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.
Thermochemical splitting of H 2 O and CO 2 applying redox materials constitutes a sustainable option for synthetic fuel production and CO 2 valorization. It consists of two-step process based on the creation of oxygen vacancies in non-stoichiometric oxides during solar-driven thermal reduction, followed by the material re-oxidation with H 2 O and/or CO 2 to generate syngas (H 2 /CO), the building block for a wide variety of synthetic hydrocarbon fuels. In this work, a monolithic solar reactor was designed and tested integrating reticulated porous ceria (open-cell foams) heated by concentrated solar energy. The influence of various operating parameters on the thermochemical reactor performance was investigated. Increasing the temperature or decreasing the pressure in the reduction step was found to enhance the maximum reduction extent reached by the redox material (CeO 2- ), thereby improving the fuel production capacity. In addition, a decrease of the oxidation temperature led to higher fuel production rate, despite an increase of the temperature swing between the reduction and oxidation steps. Increasing the oxidant concentration also sharply enhanced the oxidation rate. Peak CO production rate approaching 10 mL/min/g was achieved with ceria foams (exhibiting micron-sized grains forming an interconnected macroporous network within the struts) during their reoxidation upon free cooling with pure CO 2 stream (after reduction at 1400°C), thus strongly outperforming (by a factor of about x8) the previous maximum values reported to date. This result was attributed to the fine and stable granular microstructure of the reticulated ceria foams. The solar reactor reliability and robustness during hightemperature two-step redox cycling were demonstrated with an average cycle production of 5.1 mL/g of H 2 and CO, and peak solar-to-fuel efficiencies above 8%. The highly reactive reticulated foams with 10 and 20 ppi (pore per inch) were cycled for about 69 hours (51 cycles) of continuous on-sun operation without any decrease in performance, thus evidencing their noteworthy thermochemical and microstructural stability.
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