Ni adsorption on Al12P12 nano-cage: A DFT study

Density functional theory (DFT) calculations have been performed to evaluate the geometries and electronic properties of nickel decorated aluminum phosphide (AlP) nano-cages. At the lowest coverage of our system (one Ni per one Al12P12), four adsorption sites (P1eP4) of Ni on AlP nano-cage are studied. Band structures, binding energies, total density of states, natural bond orbital (NBO) charges, and electron density differences of Ni-adsorbed Al12P12 nano-cages are studied for each adsorption site. We found that three orientations (P1, P2, and P3) show electron transfer from the Ni to Al12P12 whereas one orientation (P4) has reverse direction of electron transfer. The adsorption energies of Ni on AlP nano-cage are -136.7, -108.5, -102.7, and -99.4 kcal mol(-1) for P4, P3, P1 and P2, respectively. Formation of new AleNi and PeNi bonds is observed concomitant with the dissociation of some Al-P bonds of the nanocage. (C) 2016 Elsevier B. V. All rights reserved.