Non-Stoichiometric Redox Active Perovskite Materials for Solar Thermochemical Fuel Production: A Review

Due to the requirement to develop carbon-free energy, solar energy conversion into chemical energy carriers is a promising solution. Thermochemical fuel production cycles are particularly interesting because they can convert carbon dioxide or water into CO or H2 with concentrated solar energy as a high-temperature process heat source. This process further valorizes and upgrades carbon dioxide into valuable and storable fuels. Development of redox active catalysts is the key challenge for the success of thermochemical cycles for solar-driven H2O and CO2 splitting. Ultimately, the achievement of economically viable solar fuel production relies on increasing the attainable solar-to-fuel energy conversion efficiency. This necessitates the discovery of novel redox-active and thermally-stable materials able to split H2O and CO2 with both high-fuel productivities and chemical conversion rates. Perovskites have recently emerged as promising reactive materials for this application as they feature high non-stoichiometric oxygen exchange capacities and diffusion rates while maintaining their crystallographic structure during cycling over a wide range of operating conditions and reduction extents. This paper provides an overview of the best performing perovskite formulations considered in recent studies, with special focus on their non-stoichiometry extent, their ability to produce solar fuel with high yield and performance stability, and the different methods developed to study the reaction kinetics.