Solvent-activated thin-film nanocomposite membranes molecularly tuned with macrocyclic cavities for efficient water desalination and boron removal

Abstract

Tuning the permeation properties of thin-film nanocomposite (TFN) membranes through the molecular redesign of their underlying nanoarchitecture is a challenging but important task for realizing reverse osmosis (RO) desalination performance above the trade-off limit. Activation by organic solvents, as one of the most facile methods to rearrange the microstructure of RO membranes, can effectively boost the water permeability but is constrained by the significant rejection loss. Here, we innovated an integrative approach whereby soluble organic macrocyclic cavitands (OMCs) with molecular-sieving open cavities were simultaneously dissolved in the activating solvent during membrane post-treatment such that their infiltration into the interfacially polymerized (IP) polyamide (PA) layer enabled the formation of a nanocomposite structure with recovered or even enhanced salt rejections. In this work, prefabricated polysulfone-supported pristine PA membranes were transformed into cavity-bearing nanocomposites after being treated with methanol solutions containing 4-sulfocalix[4]arene (SCA4), an OMC structure with a strongly size-sieving ∼ 3.0 Å cavity opening. This integrative solvent-cavitand treatment allowed their water permeability to increase by up to 129% from 1.98 to 4.53 Lm−2h−1bar−1 with uncompromised or even enhanced NaCl rejection, leading to overall separation performances that well surpassed the permeability-selectivity trade-off line. Meanwhile, these SCA4-infiltrated TFN membranes also demonstrated promising boron removal efficiency with an increase in both the water permeability and boron rejection from 1.95 to 4.17 Lm−2h−1bar−1 and 96.9% to 97.4% at pH = 10, respectively. With the wide array of solvent and soluble nanoarchitecture options, this study could provide a new and versatile direction in designing high-performance TFN membranes for environmentally important separations.