Migration of lattice oxygen during chemical looping dry reforming of methane with Ca2Fe2O5/Zr0.5Ce0.5O2 oxygen carrier

Abstract

Ca2Fe2O5/Zr0.5Ce0.5O2 exhibits excellent reactivity in chemical looping dry reforming of methane. The migration of lattice oxygen is crucial to the cyclic stability of oxygen carrier, but the lattice oxygen migration in Ca2Fe2O5/Zr0.5Ce0.5O2 were not extensively explored. This work explored the lattice oxygen migration of Ca2Fe2O5/Zr0.5Ce0.5O2 during redox process. During the reduction process, the lattice oxygen reacted with the hydrogen radical, resulting in the decrease of lattice oxygen content and the increase of oxygen vacancy. As the lattice oxygen released, the spatial structure of Ca2Fe2O5 was destroyed and transferred into Fe8Ca8O20 with oxygen defects due to lattice distortion. The exothermic reaction between H2 and Ca2Fe2O5 promoted the formation of FeH with hexagonal close-packed structure. After reduction for 160 min, the unstable FeH completely converted into FeC with stable structure and the complete reduction was reached. As for the oxidation process, Fe and CaO reacted with the oxygen radical to form Ca2Fe2O5, leading to the complete recovery of lattice oxygen within 40 min. However, crystalline phase transformation could lead to the spatial structure instability and sintering after multiple redox cycles. Overall, the migration of oxygen during redox process is clarified in detail, providing a reference for improving the cyclic stability of Ca2Fe2O5/Zr0.5Ce0.5O2.