Modulating the Asymmetry of the Active Layer in Pursuit of Nanofiltration Selectivity via Differentiating Interfacial Reactions of Piperazine

Nanofiltration (NF), highly prospective for drinking water treatment, faces a challenge in simultaneously removing emerging contaminants while maintaining mineral salts, particularly divalent cations. To overcome this challenge, NF membranes possessing small pores concomitant with highly negatively charged surfaces were synthesized via a two-step fabrication strategy. The key is to generate a polyamide active layer having a loose and carboxyl group-abundant segment on top and a dense barrier segment underneath. This was achieved by restrained interfacial polymerization between trimesoyl chloride and partly protonated piperazine to form a highly depth-heterogeneous polyamide network, followed by second amidation in an organic environment to remove untethered polyamide fragments and associate malonyl chlorides with reserved amine groups to introduce more negative charges. Most importantly, on first-principle engineering the spatial architecture of the polyamide layer, amplifying asymmetric charge distribution was paired with the thinning of the vertical structure. The optimized membrane exhibits high salt/organic rejection selectivity and water permeance superior to most NF membranes reported previously. The rejections of eight emerging contaminants were in the range of 66.0–94.4%, much higher than the MgCl₂ rejection of 41.1%. This new fabrication strategy, suitable for various diacyl chlorides, along with the new membranes so produced, offers a novel option for NF in potable water systems.