<i>In Situ</i> Characterization of Dehydration during Ion Transport in Polymeric Nanochannels

Abstract

The transport of hydrated ions across nanochannels is central to biological systems and membrane-based applications, yet little is known about their hydrated structure during transport due to the absence of <i>in situ</i> characterization techniques. Herein, we report experimentally resolved ion dehydration during transmembrane transport using modified <i>in situ</i> liquid ToF-SIMS in combination with MD simulations for a mechanistic reasoning. Notably, complete dehydration was not necessary for transport to occur across membranes with sub-nanometer pores. Partial shedding of water molecules from ion solvation shells, observed as a decrease in the average hydration number, allowed the alkali-metal ions studied here (lithium, sodium, and potassium) to permeate membranes with pores smaller than their solvated size. We find that ions generally cannot hold more than two water molecules during this sterically limited transport. In nanopores larger than the size of the solvation shell, we show that ionic mobility governs the ion hydration number distribution. Viscous effects, such as interactions with carboxyl groups inside the membrane, preferentially hinder the transport of the mono- and dihydrates. Our novel technique for studying ion solvation <i>in situ</i> represents a significant technological leap for the nanofluidics field and may enable important advances in ion separation, biosensing, and battery applications.