Ultrathin Polyamide Membrane with Decreased Porosity Designed for Outstanding Water-Softening Performance and Superior Antifouling Properties

Poly­(piperazine-amide)-based nanofiltration membranes exhibit a smooth surface and superior antifouling properties but often have lower Ca2+ and Mg2+ rejection due to their larger inner micropore and thus cannot be extensively used in water-softening applications. To decrease the pore size of poly­(piperazine-amide) membranes, we designed and synthesized a novel monomer, 1,2,3,4-cyclobutane tetracarboxylic acid chloride (BTC), which possesses a smaller molecular conformation than trimesoyl chloride (TMC). The thickness of the prepared BTC–piperazine (PIP) polyamide nanofilm via interfacial polymerization is as thin as 15 nm, significantly lower than the 50 nm thickness of the TMC–PIP nanofilm. The surface characterization reveals that the BTC–PIP polyamide membrane exhibits an enhanced hydrophilicity, a smooth surface, and a decreased surface-negative charge. The desalination performance (both rejection and water flux) of these membranes in terms of Ca2+ and Mg2+ exceeds that of the current commercial water-softening membranes. In addition, the BTC–PIP polyamide membrane also exhibits superior antifouling properties compared to the TMC-based polyamide membrane. More importantly, molecular simulations show that the BTC–PIP membrane has a lower average pore size than that of the TMC–PIP membrane, which demonstrates an enhanced steric hindrance effect, as confirmed by desalination performance. Our results demonstrate that in the household and industrial water-softening market, BTC–PIP membrane with decreased porosity, enhanced hydrophilicity, and smooth surface is preferred alternative to the conventional TMC-based polyamide membranes.