Kinetic and Thermodynamic Enhancement of Low-Temperature Oxygen Release from Strontium Ferrite Perovskites Modified with Ag and CeO2

Harrison, Alexander R. P.; Y. Kwong, Kien Y.; Zheng, Yaoyao; Balkrishna, Abhishek; Dyson, Alice; Marek, Ewa J.

Abstract

The redox behavior of the nonstoichiometric perovskite oxide SrFeO3−δ modified with Ag, CeO2, and Ce was assessed for chemical looping air separation (CLAS) via thermogravimetric analysis and by cyclic release and uptake of O2 in a packed bed reactor. The results demonstrated that the addition of ∼15 wt % Ag at the surface of SrFeO3−δ lowers the temperature of oxygen release in N2 by ∼60 °C (i.e., from 370 °C for bare SrFeO3−δ to 310 °C) and more than triples the amount of oxygen released per CLAS cycle at 500 °C. Impregnation of SrFeO3−δ with Ag increased the concentration of oxygen vacancies at equilibrium, lowering (3 - δ) under all investigated oxygen partial pressures. The addition of CeO2 at the surface or into the bulk of SrFeO3−δ resulted in more modest changes, with a decrease in temperature for O2 release of 20-25 °C as compared to SrFeO3−δ and a moderate increase in oxygen yield per reduction cycle. The apparent kinetic parameters for reduction of SrFeO3−δ, with Ag and CeO2 additives, were determined from the CLAS experiments in a packed bed reactor, giving activation energies and pre-exponential factors of Ea,reduction = 66.3 kJ mol-1 and Areduction = 152 mol s-1 m-3 Pa-1 for SrFeO3−δ impregnated with 10.7 wt % CeO2, 75.7 kJ mol-1 and 623 molO2 s-1 m -3 Pa-1 for SrFeO3−δ mixed with 2.5 wt % CeO2 in the bulk, 29.9 kJ mol-1 and 0.88 molO2 s-1 m-3 Pa-1 for Sr0.95Ce0.05FeO3−δ, and 69.0 kJ mol-1 and 278 molO2 s-1 m-3 Pa-1 for SrFeO3−δ impregnated with 12.7 wt % Ag, respectively. Kinetics for reoxidation were much faster and were assessed for two materials with the slowest oxygen uptake, SrFeO3−δ, giving the activation energy Ea,oxidation = 177.1 kJ mol-1 and pre-exponential factor Aoxidation = 3.40 × 1010 molO2 s-1 m-3 Pa-1, and Sr0.95Ce0.05FeO3−δ, giving the activation energy Ea,oxidation = 64.0 kJ mol-1, and pre-exponential factor Aoxidation = 584 molO2 s-1 m-3 Pa-1.

Citation

Harrison, A. R. P., Y. Kwong, K. Y., Zheng, Y., Balkrishna, A., Dyson, A., & Marek, E. J. (2023). Kinetic and Thermodynamic Enhancement of Low-Temperature Oxygen Release from Strontium Ferrite Perovskites Modified with Ag and CeO2. Energy and Fuels, 37(13), 9487-9499. https://doi.org/10.1021/acs.energyfuels.3c01263

• Journal Article Type: Article
• Acceptance Date: Jun 14, 2023
• Online Publication Date: Jun 14, 2023
• Publication Date: Jul 6, 2023
• Deposit Date: Apr 3, 2024
• Publicly Available Date: Apr 12, 2024
• Electronic ISSN: 0887-0624
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 37
• Issue: 13
• Pages: 9487-9499
• DOI: https://doi.org/10.1021/acs.energyfuels.3c01263
• Public URL: https://nottingham-repository.worktribe.com/output/32757509
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.energyfuels.3c01263