Proton penetration mechanism and selective hydrogen isotope separation through two-dimensional biphenylene

Hydrogen isotope separation is of prime significance in various scientific and industrial applications. Nevertheless, the existing technologies are often expensive and energy demanding. Two-dimensional carbon materials are regarded as promising candidates for cost-effective separation of different hydrogen isotopes. Herein, based on theoretical calculations, we have systematically investigated the proton penetration mechanism and the associated isotope separation behavior through two-dimensional biphenylene, a novel graphene allotrope. The unique non-uniform rings with different sizes in the biphenylene layer resemble the topological defects of graphene, serving as proton transmission channels. We found that a proton can readily pass through biphenylene with a low energy barrier in some specific patterns. Furthermore, large kinetic isotope effect ratios for proton–deuteron (13.58) and proton–triton (53.10) were observed in an aqueous environment. We thus conclude that biphenylene would be a potential carbon material used for hydrogen isotope separation. This subtle exploitation of the natural structural specificity of biphenylene provides new insight into the search for materials for hydrogen isotope separation.