Understanding Mono- and Bivalent Ion Selectivities of Nanoporous Graphene Using Ionic and Bi-ionic Potentials

Abstract

Nanoporous graphene displays salt-dependent ion permeation. In this work, we investigate the differences in Donnan potentials arising between reservoirs, separated by a perforated graphene membrane, containing different cations. We compare the case of monovalent cations interacting with nanoporous graphene with the case of bivalent cations. This is accomplished through both measurements of membrane potential arising between two salt reservoirs at different concentrations involving a single cation (ionic potential) and between two reservoirs containing different cations at the same concentration (bi-ionic potential). In our present study, Donnan dialysis experiments involve bivalent MgCl ₂, CaCl ₂, and CuCl ₂ as well as monovalent KCl and NH ₄Cl salts. For all salts, except CuCl ₂, clear Donnan and diffusion potential plateaus were observed at low and high salt concentrations, respectively. Our observations show that the membrane potential scaled to the Nernst potential for bivalent cations has a lower value (≈50%) than for monovalent cations (≈72%) in the Donnan exclusion regime. This is likely due to the adsorption of these bivalent cations on monolayer graphene. For bivalent cations, the diffusion regime is reached at a lower ionic strength compared to the monovalent cations. For Mg ²⁺ and Ca ²⁺, the membrane potential does not seem to depend upon the type of ions in the entire ionic strength range. A similar behavior is observed for the KCl and NH ₄Cl membrane potential curves. For CuCl ₂, the membrane potential curve is shifted toward lower ionic strength compared to the other two bivalent salts and the Donnan plateau is not observed at the lowest ionic strength. Bi-ionic potential measurements give further insight into the strength of specific interactions, allowing for the estimation of the relative ionic selectivities of different cations based on comparing their bi-ionic potentials. This effect of possible ion adsorption on graphene can be removed through ion exchange with monovalent salts.