Tuning Pore Size in Graphene in the Angstrom Regime for Highly Selective Ion–Ion Separation

Zero-dimensional pores spanning only a few angstroms in size in two-dimensional materials such as graphene are some of the most promising systems for designing ion–ion selective membranes. However, the key challenge in the field is that so far a crack-free macroscopic graphene membrane for ion–ion separation has not been realized. Further, methods to tune the pores in the Å-regime to achieve a large ion–ion selectivity from the graphene pore have not been realized. Herein, we report an Å-scale pore size tuning tool for single layer graphene, which incorporates a high density of ion–ion selective pores between 3.5 and 8.5 Å while minimizing the nonselective pores above 10 Å. These pores impose a strong confinement for ions, which results in extremely high selectivity from centimeter-scale porous graphene between monovalent and bivalent ions and near complete blockage of ions with the hydration diameter, DH, greater than 9.0 Å. The ion diffusion study reveals the presence of an energy barrier corresponding to partial dehydration of ions with the barrier increasing with DH. We observe a reversal of K+/Li+ selectivity at elevated temperature and attribute this to the relative size of the dehydrated ions. These results underscore the promise of porous two-dimensional materials for solute–solute separation when Å-scale pores can be incorporated in a precise manner.