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  Redox chemistry of CaMnO3 and Ca0.8Sr0.2MnO3 oxygen storage perovskites

Bulfin, B., Vieten, J., Starr, D. E., Azarpira, A., Zachäus, C., Hävecker, M., et al. (2017). Redox chemistry of CaMnO3 and Ca0.8Sr0.2MnO3 oxygen storage perovskites. Journal of Materials Chemistry A, 2017(5), 7912-7919. doi:10.1039/c7ta00822h.

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 Creators:
Bulfin, Brandon1, Author
Vieten, J.1, Author
Starr, D. E.2, Author
Azarpira, A2, Author
Zachäus, C.2, Author
Hävecker, Michael3, Author              
Skorupska, Katarzyna3, Author              
Schmücker, M.4, Author
Roeb, M.1, Author
Sattler, C.1, Author
Affiliations:
1Institute of Solar Research, German Aerospace Center, 51147 Cologne, Germany , ou_persistent22              
2Institute of Solar Fuels, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, Germany, ou_persistent22              
3Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, ou_24023              
4Institute of Materials Research, German Aerospace Center 51147, 51147 Cologne, Germany, ou_persistent22              

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 Abstract: Perovskite oxides CaMnO3 and Ca0.8Sr0.2MnO3 show continuous non-stoichiometry over a range of temperatures and oxygen partial pressures. In this work a thermobalance equipped with an oxygen pump was used to measure the equilibrium non-stoichiometry of both materials for temperatures in the range 400–1200 °C and oxygen partial pressures in the range 1–10−5 bar. Analysis of the data showed that Ca0.8Sr0.2MnO3 has a lower enthalpy of reduction and thus can be more easily reduced. The strontium added sample was also robust against a phase transition that was seen in CaMnO3 at high temperatures. A statistical thermodynamic model of the system suggests that the defects form clusters of the form Image (Mn´MnVöMn´)x. The oxidation kinetics were also investigated with Ca0.8Sr0.2MnO3 showing faster kinetics and maintaining activity at lower temperatures. Overall, Ca0.8Sr0.2MnO3 shows very promising properties for redox applications, including gravimetric oxygen storage up to 4% by mass, high stability and rapid reversibility, with re-oxidation in less than 1 min at 400 °C. Finally, the redox chemistry of Ca0.8Sr0.2MnO3 was also investigated using in situ X-ray photoelectron spectroscopy and near-edge X-ray absorption measurements at near ambient pressure in oxygen atmospheres.

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Language(s): eng - English
 Dates: 2017-01-242017-03-192017-03-202017-05-07
 Publication Status: Published in print
 Pages: 8
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/c7ta00822h
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Title: Journal of Materials Chemistry A
  Abbreviation : J. Mater. Chem. A
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: 8 Volume / Issue: 2017 (5) Sequence Number: - Start / End Page: 7912 - 7919 Identifier: ISSN: 2050-7488
CoNE: https://pure.mpg.de/cone/journals/resource/2050-7488