15 June 2017
Source:Materials Chemistry and Physics, Volume 194
Author(s): Ali Shokuhi Rad, Khurshid Ayub
We present here theoretical results on adsorption of two important industrial gases (C2H2 and C2H4) on free Al12N12 and Ni-decorated Al12N12 fullerene-like nanoclusters. Binding energies have been calculated with B3LYP and wB97XD methods of density functional theory. The binding energies were corrected for the basis set superposition error (BSSE) for 6-31G (d,p) basis set. Despite both molecules could be adsorbed on the surface of free Al12N12 with moderate binding energies of ∼ −37 (BSSE corrected: −25.7) kJ/mole for ethylene and ∼−58 (BSSE corrected: 44.6) kJ/mole for acetylene, based on wb97xd functional, however much strong interaction is achieved for Ni-decorated nano-cages over pure Al12N12. Adsorption energy of acetylene varies depending on the position of nickel decoration whereas the adsorption of ethylene is independent of the position of nickel decoration. The adsorption energies for acetylene and ethylene on Al12N12 nano-cage range from −294 to −410 (−202.1 to −281.3, BSSE corrected) kJ/mol. Along with high values of adsorption energy for Ni-decorated Al12N12 nano-cage, we found relatively low interaction distance, and high orbital hybridization upon adsorption of mentioned molecules on the surface Ni-AlN. Results of charge analyses show that upon adsorption of these molecules on free Al12N12, it acts as p-type semiconductor which interestingly, changes to n-type semiconductor when nickel is decorated on its surface.