Dinitrosyl formation as an intermediate stage of the reduction of NO in the presence of MoO3

Abstract

We present first-principles calculations in the framework of density-functional theory and the pseudopotential approach, aiming to model the intermediate stages of the reduction of NO in the presence of MoO3(010). In particular, we study the formation of dinitrosyl, which proves to be an important intermediate stage in the catalytic reduction. We find that the replacement of an oxygen of MoO3 by NO is energetically favorable, and that the system lowers further its energy by the formation of (NO)2. Moreover, the geometry and charge distribution for the adsorbed dinitrosyl indicates a metal-oxide mediated coupling between the two nitrogen and the two oxygen atoms. We discuss the mechanisms for the dinitrosyl formation and the role of the oxide in the reaction.