A new approach to the mechanism of heterogeneously catalysed reactions: the oxydehydrogenation of ammonia at a Cu(111) surface

Abstract

The oxydehydrogenation of ammonia at a Cu(111) surface is a highly efficient process at 295 K, with the selectivity sensitive to the dioxygen-ammonia ratio. However, there is no evidence from either XPS or HREELS for surface oxygen being present during the reaction and, in effect, catalysis occurs at a clean Cu(111) surface. The rate of NH _x (a) formation is indistinguishable from the rate of the dissociative chemisorption of oxygen at close to zero coverage suggesting that the reactive oxygen species are the hot transients O-(s). The chemisorbed oxygen overlayer, the O^2-(a)-like species are, by comparison, unreactive. The reaction is, therefore, not characteristic of either Eley-Rideal or Langmuir-Hinshelwood mechanisms but involves the interaction of rapidly diffusing ammonia molecules and hot transient O-(s)-like species. Models for this type of reaction have been discussed previously, while very recent studies by scanning tunnelling microscopy have provided further evidence for such oxygen transients.