion coefficient for Pa-PTSA complex (6.49 × 10−5–8.87 × 10−5 cm2 s−1, Pa > 0.05 wt%) higher than Tp (3.53 × 10−6–6.39 × 10−6 cm2 s−1, Tp > 0.006 wt%) by one order of magnitude promoted structural crystallinity and regulated assembly at the interface, resulting in sub-nanopore TpPa-COF layers. This study highlighted the importance of monomer concentration on the COF membrane formation, providing valuable insights for the highly crystalline COF membrane fabrication.