Investigation of Perovskite Structures as Oxygen-Exchange Redox Materials for Hydrogen Production from Thermochemical Two-Step Water-Splitting Cycles

This study addresses the synthesis, characterization, and thermochemical redox performance evaluation of perovskites and parent structures (Ruddlesden–Popper phases) as a class of oxygen-exchange materials for hydrogen generation via solar two-step water splitting. The investigated materials are La_xSr_1–xMO₃ (M = Mn, Co, Fe), Ba_xSr_1–x(Co,Fe)­O₃, LaSrCoO₄, and LaSrFeO₄, also used as mixed ionic-electronic conductors in fuel cells. Temperature-programmed reduction, powder X-ray diffraction, and thermogravimetric analysis were used to obtain a preliminary assessment of these materials performances. Most of the perovskites studied here stand out by larger thermal reduction capabilities and oxygen vacancies formation at modest temperatures in the range 1000–1400 °C when compared with reference nonstoichiometric compounds such as spinel ferrites or fluorite-structured ceria-based materials. In addition, these materials offer noticeable access to metallic valence transitions during reoxidation in steam atmosphere that are not available in stoichiometric oxides. The promising behaviors characterized here are discussed in regard to the crystal chemistry of the perovskite and parent phases.