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

[Image: see text] Conversion of free-standing graphene into pure graphane—where each C atom is sp(3) bound 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 sp(3) bonds) 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 π states, in excellent agreement with the experimental results.