Gap Opening in Double-Sided Highly Hydrogenated Free-Standing Graphene

Conversion of free-standing graphene into pure graphane-where each C atom is sp3bound to a hydrogen atom-has not been achieved so far, in spite of numerous experimental attempts. Here, we obtain an unprecedented level of hydrogenation (?90% of sp3bonds) by exposing fully free-standing nanoporous samples-constituted by a single to a few veils of smoothly rippled graphene-to atomic hydrogen in ultrahigh vacuum. Such a controlled hydrogenation of high-quality and high-specific-area samples converts the original conductive graphene into a wide gap semiconductor, with the valence band maximum (VBM) ~3.5 eV below the Fermi level, as monitored by photoemission spectromicroscopy and confirmed by theoretical predictions. In fact, the calculated band structure unequivocally identifies the achievement of a stable, double-sided fully hydrogenated configuration, with gap opening and no trace of ?states, in excellent agreement with the experimental results. © 2022 American Chemical Society. All rights reserved.