Abstract
The oxidation of NO was explored on a mixed Fe+Cr oxide surface using temperature-programmed desorption (TPD). NO desorbs from (Fe,Cr)3O4(111) in two main peaks at 220 and 370K, with a third minor peak at ∼315K. O2 TPD shows similar behavior. The strongly and weakly bound molecules are due to adsorption at Fe2+ and Fe3+ sites, respectively, and the minor states are assigned to Cr3+ sites. No thermal decomposition was detected for adsorbed NO, whereas ∼10% of the adsorbed O2 dissociated at Fe2+ sites. NO reacts with preadsorbed O2 to produce surface nitrate, as confirmed by isotopic labeling, which decomposes in TPD at 425K. Atomically adsorbed O does not react with NO. Fe3+ and Cr3+ sites do not appear to participate in NO oxidation. Irradiation of adsorbed NO or NO+O2 with 460nm light results predominantly in photodesorption, which limits the extent of possible surface photoreactions.
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