Abstract
While polymer membranes are used to remove salts from environmental and industrial electrolytes, it remains a significant challenge to engineer them to isolate a single dissolved species from complex mixtures, which is important for lithium mining, battery and magnet recycling, and microelectronics. Underpinning this challenge has been a lack of understanding of rate-limiting mechanisms in selective ion transport. Here, we show that hydrated ions exhibit higher free energies of activation when crossing solution-membrane interfaces (i.e., partitioning) than when diffusing through polymers, which challenges historical assumptions embedded in widely used models of membrane performance. We further articulate a framework benchmarked with quantitative capabilities for predicting how functionality within polymer membranes or at their surfaces affects selectivity toward individual dissolved species.