Perfect proton selectivity in ion transport through two-dimensional crystals

Defect-free monolayers of graphene and hexagonal boron nitride are surprisingly permeable to thermal protons, despite being completely impenetrable to all gases. It remains untested whether small ions can permeate through the two-dimensional crystals. Here we show that mechanically exfoliated graphene and hexagonal boron nitride exhibit perfect Nernst selectivity such that only protons can permeate through, with no detectable flow of counterions. In the experiments, we use suspended monolayers that have few, if any, atomic-scale defects, as shown by gas permeation tests, and place them to separate reservoirs filled with hydrochloric acid solutions. Protons account for all the electrical current and chloride ions are blocked. This result corroborates the previous conclusion that thermal protons can pierce defect-free two-dimensional crystals. Besides the importance for theoretical developments, our results are also of interest for research on various separation technologies based on two-dimensional materials.