Porosity in Sr1_xCaxFeO3- oxygen carriers: The role of surface area and pretreatment on storage activity

Perovskite oxides have generated interest as robust, low-temperature oxygen carrier materials for a variety of clean energy applications, including chemical looping gasification and air separations. Methods to improve O2 desorption kinetics are vital to allow these carriers to compete economically with traditional metal oxide carriers or cryogenic separations. Herein, we investigated the cumulative roles that surface area, pretreatment, and elemental composition have on the oxygen storage properties of a state-of-the-art carrier system, Sr1_xCaxFeO3-delta (x = 0.20, 0.25, 0.30) synthesized using multiple methods. Porous materials synthesized by the Pechini, or citrate, method had their surface area controlled using the synthesis temperature. The high surface area of the Sr0.7Ca0.3FeO3-delta materials is most beneficial at low operating temperatures, such as 350 and 400 degrees C, as their reduction rates are twice as fast as those obtained with their bulk counterparts. These effects are observed at higher operating temperatures and within a single composition, but temperature tunability using variable Ca2+ substitution in the Sr1_xCaxFeO3-delta overshadows the improvements gained from higher surface areas. Additionally, we establish that pretreatment in N2 at an elevated temperature is necessary to enhance kinetics further. For maximum efficiency, pretreatment at the synthesis temperature is suggested for the Pechini method-synthesized systems, whereas 800 degrees C is adequate for bulk materials.