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

Bulfin, Brendan and Vieten, Josua and Starr, D.E. and Azarpira, A. and Zachäus, C. and Hävecker, M. and Skorupska, K. and Schmücker, Martin and Roeb, Martin and Sattler, Christian (2017) Redox chemistry of CaMnO3 and Ca0.8Sr0.2MnO3 oxygen storage perovskites. Journal of Materials Chemistry A, 5, pp. 7912-7919. Royal Society of Chemistry. DOI: 10.1039/C7TA00822H ISSN 2050-7488

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Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/2017/TA/C7TA00822H#!divAbstract

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 ID:c7ta00822h-t1.gif. 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.

Item URL in elib:https://elib.dlr.de/113385/
Document Type:Article
Title:Redox chemistry of CaMnO3 and Ca0.8Sr0.2MnO3 oxygen storage perovskites
Authors:
AuthorsInstitution or Email of AuthorsAuthors ORCID iD
Bulfin, Brendanbrendan.bulfin (at) dlr.deUNSPECIFIED
Vieten, JosuaJosua.Vieten (at) dlr.deUNSPECIFIED
Starr, D.E.Institute of Solar Fuels, Helmholtz-Zentrum Berlin für Materialien und Energie GmbHUNSPECIFIED
Azarpira, A.Institute of Solar Fuels, Helmholtz-Zentrum Berlin für Materialien und Energie GmbHUNSPECIFIED
Zachäus, C.Institute of Solar Fuels, Helmholtz-Zentrum Berlin für Materialien und Energie GmbHUNSPECIFIED
Hävecker, M.Department of Inorganic Chemistry, Fritz Haber Institute of the Max Plank SocietyUNSPECIFIED
Skorupska, K.Department of Inorganic Chemistry, Fritz Haber Institute of the Max Plank SocietyUNSPECIFIED
Schmücker, MartinMartin.Schmuecker (at) dlr.deUNSPECIFIED
Roeb, MartinMartin.Roeb (at) dlr.deUNSPECIFIED
Sattler, ChristianChristian.Sattler (at) dlr.dehttps://orcid.org/0000-0002-4314-1124
Date:April 2017
Journal or Publication Title:Journal of Materials Chemistry A
Refereed publication:Yes
Open Access:No
Gold Open Access:No
In SCOPUS:Yes
In ISI Web of Science:Yes
Volume:5
DOI :10.1039/C7TA00822H
Page Range:pp. 7912-7919
Publisher:Royal Society of Chemistry
ISSN:2050-7488
Status:Published
Keywords:perovskites, redox chemistry,oxygen storage, syncrotron, BESSY
HGF - Research field:Energy
HGF - Program:Renewable Energies
HGF - Program Themes:Solar Fuels
DLR - Research area:Energy
DLR - Program:E SW - Solar and Wind Energy
DLR - Research theme (Project):E - Solar Fuels
Location: Köln-Porz
Institutes and Institutions:Institute of Solar Research > Solar Chemical Engineering
Institute of Materials Research > Structural and Functional ceramics
Deposited By: Sattler, Prof. Dr. Christian
Deposited On:09 Aug 2017 10:44
Last Modified:06 Sep 2019 15:30

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