In view of the high risks brought about by organic micropollutants (OMPs), nanofiltration (NF) processes have been playing a vital role in advanced water and wastewater treatment, owing to the high membrane performance in rejection of OMPs, permeation of water, and passage of mineral salts. Though numerous studies have been devoted to evaluating and technically enhancing membrane performance in removing various OMPs, the trade-off effect between water permeance and water/OMP selectivity for state-of-the-art membranes remains far from being understood. Knowledge of this effect is significant for comparing and guiding membrane development works toward cost-efficient OMP removal. In this work, we comprehensively assessed the performance of 88 NF membranes, commercialized or newly developed, based on their water permeance and OMP rejection data published in the literature. The effectiveness and underlying mechanisms of various modification methods in tailoring properties and in turn performance of the mainstream polyamide (PA) thin-film composite (TFC) membranes were quantitatively analyzed. The trade-off effect was demonstrated by the abundant data from both experimental measurements and machine learning-based prediction. On this basis, the advancement of novel membranes was benchmarked by the performance upper-bound revealed by commercial membranes and lab-made PA membranes. We also assessed the potentials of current NF membranes in selectively separating OMPs from inorganic salts and identified the future research perspectives to achieve further enhancement in OMP removal and salt/OMP selectivity of NF membranes.

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.

Interfacial free energy is a quantitative basis for explaining and predicting interfacial behavior that is ubiquitous in nature. The contact angle (CA) method can determine the surface free energy (γ) as well as Lifshitz–van der Waals (γLW) and Lewis acid/base (γ+/γ–) components of a solid material from its CAs with a set of known test liquids according to the extended Young–Dupré equation. However, the reliability of the “known” parameters of the test liquids is questioned due to the long-neglected surface roughness effect during calibration of the liquids. This study proposed a simple and practicable two-step approach to correct the energy parameters of several test liquids by incorporating Wenzel’s surface roughness relationship into CA measurement. Step 1: water and two apolar liquids (diiodomethane and α-bromonaphthalene) were used as benchmarks to calibrate the surface roughness and energy parameters of two reference solids [apolar poly­(tetrafluoroethylene) and monopolar poly­(methyl methacrylate)], and step 2: the reference solids were used to calibrate any other test liquids by solving the energy parameters from their CAs in the extended Young–Dupré–Wenzel model. Monte Carlo simulation was used to evaluate error transmission and robustness of the model solutions. The obtained energy parameters (γLW/γ+/γ–) of four test liquids (dimethyl sulfoxide, formamide, ethylene glycol, and glycerol) are 28.01/13.68/4.67, 34.95/3.53/37.62, 26.26/7.51/15.74, and 32.99/9.24/26.02 mJ/m2, respectively, and different from the literature values. The liquids were applied to characterize an example solid surface with true γLW/γ+/γ– values of 28.00/1.00/8.00 mJ/m2 and a roughness index (r) of 1.60. Without correction of the liquid parameters, the calculated surface energy, hydration energy, and hydrophobic attraction energy of the solid sample can deviate by 50, 13, and 27%, respectively. This proves the necessity of correcting parameters of the test liquids before they can be used in CA and interfacial energy studies in the presence of surface roughness.