Fluoride Action Network

Interaction-based ion selectivity exhibited by self-assembled, cross-linked zwitterionic copolymer membranes

Source: PNAS 118 (37) e2022198118. (Proceedings of the National Academy of Sciences of the United States of America) | September 14th, 2021 | By Samuel J. Lounder and Ayse Asatekin.
Location: International
Industry type: Water Treatment


The separation of ions is challenging yet crucial for providing access to safe water resources as well as recovering valuable ions from water and wastewater. Yet, membranes rarely exhibit selectivity between ions of similar charge and size. We demonstrate that membranes, prepared by a fully scalable method that uses self-assembling zwitterionic copolymers, exhibit exceptional selectivity between salt anions of similar size and charge. We show that this unusual capability is derived from selective zwitterion–ion interactions occurring within the nanochannels, similarly to biological ion channels. We further demonstrate these membranes exhibit Cl/F permselectivity more than twice the values reported in previous studies, with applications in treating groundwater streams to prevent fluorosis and in wastewater treatment.


Water filtration membranes with advanced ion selectivity are urgently needed for resource recovery and the production of clean drinking water. This work investigates the separation capabilities of cross-linked zwitterionic copolymer membranes, a self-assembled membrane system featuring subnanometer zwitterionic nanochannels. We demonstrate that selective zwitterion–anion interactions simultaneously control salt partitioning and diffusivity, with the permeabilities of NaClO4, NaI, NaBr, NaCl, NaF, and Na2SO4 spanning roughly three orders of magnitude over a wide range of feed concentrations. We model salt flux using a one-dimensional transport model based on the Maxwell–Stefan equations and show that diffusion is the dominant mode of transport for 1:1 sodium salts. Differences in zwitterion–Cl and zwitterion–F interactions granted these membranes with the ultrahigh Cl/F permselectivity (PCl-/PF- = 24), enabling high fluoride retention and high chloride passage even from saline mixtures of NaCl and NaF.

Read the full article at https://www.pnas.org/content/118/37/e2022198118