Ion-Specific Nanoconfinement Effect in Multilayered Graphene Membranes: A Combined Nuclear Magnetic Resonance and Computational Study

Ion adsorption within nanopores is involved in numerous applications. However, a comprehensive understanding of the fundamental relationship between in-pore ion concentration and pore size, particularly in the sub-2 nm range, is scarce. This study investigates the ion-species-dependent concentration in multilayered graphene membranes (MGMs) with tunable nanoslit sizes (0.5-1.6 nm) using nuclear magnetic resonance and computational simulations. For Na⁺-based electrolytes in MGMs, the concentration of anions in graphene nanoslits increases in correlation with their chaotropic properties. As the nanoslit size decreases, the concentration of chaotropic ion (BF₄^-) increases, whereas the concentration of kosmotropic ions (Cit^3-, PO₄^3-) and other ions (Ac^-, F^-) decreases or changes slightly. Notably, anions remain more concentrated than counter Na⁺ ions, leading to electroneutrality breakdown and unipolar anion packing in MGMs. A continuum modeling approach, integrating molecular dynamic simulation with the Poisson-Boltzmann model, elucidates these observations by considering water-mediated ion-graphene non-electrostatic interactions and charge screening from graphene walls.