O2 activation by AuAg clusters on a defective (100)MgO surface.

In the present work, we discuss the electronic properties of supported dispersed bimetallic clusters with respect to their size, geometry, and Aun/Agm (n + m = 6) composition. We have studied with supercell-density functional theory calculations the role of the charge transfer from the MgO defective support toward the cluster in the activation of O2 by AunAgm clusters. We first considered gas-phase clusters with different atomic compositions; then, we deposited all of them on a pristine (100)MgO surface and finally on a more realistic (100)MgO F-center. We performed a global and unrestricted search of the (cluster + surface) geometry. The Mexican enhanced genetic algorithm has been used to exhaustively explore the potential energy surface. Our results show that O2 activation depends on the Aun/Agm ratio. It has been found that both metals involved play different and important roles toward (a) the actual O2 dissociation and (b) weakening of the oxygen-cluster bond, which, in turn, may promote the possibility of a catalytic process to take place, such as the oxidation process of CO and NOx among others.