???????Selective penetration mechanism of hydrogen isotope through graphene membrane

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.

Automated summary

The high selectivity of protons over deuterons in one-atom-thick graphene membranes has been experimentally demonstrated, but the underlying mechanism remains controversial. In this study, it is found that proton penetration through perfect graphene is nearly impermeable, while the lowest barrier is observed for lateral ring chemically bonded protons adjacent to hydrogenated hexacyclohydrides. The penetration process involves slip of chemically bonded protons into C-C to form C-H-C bridge bonds, followed by flipping over the graphene membrane.