There is increasing interest in understanding the properties of solutions confined within nanotubes and synthetic or biological nanopores. How the ionic content of a nanopore-confined solution differs from that of a contacting bulk salt solution is of particular importance, for example, to water desalinization, industrial electrolysis, and all living systems. This paper explores ionic content, ionic interactions, and ion-transport properties of solutions confined within the 10 nm diameter pores of a synthetic polymer membrane. The membrane has a fixed negative pore-wall and surface charge due to ionizable carbonate groups. As a result, under some conditions, the nanopore-confined solution contains only cations and no anions or salt present in a contacting solution, ideal cation permselectivity. This anion- and salt-rejecting ability varies greatly with the cation of the salt, a result that is in contradiction to the prevailing model for permselectivity in nanopores. The extant model fails because it does not account for specific chemical interactions between the cation and the carbonate groups. The nature of these ion-selective interactions is discussed here.
Keywords: confined electrolyte solutions; law of matching water affinities; nanoionics; nanopore membranes; nanopores; permselectivity; potentiometry.