Graphene-based laminar membranes exhibit remarkable ion sieving properties, but their monovalent ion selectivity is still low and much less than the natural ion channels. Inspired by the elementary structure/function relationships of biological ion channels embedded in biomembranes, a new strategy is proposed herein to mimic biological K+ channels by using the graphene laminar membrane (GLM) composed of two-dimensional (2D) angstrom(Å)-scale channels to support a simple model of semi-biomembrane, namely oil/water (O/W) interface. It is found that K+ is strongly preferred over Na+ and Li+ for transferring across the GLM-supported water/1,2-dichloroethane (W/DCE) interface within the same potential window (-0.1-0.6 V), although the monovalent ion selectivity of GLM under the aqueous solution is still low (K+/Na+~1.11 and K+/Li+~1.35). Moreover, the voltammetric responses corresponding to the ion transfer of NH4+ observed at the GLM-supported W/DCE interface also show that NH4+ can often pass through the biological K+ channels due to their comparable hydration-free energies and cation-π interactions. The underlying mechanism of as-observed K+ selective voltammetric responses is discussed and found to be consistent with the energy balance of cationic partial-dehydration (energetic costs) and cation-π interaction (energetic gains) as involved in biological K+ channels.
Keywords: angstrom-scale; cation-π interaction; graphene laminar membrane; ion transfer; oil/water interface.