Unidirectional diffusion synthesis of covalent organic frameworks (COFs) on polymeric substrates for dye separation

Covalent organic frameworks (COFs) are regarded as important candidates for the preparation of advanced membranes with remarkable performances on account of their uniform and tailorable channels and good chemical stability. The development of COFs-based membranes is burgeoning, and there remains lacking of facile and mild methods to prepare to these membranes. Herein, we report on the unidirectional diffusion synthesis (UDS) of TpPa (an imine-based COFs) on commercial polyvinylidene fluoride (PVDF) microfiltration substrates for the preparation of composite COFs-based membranes at room temperature. The p-phenylenediamine (Pa) aqueous solution and 1,3,5-triformylphloroglucinol (Tp) n-hexane solution were separately charged into the two sides of a diffusion cell. With the suitable solution pairs and molar ratio of two precursors, only Pa molecules can pass through the macropores of PVDF to react with Tp molecules at the phase interface formed by this solution pairs, leading to the in situ synthesis of TpPa layer on the top side of PVDF substrates. The membrane fabricated with a synthesized duration of 24 h exhibits a superior selectivity for dyes (>90%) and appreciable water permeance (60 L·m⁻²·h⁻¹·bar⁻¹). The permeance of the resultant membrane is ∼2–20 times higher than other reported membranes with comparable dye rejections. The UDS offers a facile and mild process to directly grow COFs on porous polymeric substrates to construct composite membranes capable of efficient separations of dye molecules.