Towards advanced structural analysis of iron oxide clusters on the surface of γ-Al2O3 using EXAFS

Abstract Iron oxide centres are structurally investigated in 0.1% Fe/γ-Al 2 O 3 , which is known as highly active catalyst, for instance in the oxidation of CO. The sample was characterised by using X-ray absorption spectroscopy (XAS) in terms of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), Mossbauer spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). These analyses evidenced high dispersion of the iron oxide entities without significant presence of bulk-like aggregates associated with the low Fe content of the catalyst. A library of structural models of Al 2 O 3 -supported surface Fe was created as input for EXAFS fitting. Additionally, several model structures of Fe substituting Al ions in bulk γ-Al 2 O 3 were created with optimised geometry based on density-functional theory (DFT) calculations. From EXAFS refinement of the best 8 out of 24 models, it was found that the trivalent Fe ions are coordinated by 4–5 oxygen atoms and are located on octahedral lattice sites of the exposed surfaces of γ-Al 2 O 3 . These iron oxide species exist mainly as a mixture of monomeric and binuclear species and due to the low concentration represent suitable model systems as alternative to single crystal systems for structure-function relationships.