Abstract
DFT calculations using the PBE-D3 level of theory were conducted on the C24 and MC23 (M = V, Mn, Ru, Pd, Rh and Au) clusters in order to determine their stability and electronic and magnetic properties. The interaction of the N2O molecule with the above clusters has also been examined in order to assess their adsorption and catalytic properties. The results show that the reactivity of the C24 fullerene was greatly improved after doping with a TM atom, and the metal atom which was replaced the carbon atom in the pure C24 fullerene is considered as the most favorable site to adsorb and dissociate the N2O molecule. The molecular adsorption of the N2O on the surface of the MC23 clusters from its oxygen atom was found to be less energetically favorable than by nitrogen atom, and the calculated adsorption energies (Eads) are in the range of - 6.5 to - 24.7 kcal mol-1. The N2O adsorption on the metal site of the clusters could also lead to the dissociation of the N2O into O* and N2 molecule with adsorption energies which vary from - 2.3 to - 86.8 kcal mol-1. The mechanism of the N2O dissociation on the clusters surface was studied, and the activation energies for each system were calculated in order to find the most catalytically active clusters in the N2O decomposition. The results indicate that the activation energies of the VC23 and MnC23 clusters are much lower than those obtained for the other clusters, reflecting high catalytic activity of the two clusters in the N2O decomposition reaction compared to the other studied clusters. The values of Eac of the reaction over the VC23 and MnC23 cluster are 9.3 and 7.9 kcal mol-1, respectively, indicating that both clusters could be employed as greatly active and efficient nanocatalysts for the N2O decomposition reaction.
Associative and Dissociative Adsorption of N2O Molecule Over C24 Fullerene Doped With V, Mn, Ru, Pd and Rh: A DFT Investigation
