Density functional theory study of the adsorption of acetone on the pure and transition metal doped (TiO2)38 clusters

The adsorption of acetone on the pure and V-, Cr-, Mn-, Fe-, Co-, Ni-doped (TiO2)(38) clusters was studied by the density functional theory (DFT) with the generalized gradient approximation (GGA) developed by the Perdew and Wang (PW91) exchange-correlation functional. The structural studies indicate that acetone adsorption prefers to take place on the top site with the symmetry plane of acetone perpendicular to the bridge oxygen rows. The properties of transition metal doped clusters were also been discussed. The calculated substitution energies show that the 3d transition metal doping is getting harder with the increase of atomic number of the doping atom. Furthermore, the adsorption of acetone on the doped clusters was investigated. The adsorption energies of Mn-, Co- and Ni-doped clusters are obviously larger than that of pure TiO2 cluster. The Mn, Co or Ni doping leads to acetone activation mainly on the C = O group, but the Fe doping may reduce the activity. (C) 2015 Elsevier Ltd. All rights reserved.