Ammoxidation of propane to acrylonitrile was examined over a Fe3BiOx/SiO2 sample prepared by thermal decarbonylation of [Et4N][Fe-3(CO)(10)(mu(3)-Bi)] on the surface of mesoporous silica. Catalytic measurements performed at 500 degrees C showed that this sample yields 49% acrylonitrile selectivity at 36% propane conversion when a 5.5%C3H8/30%O-2/11%NH3/He balance reaction mixture was used at a GHSV of 1360 h(-1). HRSTEM, EDS, and XPS measurements indicate that mixed Fe3BiO6 oxide particles less than 2 nm in size were formed on the surface of this material under reaction conditions. A Fe/Bi atomic ratio in these particles is approximately 3:1 and the Fe and Bi ions both are in the +3 oxidation state. A Fe-Bi/SiO2 sample prepared by co-impregnation of individual Fe and Bi salts had very low activity and low selectivity for acylonitrile formation from propane under similar experimental conditions due to larger sizes of particles formed under reaction conditions and enrichment of their surface with Fe. (C) 2015 Elsevier B.V. All rights reserved.