Substrate-Mediated Borophane Polymorphs through Hydrogenation of Two-Dimensional Boron Sheets

The two-dimensional boron monolayer (borophene) stands out from the two-dimensional atomic layered materials due to its structural flexibility and tunable electronic and mechanical properties from a large number of allotropic materials. The stability of pristine borophene polymorphs could possibly be improved via hydrogenation with atomic hydrogen (referred to as borophane). However, the precise adsorption structures and the underlying mechanism are still elusive. Employing first-principles calculations, we demonstrate the optimal configurations of freestanding borophanes and the ones grown on metallic substrates. For freestanding borophenes, the energetically favored hydrogen adsorption sites are sensitive to the polymorphs and corresponding coordination numbers of boron atoms. With various metal substrates, the hydrogenation configurations of borophenes are modulated significantly, attributed to the overlap between B p z and H s orbitals. These findings provide a deep insight into the hydrogenating borophenes and facilitate the stabilization of two-dimensional boron polymorphs by engineering hydrogen adsorption sites and concentrations.