Two-step model for reduction reaction of ultrathin nickel oxide by hydrogen

Abstract

Nickel (Ni) is used as a catalyst for nitric oxide decomposition and ammonia production but it is easily oxidized and deactivated. Clarification of the reduction process of oxidized Ni is essential to promote more efficient use of Ni catalysts. In this study, the reduction processes of ultrathin oxide films formed on Ni(111) surfaces by thermal oxidation under vacuum and a hydrogen atmosphere were investigated by in situ time-resolved photoelectron spectroscopy. On the basis of these results, we propose a reaction model for the reduction of Ni oxide films. Our results show that the reduction of Ni oxide films on heating under vacuum does not yield a clean Ni(111) surface owing to formation of a residual stable suboxide structure on the Ni(111) surface. Conversely, in a hydrogen atmosphere of 1 × 10−5 Pa, the Ni oxide was completely reduced and a clean Ni(111) surface was obtained, even when heating below 300 °C. The reduction in a hydrogen atmosphere was best described by a two-step reaction model. The rate of the first step depends on the reduction temperature, and the rate of the second step depends on the H2 pressure. The rate-limiting process for the first step is surface precipitation of O atoms and that of the second step is dissociation of H2 molecules.