▎ 摘　　要

High selectivity of protons over deuterons transport through one-atom-thick graphene membrane has been demonstrated experimentally, but its fundamental mechanism has been controversially discussed. Proposed hypotheses involve local hydrogenation, but the detailed penetration process has not been rigorously explained. In the present study, based on electron cloud density, transition path selection and corresponding barrier cal-culations, perfect graphene is quasi-impermeable to protons, yet lateral ring chemically bonded protons adjacent hydrogenated hexa-cyclohydride shows the lowest barrier for the penetration of proton. The bridge-flip as a link provides the site for the penetration of the proton through the graphene. The chemically bonded protons slip into C-C to forms a C-H-C bridge bonds, and then flip over the graphene membrane to complete the penetration process.