Synthesis, structure and catalytic properties of Fe-substituted barium hexaaluminates

A sol–gel method using Ba and Al isopropylates and iron nitrate has been used to synthesise barium hexaaluminate partially substituted with iron. After calcination under oxygen at 1200°C the -alumina structure was obtained. Formation of the mixed BaFe_xAl_12-xO₁₉ phase occurred for x=1–4. XRD measurements showed a good crystallinity of the structure and expansion of unit cell parameters due to the presence of larger Fe³⁺ ions substituting Al³⁺ ones in octahedral sites only. Mössbauer spectroscopy revealed that Fe³⁺ ions are present in four different octahedral sites slightly distorted. Catalytic activity in methane combustion showed that an optimum was obtained for solid containing 2 Fe ions per unit cell: the increase of the amount of introduced iron was counterbalanced by the decrease of specific surface area. Intrinsic activities have been calculated for the four solids in both the fresh and aged states. It is observed that increasing iron content increases relative activities in the same ratio as the populations of iron located in two sites as deduced from Mössbauer spectroscopy. It is then tentatively assumed that activity is attributed to octahedrally coordinated Fe³⁺ ions in some specific sites.