Advancing ion-exchange membranes to ion-selective membranes: principles,status, and opportunities

● IEM ion/ion selectivities of charge, valence, & specific ion are critically assessed. ● Ion/molecule selectivities of ion/solvent and ion/uncharged solute are reviewed. ● Approaches to advance the selectivities through sorption and migration are analyzed. ● The permeability-selectivity tradeoff appears to be pervasive. ● Ion/molecule selectivities are comparatively underdeveloped and poorly understood. Ion-exchange membranes (IEMs) are utilized in numerous established, emergent, and emerging applications for water, energy, and the environment. This article reviews the five different types of IEM selectivity, namely charge, valence, specific ion, ion/solvent, and ion/uncharged solute selectivities. Technological pathways to advance the selectivities through the sorption and migration mechanisms of transport in IEM are critically analyzed. Because of the underlying principles governing transport, efforts to enhance selectivity by tuning the membrane structural and chemical properties are almost always accompanied by a concomitant decline in permeability of the desired ion. Suppressing the undesired crossover of solvent and neutral species is crucial to realize the practical implementation of several technologies, including bioelectrochemical systems, hypersaline electrodialysis desalination, fuel cells, and redox flow batteries, but the ion/solvent and ion/uncharged solute selectivities are relatively understudied, compared to the ion/ion selectivities. Deepening fundamental understanding of the transport phenomena, specifically the factors underpinning structure-property-performance relationships, will be vital to guide the informed development of more selective IEMs. Innovations in material and membrane design offer opportunities to utilize ion discrimination mechanisms that are radically different from conventional IEMs and potentially depart from the putative permeability-selectivity tradeoff. Advancements in IEM selectivity can contribute to meeting the aqueous separation needs of water, energy, and environmental challenges.