Redox Performance and Optimization of the Chemical Composition of Lanthanum–Strontium–Manganese-Based Perovskite Oxide for Two-Step Thermochemical CO 2 Splitting.

The effects of substitution at the A- and B sites on the redox performance of a series of lanthanum–strontium–manganese (LSM)-based perovskite oxides (Z = Ni, Co, and Mg) were studied for application in a two-step thermochemical CO₂ splitting cycle to produce liquid fuel from synthesis gas using concentrated solar radiation as the proposed energy source and CO₂ recovered from the atmosphere as the prospective chemical source. The redox reactivity, stoichiometry of oxygen/CO production, and optimum chemical composition of Ni-, Co-, and Mg-substituted LSM perovskites were investigated to enhance oxygen/CO productivity. Furthermore, the long-term thermal stabilities and thermochemical repeatabilities of the oxides were evaluated and compared with previous data. The valence changes in the constituent ionic species of the perovskite oxides were studied and evaluated by X-ray photoelectron spectroscopy (XPS) for each step of the thermochemical cycle. From the perspectives of high redox reactivity, stoichiometric oxygen/CO production, and thermally stable repeatability in long-term thermochemical cycling, Ni_0.20-, Co_0.35-, and Mg_0.125-substituted La_0.7Sr_0.3Mn perovskite oxides are the most promising materials among the LSM perovskite oxides for two-step thermochemical CO₂ splitting, showing CO productivities of 387–533 μmol/g and time-averaged CO productivities of 12.9–18.0 μmol/(min·g) compared with those of LSM perovskites reported in the literature. [ABSTRACT FROM AUTHOR]