LAUSR

Abstract The influences of transition metal Ni and nonmetal N co-substitution for partial metal Mg and nonmetal B elements on the hydrogen dissociation behavior of Mg(BH4)2 (100) surface are investigated using the first-principles calculations in this work. The calculations results indicate that the co-substitution of Ni + N is a feasible and effective method for reducing the thermal stability and hydrogen dissociation energy, which helps to enhance the dehydrogenation performance of Mg(BH4)2 accordingly. The Ni + N co-substitution causes the hydrogen dissociation energy of the (100) surface to reduce from 2.267 to 1.720 eV/atom because of the co-existence of dual anionic groups NiH6 and NH2. The co-existence breaks stable BH4 group into unstable BH3 or BH2 groups. Besides, the first H atom dissociated from the borohydride (100) surface is shifted from the initial B H bond to a weaker Ni H bond with a longer bond length. The shift suggests that the hydrogen dissociation process on the (100) surface is facilitated by the Ni + N co-substitution.