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We investigated, herein, the redox activity of partial substitution of the B-site in a series of lanthanum/strontium-manganese-based (LSM) perovskite oxide, La0.7Sr0.3Mn0.9X0.1O3 for solar two-step thermochemical fuel production using concentrated solar radiation as an energy source. We systematically investigated the effects of partial substitution in LaSrMnO3 in terms of their kinetics behavior, oxygen/CO productivity, thermal reduction/oxidation temperatures. Furthermore, repeatability was evaluated and compared among the samples prepared using the same procedure and studied using the same test method. We observed and evaluated the long-term thermal stability of the redox activity and valence variation of the constituting ionic species of the perovskite in the two-step thermochemical CO2 splitting. From the perspectives of superior activity and long-term repeatability, Ni-, Co-, and Mg-substituted LSM perovskites are promising for thermochemical two-step CO2/H2O splitting to produce synthetic gas.

The heat-discharging kinetics of an iron-substituted Mn2O3/Mn3O4 redox pair subjected to long-term thermal cycling tests using a temperature swing process at high temperatures was investigated for next-generation concentrated solar power plants equipped with thermochemical energy storage. The heat-discharge mode kinetics for long-term thermal-cycled samples have never been reported. Additionally, comparisons of the heat-discharge mode kinetics for both long-term thermal-cycled and as-prepared samples have never been discussed. In terms of the reproducibility and sustainability of thermochemical energy storage, kinetic evaluations of samples with thermally stable morphologies subjected to long-term thermal cycling at high temperatures are important for next-generation solar thermal power plants. For the long-term thermal-cycled sample, the A2 model based on the Avrami–Erofeev reaction describes the discharging mode behavior in a fractional conversion range of 0–0.24, the contracting area (R2) model best fits in a fractional conversion range of 0.24–0.50, and the third-order (F3) model matches in a fractional conversion range of 0.50–0.70. For the as-prepared sample, the power-law (P2) model describes the behavior of the first part of the discharging mode, whereas the Avrami–Erofeev (A4) model best fits the last half of the discharging mode. The predicted theoretical models for both samples were compared with previous kinetic data.

We studied the performance in terms of the long-term cyclic thermal storage and heat-charging kinetics of Fe-substituted manganese oxide for use in thermochemical energy storage at temperatures exceeding 550 °C in a next-generation concentrated solar power system in which a gas stream containing oxygen is used for reversible thermochemical processes. The Fe-substituted Mn2O3 was evaluated from the viewpoint of its microstructural characteristics, thermodynamic phase transitions, and long-term cycling stability. A kinetic analysis of the heat-charging mode was performed at different heating rates to formulate the kinetic equation and describe the reaction mechanism by determining the appropriate reaction model. Finally, the kinetics data for the sample obtained after the long-term cycling test were compared and evaluated with those of the as-prepared sample and kinetic literature data tested under different conditions. For the long-term cycled sample, the Avrami–Erofeev reaction model (An) with n = 2 describes the behavior of the first part of the charging mode, whereas the contracting area (R2) reaction model best fits the last half of the charging mode. For the as-prepared sample, except for the early stage of the charging mode (fractional conversion < 0.2), the contracting volume (R3) reaction model fits the charging mode over a fractional conversion range of 0.2–1.0 and the first-order (F1) reaction model fits in the fractional conversion range of 0.4–1.0. The predicted kinetic equations for both the samples were in good agreement with the experimental kinetic data.