Density functional calculations of hydrogen adsorption on boron nanotubes and boron sheets

Hydrogen adsorption on the recently discovered boron nanotubes, BNTs, and on boron sheets is investigated by density functional calculations. Both molecular physisorption and dissociative atomic chemisorption are considered. The geometric and electronic structures of BNTs and boron sheets have been elucidated. These two novel boron structures present buckled surfaces with alternating up and down rows of B atoms, with a large buckling height of about 0.8 Å. The buckled structures are about 0.20 eV/atom more stable than the corresponding flat ones. However, the helicity of some BNTs does not allow for the formation of alternating up and down B rows in the surface and, therefore, these nanotubes have flat surfaces. The buckled and flat nanostructures have different geometric and bonding characteristics, but both are metallic. Molecular hydrogen physisorption energies are about 30-60 meV/molecule on boron sheets and nanotubes, actually lower than in graphene and in carbon nanotubes and far from the energies of 300-400 meV/molecule necessary for efficient hydrogen storage at room temperature and moderate pressures for onboard automotive applications. Chemisorption binding energies on BNTs are about 2.4-2.9 eV/H atom, similar to the ones obtained in CNTs. Finally, the energy barrier from molecular physisorption to dissociative chemisorption of hydrogen is about 1.0 eV /molecule. Therefore, the calculations predict physisorption as the leading adsorption mechanism of hydrogen at moderate temperatures and pressures. The expected hydrogen adsorption capacity of these novel B materials is even smaller than that of CNTs.