Theoretical Understanding of Mechanisms of Proton Exchange Membranes Made of 2D Crystals with Ultrahigh Selectivity.

Recent reports on proton conduction across pristine graphene and hexagonal boron nitride (h-BN) provide a new avenue for the design of proton exchange membranes. The uniform pores formed by the electron clouds of two-dimensional (2D) crystals can effectively block the undesired transportation of other species thus ultrahigh selectivity can be achieved. With the aid of first-principles calculations, we investigate the proton conduction process across six kinds of intact 2D crystals, namely graphene, h-BN, β12 boron sheet, χ3 boron sheet, phosphorene, and silicene. To clarify the proton conduction mechanism, three proton penetration modes are proposed: dissociation-penetration, adsorption-penetration, and direct penetration. Based on our calculation results, for graphene and h-BN without atomic defects, they are unlikely to provide sufficient proton conductivity at room temperature when no bias potential is applied. By contrast, the β12 boron sheet, χ3 boron sheets, and silicene exhibit relatively lower proton penetration energy barriers, making them prospective candidates for future proton exchange membrane applications.