Membrane Functionalization Approaches toward Per- and Polyfluoroalkyl Substances and Selected Metal Ion Separations.

Adsorption and ion exchange technologies are two of the most widely used approaches to separate pollutants from water; however, their intrinsic diffusion limitations continue to be a challenge. Pore functionalized membranes are a promising technology that can help overcome these challenges, but the extents of their competitive benefits and broad applicability have not been systematically evaluated. Herein, three types of adsorptive/ion exchange (IX) polymers containing strong/weak acid, strong base, and iron-chitosan complex groups were synthesized in the pores and partially on the surface of microfiltration (MF) membranes and tested for the removal of organic and inorganic cations and anions from water, including arsenic, per- and polyfluoroalkyl substances (PFAS), and calcium (hardness). When directly compared with beads (0.5-6 mm) and crushed resins (0.05 mm), adsorptive/IX pore-functionalized membranes demonstrated an increased relative sorption capacity, up to 2 orders of magnitude faster kinetics and the ability to regenerate up to 70-100% of their capacity while concentrating the initial solution concentration up to 12 times. The simple and versatile synthesis approach used to functionalize membranes, notably independent of the polymer type of the MF membrane, utilized pores throughout the entire cross section of the membrane to immobilize the polymers that contain the functional groups. Utilizing the pore volume of commercial membranes (6-112 mL/m2), the scientific weight capacity of the polymer (3.1-11.5 mequiv/g), and the synthesis conditions (e.g., monomer concentration), the theoretical adsorption/IX capacities per area of the membranes were calculated to be as high as 550 mequiv/m2, substantially higher than the 175 mequiv/m2 value needed to compete with commercially available IX resins. This work therefore shows that pore functionalized membranes are a promising path to tackle water contamination challenges, lowering separation diffusion limitations.

Dual-Functional Nanofiltration and Adsorptive Membranes for PFAS and Organics Separation from Water.

Challenges associated with water separation technologies for per- and polyfluoroalkyl substances (PFASs) require efficient and sustainable processes supported by a proper understanding of the separation mechanisms. The solute rejections by nanofiltration (NF) at pH values near the membrane isoelectric point were compared to the size- and mass-transfer-dependent modeled rejection rates of these compounds in an ionized state. We find that the low pK a value of perfluorooctanoic acid (PFOA) relates to enhanced solute exclusions by minimizing the presence and partitioning of the protonated organic compound into the membrane domain. The effects of Donnan exclusion are moderate, and co-ion transport also contributes to the PFAS rejection rates. An additional support barrier with thermo-responsive (quantified by water permeance variation) adsorption/desorption properties allows for enhanced separations of PFAS. This was possible by successfully synthesizing an NF layer on top of a poly-N-isopropylacrylamide (PNIPAm) pore-functionalized microfiltration support structure. The support layer adsorbs organics (178 mg PFOA adsorbed/m2 membrane at an equilibrium concentration of 70 mg/L), and the simultaneous exclusion from the NF layer allows separations of PFOA and the smaller sized heptafluorobutyric acid from solutions containing 70 µg/L of these compounds at a high water flux of 100 L/m2-h at 7 bar.

Positively charged nanofiltration membrane synthesis, transport models, and lanthanides separation.

The design and understanding of rejection mechanisms for both positively and negatively charged nanofiltration (NF) membranes are needed for the development of highly selective separation of multivalent ions. In this study, positively charged nanofiltration membranes were created via an addition of commercially available polyallylamine hydrochloride (PAH) by conventional interfacial polymerization technique. Demonstration of real increase in surface zeta potential, along with other characterization methods, confirmed the addition of weak basic functional groups from PAH. Both positively and negatively charged NF membranes were tested for evaluating their potential as a technology for the recovery or separation of lanthanide cations (neodymium and lanthanum chloride as model salts) from aqueous sources. Particularly, the NF membranes with added PAH performed high and stable lanthanides retentions, with values around 99.3% in mixtures with high ionic strength (100 mM, equivalent to ~6,000 ppm), 99.3% rejection at 85% water recovery (and high Na+/La3+ selectivity, with 0% Na+ rejection starting at 65% recovery), and both constant lanthanum rejection and permeate flux at even pH 2.7. Donnan steric pore model with dielectric exclusion elucidated the transport mechanism of lanthanides and sodium, proving the potential of high selective separation at low permeate fluxes using positively charged NF membranes.