Activation in the rate of oxygen release of Sr(0.8)Ca(0.2)FeO(3−δ) through removal of secondary surface species with thermal treatment in a CO(2)-free atmosphere

We elucidate the underlying cause of a commonly observed increase in the rate of oxygen release of an oxygen carrier with redox cycling (here specifically for the perovskite Sr(0.8)Ca(0.2)FeO(3−δ)) in chemical looping applications. This phenomenon is often referred to as activation. To this end we probe the evolution of the structure and surface elemental composition of the oxygen carrier with redox cycling by both textural and morphological characterization techniques (N(2) physisorption, microscopy, X-ray powder diffraction and X-ray absorption spectroscopy). We observe no appreciable changes in the surface area, pore volume and morphology of the sample during the activation period. X-ray powder diffraction and X-ray absorption spectroscopy analysis (at the Fe and Sr K-edges) of the material before and after redox cycles do not show significant differences, implying that the bulk (average and local) structure of the perovskite is largely unaltered upon cycling. The analysis of the surface of the perovskite via X-ray photoelectron and in situ Raman spectroscopy indicates the presence of surface carbonate species in the as-synthesized sample (due to its exposure to air). Yet, such surface carbonates are absent in the activated material, pointing to the removal of carbonates during cycling (in a CO(2)-free atmosphere) as the underlying cause behind activation. Importantly, after activation and a re-exposure to CO(2), surface carbonates re-form and yield a deactivation of the perovskite oxygen carrier, which is often overlooked when using such materials at relatively low temperature (≤500 °C) in chemical looping.