Aminal-Linked Covalent Organic Framework Membranes Achieve Superior Ion Selectivity

Abstract

High-salinity wastewater treatment is perceived as a global water resource recycling challenge that must be addressed to achieve zero discharge. Monovalent/divalent salt separation using membrane technology provides a promising strategy for sulfate removal from chlor-alkali brine. However, existing desalination membranes often show low water permeance and insufficient ion selectivity. Herein, an aminal-linked covalent organic framework (COF) membrane featuring a regular long-range pore size of 7 Å and achieving superior ion selectivity is reported, in which a uniform COF layer with subnanosized channels is assembled by the chemical splicing of 1,4-phthalaldehyde (TPA)-piperazine (PZ) COF through an amidation reaction with trimesoyl chloride (TMC). The chemically spliced TPA-PZ (sTPA-PZ) membrane maintains an inherent pore structure and exhibits a water permeance of 13.1 L m^-2 h^-1 bar^-1, a Na₂SO₄ rejection of 99.1%, and a Cl^-/SO₄ ^2- separation factor of 66 for mixed-salt separation, which outperforms all state-of-the-art COF-based membranes reported. Furthermore, the single-stage treatment of NaCl/Na₂SO₄ mixed-salt separation achieves a high NaCl purity of above 95% and a recovery rate of ≈60%, offering great potential for industrial application in monovalent/divalent salt separation and wastewater resource utilization. Therefore, the aminal-linked COF membrane developed in this work provides a new research avenue for designing smart/advanced membrane materials for angstrom-scale separations.

Keywords: aminal‐linked covalent organic framework COF; chemical splicing; ion selectivity; monovalent/divalent salt separation; nanofiltration membrane.