Structure and self-diffusivity of alkali-halide electrolytes in neutral and charged graphene nanochannels

Understanding the microscopic behaviour of aqueous electrolyte solutions in graphene-based ultrathin nanochannels is important in nanofluidic applications such as water purification, fuel cells, and molecular sensing. Under extreme confinement (<2 nm), the properties of water and ions differ drastically from those in the bulk phase. We studied the structural and diffusion behaviour of prototypical aqueous solutions of electrolytes (LiCl, NaCl, and KCl) confined in both neutral and positively-, and negatively-charged graphene nanochannels. We performed molecular dynamics simulations of the solutions in the nanochannels with either one, two- or three-layer water structures using the effectively polarisable force field for graphene. We analysed the structure and intermolecular bond network of the confined solutions along with their relation to the self-diffusivity of water and ions. The simulations show that Na and K cations can more easily rearrange their solvation shells under the graphene nanoconfinement and adsorb on the graphene surfaces or dissolve in the confinement-induced layered water than the Li cation. The negative surface charge together with the presence of ions orient water molecules with hydrogens towards the graphene surfaces, which in turn weakens the intermolecular bond network. The one-layer nanochannels have the biggest effect on the water structure and intermolecular bonding as well as on the adsorption of ions with only co-ions entering these nanochannels. The self-diffusivity of confined water is strongly reduced with respect to the bulk water and decreases with diminishing nanochannel heights except for the negatively-charged one-layer nanochannel. The self-diffusivity of ions also decreases with the reducing the nanochannel heights except for the self-diffusivity of cations in the negatively-charged one-layer nanochannel, evidencing cooperative diffusion of confined water and ions. Due to the significant break-up of the intermolecular bond network in the negatively-charged one-layer nanochannel, self-diffusion coefficients of water and cations exceed those for the two- and three-layer nanochannels and become comparable to the bulk values.