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Ceria-modified Pt/Al₂O₃ catalyst has been commonly prepared by the impregnation of platinum on ceria-modified alumina and widely applied in the chemical industry and automotive industry. The in situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS), and thermogravimetric (TG) analysis techniques were employed to investigate the typical mechanisms of the bis(ethanolammonium)hexahydroxyplatinate(IV) and cerium nitrate decomposition catalyzed by Pt^δ+ species for the facile synthesis of CeO₂-Pt/Al₂O₃ catalyst. It was found that Pt⁴⁺-catalyzed decomposition of cerium nitrate leads to the higher dispersity of ceria and forming more active oxygen species, on the basis of X-ray diffraction (XRD) and H₂ temperature-programmed reduction (H₂-TPR) results. The in situ activity measurements were also performed to investigate the reaction mechanisms and the specific activities for the catalytic CO, NO, C₃H₆ and C₃H₈ co-oxidation. The results indicate that undesirable N₂O by-product is formed by the selective catalytic reduction (SCR) of NO by C₃H₆ below 350 °C. The cerium addition effectively improves the activity of catalytic oxidation, but exhibits an increased N₂O yield, due to the increased reducibility.