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

Zhao, Kangning; Lee, Wan-Chi; Rezaei, Mojtaba; Chi, Heng-Yu; Li, Shaoxian; Villalobos, Luis Francisco; Hsu, Kuang-Jung; Zhang, Yuyang et al. · ACS Nano · 2024

basic_science · Level V

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Abstract

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, <i>D</i><sub><i>H</i></sub>, 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 <i>D</i><sub><i>H</i></sub>. We observe a reversal of K<sup>+</sup>/Li<sup>+</sup> 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.