Abstract
In this study, perovskite-type La0.7Ca0.3Co0.3Fe0.6M0.1O3–δ (M = Cu, Zn) powders were synthesized using a scalable reverse co-precipitation method, presenting them as novel materials for oxygen transport membranes. The comprehensive study covered various aspects including oxygen permeability, crystal structure, conductivity, morphology, CO2 tolerance, and long-term regenerative durability with a focus on phase structure and composition. The membrane La0.7Ca0.3Co0.3Fe0.6Zn0.1O3–δ exhibited high oxygen permeation fluxes, reaching up to 0.88 and 0.64 mL·min−1·cm−2 under air/He and air/CO2 gradients at 1173 K, respectively. After 1600 h of CO2 exposure, the perovskite structure remained intact, showcasing superior CO2 resistance. A combination of first principles simulations and experimental measurements was employed to deepen the understanding of Cu/Zn substitution effects on the structure, oxygen vacancy formation, and transport behavior of the membranes. These findings underscore the potential of this highly CO2-tolerant membrane for applications in high-temperature oxygen separation. The enhanced insights into the oxygen transport mechanism contribute to the advancement of next-generation membrane materials.
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