The impact of CeO2 in the Al2O3-20 wt% CeO2 support prepared by the co-precipitation method on the Ir particle size, morphology and oxidation state, and in turn on the deN(2)O catalytic activity (1000 ppm N2O) of supported Ir catalysts were investigated in the absence and presence of excess O-2 (2 vol%) conditions. It was demonstrated that the deN(2)O activity of Ir/Al2O3 is notably suppressed by the presence of oxygen in the feed stream, namely, the N2O conversion at 600 degrees C is declined to 65% in the presence of oxygen as compared to 100% in the absence of oxygen. A similar detrimental catalytic effect was also observed for the Ir/CeO2 solid. On the contrary, the deN(2)O performance of CeO2-modified Ir/Al2O3 catalyst is only slightly affected by the presence of oxygen. An extensive characterization study involving surface texture analysis (N-2 adsorption-desorption at -196 degrees C), temperature-programmed reduction in H-2 (H-2-TPR), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS) and diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption and desorption (CO-DRIFTS) was carried out to gain insight into the origin of the CeO2-induced promotional effect. The characterization results revealed the existence of IrO2 phase (H-2-TPR, XRD, HRTEM, EELS and CO-DRIFTS) as well as of very small isolated particles of Ir on the Al2O3, CeO2 and CeO2-Al2O3 supports (STEM) but to a notably different extent. The coexistence of large IrO2 particles of perfect crystallite structure and very small Ir particles located at the Ir-ceria interface was revealed only in Ir/AlCe. The establishment of a certain Ir delta+/Ir-0 ratio and oxygen vacant sites (V-o) concentration in ceria around very small Ir particles under oxidative reaction conditions seem to largely promote N2O adsorption and subsequent decomposition into N-2 and O-2 over the CeO2-promoted Ir/Al catalyst. In the case of Ir/Al, a different deN(2)O decomposition mechanism occurs, where the site reactivity of Ir delta+/Ir-0 established under oxidizing conditions is reduced significantly. (C) 2016 Elsevier B.V. All rights reserved.