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Reversible Phase Transformations in Novel Ce-Substituted Perovskite Oxide Composites for Solar Thermochemical Redox Splitting of CO2


Naik, J Madhusudhan; Ritter, Clemens; Bulfin, Brendan; Steinfeld, Aldo; Erni, Rolf; Patzke, Greta R (2021). Reversible Phase Transformations in Novel Ce-Substituted Perovskite Oxide Composites for Solar Thermochemical Redox Splitting of CO2. Advanced Energy Materials, 11(16):2003532.

Abstract

Thermochemical splitting of CO2 and H2O via two-step metal oxide redox cycles offers a promising approach to produce solar fuels. Perovskite-type oxides with the general formula ABO3 have recently gained attention as an attractive redox material alternative to the state-of-the-art ceria, due to their high structural and thermodynamic tunability. A novel Ce-substituted lanthanum strontium manganite perovskite-oxide composite, La3+0.48Sr2+0.52(Ce4+0.06Mn3+0.79)O2.55 (LSC25M75) is introduced, aiming to bridge the gap between ceria and perovskite oxide-based materials by overcoming their individual thermodynamic constraints. Thermochemical CO2 splitting redox cyclability of LSC25M75 evaluated with a thermogravimetric analyzer and an infrared furnace reactor over 100 consecutive redox cycles demonstrates a twofold higher conversion extent to CO than one of the best Mn-based perovskite oxides, La0.60Sr0.40MnO3. Based on complementary in situ high temperature neutron, synchrotron X-ray, and electron diffraction experiments, unprecedented structural and mechanistic insight is obtained into thermochemical perovskite oxide materials. A novel CO2 splitting reaction mechanism is presented, involving reversible temperature induced phase transitions from the n = 1 Ruddlesden–Popper phase (Sr1.10La0.64Ce0.26)MnO3.88 (I4/mmm, K2NiF4-type) at reduction temperature (1350 °C) to the n = 2 Ruddlesden–Popper phase (Sr2.60La0.22Ce0.18)Mn2O6.6 (I4/mmm, Sr3Ti2O7-type) at re-oxidation temperature (1000 °C) after the CO2 splitting step.

Abstract

Thermochemical splitting of CO2 and H2O via two-step metal oxide redox cycles offers a promising approach to produce solar fuels. Perovskite-type oxides with the general formula ABO3 have recently gained attention as an attractive redox material alternative to the state-of-the-art ceria, due to their high structural and thermodynamic tunability. A novel Ce-substituted lanthanum strontium manganite perovskite-oxide composite, La3+0.48Sr2+0.52(Ce4+0.06Mn3+0.79)O2.55 (LSC25M75) is introduced, aiming to bridge the gap between ceria and perovskite oxide-based materials by overcoming their individual thermodynamic constraints. Thermochemical CO2 splitting redox cyclability of LSC25M75 evaluated with a thermogravimetric analyzer and an infrared furnace reactor over 100 consecutive redox cycles demonstrates a twofold higher conversion extent to CO than one of the best Mn-based perovskite oxides, La0.60Sr0.40MnO3. Based on complementary in situ high temperature neutron, synchrotron X-ray, and electron diffraction experiments, unprecedented structural and mechanistic insight is obtained into thermochemical perovskite oxide materials. A novel CO2 splitting reaction mechanism is presented, involving reversible temperature induced phase transitions from the n = 1 Ruddlesden–Popper phase (Sr1.10La0.64Ce0.26)MnO3.88 (I4/mmm, K2NiF4-type) at reduction temperature (1350 °C) to the n = 2 Ruddlesden–Popper phase (Sr2.60La0.22Ce0.18)Mn2O6.6 (I4/mmm, Sr3Ti2O7-type) at re-oxidation temperature (1000 °C) after the CO2 splitting step.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Renewable Energy, Sustainability and the Environment
Physical Sciences > General Materials Science
Uncontrolled Keywords:General Materials Science, Renewable Energy, Sustainability and the Environment
Language:English
Date:1 April 2021
Deposited On:08 Feb 2022 15:19
Last Modified:28 Jan 2024 02:43
Publisher:Wiley-VCH Verlag
ISSN:1614-6832
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/aenm.202003532
  • Content: Published Version
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)