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/m 2 ), 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/m 2 , substantially higher than the 175 mequiv/m 2 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.