Covalent Organic Framework-Mediated Thin-Film Composite Polyamide Membranes toward Precise Ion Sieving

Covalent organic frameworks (COFs) have evinced a potential solution that promises for fast and efficient molecular separation due to the presence of orderly arranged pores and regulable pore apertures. Herein, the synthesized COF (TPB-DMTP-COF) with the pore aperture matching the pore size of the nanofiltration (NF) membrane was utilized to modulate the physicochemical characters of the polyamide (PA) membranes. It is demonstrated that COFs with superior polymer affinity and hydrophilicity not only circumvent the nonselective interfacial cavities but also improve the hydrophilicity of the resultant thin-film nanocomposite (TFN) membranes. Furthermore, the predeposited COF layer is able to slow down the diffusion rate toward the reaction boundary through hydrogen bonding, which is consistent with the results of molecular dynamic (MD) and dissipative particle dynamic (DPD) simulations. In this context, COF-modulated TFN membranes show a roughened and thickened surface with bubble-shaped structures in contrast to the nodular structure of original polyamide membranes. Combined with the introduced in-plane pores of COFs, the resultant TFN membranes display a significantly elevated water permeance of 35.7 L m² h^-1 bar^-1, almost 4-fold that of unmodified polyamide membranes. Furthermore, the selectivity coefficient of Cl^-/SO₄^2- for COF-modulated TFN membranes achieves a high value of 84 mainly related to the enhanced charge density, far exceeding the traditional NF membranes. This work is considered to provide a guideline of exploring hydrophilic COFs as an interlayer for constructing highly permeable membranes with precise ion-sieving ability.