Zooming in on the initial steps of catalytic NO reduction using metal clusters

The study of reactions relevant to heterogeneous catalysis on the surface of well-defined metal clusters with full control over the number of consituent atoms and elemental composition can lead to a detailed insight into the interactions between metal and reactants. We here review experimental and theoretical studies involving the adsorption of NO molecules on mostly rhodium-based clusters under near-thermal conditions in a molecular beam. We show how IR spectrosopic characterization can give information on the binding nature of NO to the clusters for at least the first three NO molecules. The complementary technique of thermal desorption spectrometry reveals at what temperatures multiple NO molecules on the cluster surface desorb or combine to form rhodium oxides followed by N₂ elimination. Variation of the cluster elemental composition can be a powerful method to identify how the propensity of the critical first step of NO dissociation can be increased. The testing of such concepts with atomic detail can be of great help in guiding the choices in rational catalyst design.