Synthetic polymer membranes are enabling components in key technologies at the water–energy nexus, including desalination and energy conversion, because of their high water/salt selectivity or ionic conductivity. However, many applications at the water–energy nexus require ion selectivity, or separation of specific ionic species from other similar species. Here, the ion selectivity of conventional polymeric membrane materials is assessed and recent progress in enhancing selective transport via tailored free volume elements and ion–membrane interactions is described. In view of the limitations of polymeric membranes, three material classes—porous crystalline materials, 2D materials, and discrete biomimetic channels—are highlighted as possible candidates for ion‐selective membranes owing to their molecular‐level control over physical and chemical properties. Lastly, research directions and critical challenges for developing bioinspired membranes with molecular recognition are provided.
State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu
2+
, Ni
2+
, Zn
2+
, Co
2+
, and Mg
2+
. We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.
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