Renormalization of Ionic Solvation Shells in Nanochannels.

Recently, experimental studies on selective ion transport across nanoporous membranes or through single nanochannels have unveiled interesting behaviors of dissolved ions under nanoconfinement. However, the exploration was limited by the resolution of experimental characterization. In this work, we present an atomistic simulation-based study, showing how the nanoconfinement and surface functionalization of graphene and graphene oxide nanochannels renormalize the solvation of ions (Na+ , K+ , Mg2+ , Ca2+ , Cl- ). We find that the spatial distribution of dissolved ions demonstrates a layered order in nanochannels. The 1st hydration shell structures of cations are well defined in channels with width beyond ∼1.0 nm, although the rotational degree of freedom is constrained, while the 2nd hydration shells could be destructed. In the graphene oxide nanochannels, oxygen-containing functional groups can participate in the hydration shells of univalent ions but not for the divalent ions, and the valence-dependent reduction in the ionic diffusivity offers good selectivity between the divalent and univalent ions with the interlayer spacing of ∼1.0 nm, which is absent in the graphene nanochannels. With these findings, we conclude that the assessment of permeability and selectivity of ions has to take the renormalized nature of ionic solvation shells into account in the design of nanoporous membranes or nanofluidic devices for energy and environmental applications.