No abstract

The attachment of H to the full set of transition metal (TM) adatoms supported on graphene is studied by using density functional theory. Methodology validation calculations on the interactions of H with benzene and graphene show that any of the vdW corrections under study, the Grimme D2, D3, D3 with Becke-Jonson damping (D3BJ), and Tkatchenko-Scheffler methods, applied on the PBE functional, are similarly accurate in describing such subtle interactions, with an accuracy of almost 2 kJ mol compared to experiments. The PBE-D3 results show that H physisorbs on especially stable d or d TMs. In other 5d metals, and the rightmost 3d and 4d ones, H dissociates, and only for Y, Mn, Fe, and Zr the H binds strongly enough for its storage in the so-called Kubas mode, where the H bond is sensibly elongated. Other metals (Co, Ni, Ru, Rh and Pd) feature also an elongated Kubas mode, interesting as well for H storage. Sc and Ti display a Kubas modes especially suited, given their lightness, for meeting the gravimetric requirements. The H interactions with TM adatoms imply a TM → H charge transfer, although the magnetic moment of the system tends to remain intact, except for the early 5d TMs, where the unpaired electron transfer seems to be associated with the H bond breakage.