Evidence of A–B site cooperation in the EuFeO3 perovskite from 151Eu and 57Fe Mössbauer spectroscopy, EXAFS, and toluene catalytic oxidation

• Nearest oxygen surroundings and an oxygen depletion of the higher neighboring shells of Eu by EXAFS.
• Local defects in the proximity of the Eu cations during the reaction from Mössbauer parameters.
• 151Eu and 57Fe Mössbauer spectroscopy suggested a cooperative effect of the cations.
• A relatively strong ionicity of Fe–O chemical bonds from XPS.
• Catalytic oxidation of toluene occurring preferentially through a Volkenstein mechanism.

EuFeO3 perovskite was considered as a case study of the cooperative effects of the rare earth and transition metal elements in the total catalytic oxidation of aromatic hydrocarbons. For this purpose, a EuFeO3 perovskite was prepared using the citrate route. Extensive characterization was performed via ex situ and in situ methods. EXAFS revealed that oxygen vacancies are formed in the nearest neighborhood of Fe and next-nearest neighborhood of Eu. Combining 151Eu and 57Fe Mössbauer experiments also suggested local oxygen defects in the proximity of the Eu cations during the reaction, as well as cooperative electron delocalization effects between Eu and Fe. XPS has shown the +3 oxidation state of both Eu and Fe cations and the relatively strong ionicity of the Fe–O chemical bonds, as suggested by the weakened 2p3/2 satellite in the Fe2p spectrum. A systematic change of this satellite with the A cation in AFeO3 perovskites was also discussed. The thermal treatment of the catalyst at 623 K, in air or toluene, was accompanied by a partial reduction of Fe and a partial oxidation of Eu, respectively. The interaction between the two elements appeared to be influenced mainly by the temperature and only slightly by the sample environment during further treatments. Catalytic oxidation of toluene on this perovskite led only to the production of carbon dioxide and water with no side-product formation from partial oxidation reactions. All the characterization and catalytic results preferably agree with a Volkenstein mechanism.

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