High-flux filtration membranes constructed through scalable and sustainable methods are desirable for energy-efficient separations. Often, these criteria are difficult to be reconciled with one another. Polymeric membranes can provide high flux but frequently involve organic solvents in processing steps. Solubility of many polymeric membranes in organic media also restricts their implementation in solvent filtration. In the present work, we report a simple and high-throughput aqueous processing approach for polyelectrolyte complex (PEC) membranes with controllable porosity and stability in various aqueous and organic environments. PECs are materials composed of oppositely charged polymer chains that can form solids in aqueous environments, yet which can be dissolved in very specific salt solutions capable of breaking the interpolymer ion pairs. By exploiting the salt-induced dissolution and subsequent reformation of the complex, nano- to microporous films are rapidly synthesized which resemble membranes obtained through conventional solvent-phase inversion techniques. PECs remain stable in organic solvents because of the low dielectric constant of the environment, which enhances electrostatic interactions, making them suitable for a wide range of water and solvent filtration applications. Here, we elucidate how the polymer-phase behavior can be manipulated to exercise morphological control, test membrane performance for water and solvent filtration, and quantify the mechanical stability of PECs in relevant conditions.

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Polyelectrolyte complex (PEC) materials show promise in the development of tunable membranes for aqueous and organic solvent separations, as well as in the creation of surface layers for fouling control. In this study, we developed a polyelectrolyte complex (PEC) functionalized by negatively charged carboxymethyl chitosan (CMC−) and positively charged quaternized chitosan (QC+) to tailor its surface properties and antibacterial efficacy. CMC− and QC+ were prepared and characterized using FT-IR and 1 H NMR, which confirmed the presence of the carboxymethyl group and trimethylammonium group in CMC− and QC+ with 65.6% and 83.9% substitution, respectively. The CMC− functionalized PEC (CMC−/PEC) and QC+ functionalized PEC materials (QC+/PEC) were evaluated for their stability in water, resistance to organic and inorganic adsorption, and antibacterial action against a model microorganism, Pseudomonas putida. The results showed no release of chitosan derivatives after adsorption, and CMC−/PEC and QC+/PEC exhibited charge-based, selective repulsion of model organic and inorganic substances. Moreover, the functionalized PEC surfaces displayed lower bacterial attachment due to their smoother surfaces as compared to the bare ceramic membrane and their antimicrobial properties. Among the PEC samples, CMC−/PEC had the lowest cell attachment, while QC+/PEC showed the highest attachment due to electrostatic attraction. The ceramic and bare PEC surfaces were negligibly bactericidal, while cell viability decreased to 34.4 ± 10.2% and 30.6 ± 8.2% with the CMC−/PEC and QC+/PEC surfaces, respectively. In the filtration experiments, the unmodified PEC and CMC−/PEC showed lower rates of flux decline due to organic fouling than did the bare ceramic or QC+/PEC due to electrostatic repulsion. Furthermore, PECs as protective layers promoted much higher flux recoveries than simply backwashing the uncoated membranes. This surface tunability, then, enhances the potential of PECs either as fouling resistant materials or as a method to create a sacrificial, protective layer on surfaces that once fouled can be dissolved and reestablished.