Oxygen nonstoichiometry in (Ca2CoO3)0.62(CoO2): a combined experimental and computational study

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dc.contributor.authorSchrade, Men_AU
dc.contributor.authorCasolo, Sen_AU
dc.contributor.authorGraham, PJen_AU
dc.contributor.authorUlrich, Cen_AU
dc.contributor.authorLi, Sen_AU
dc.contributor.authorLøvvik, OMen_AU
dc.contributor.authorFinstad, TGen_AU
dc.contributor.authorNorby, Ten_AU
dc.date.accessioned2016-10-26T00:08:24Zen_AU
dc.date.available2016-10-26T00:08:24Zen_AU
dc.date.issued2014-07-28en_AU
dc.date.statistics2016-10-26en_AU
dc.description.abstractThe oxygen nonstoichiometry in the misfit calcium cobaltite (Ca2CoO3)0.62(CoO2) has been studied experimentally and by density functional theory (DFT) calculations. The standard oxidation enthalpy ΔH0Ox of oxygen deficient (Ca2CoO3)0.62(CoO2) was measured directly using simultaneous thermogravimetry and differential scanning calorimetry. ΔH0Ox was found to be in agreement with the prediction from a previously published defect chemical model based on purely thermogravimetrical analysis. A series of samples with different oxygen vacancy concentration was prepared by annealing in air, followed by rapid quenching. Room-temperature Raman spectroscopy showed a sharp mode at 700 cm–1 decreasing in intensity with increasing vacancy concentration. We discuss this observation as evidence for oxygen vacancies being preferably formed within the central layer of the Ca2CoO3 subsystem. DFT calculations demonstrated that the calculated electronic structure is sensitive to the chosen model of the crystal structure. Still, for all investigated models, the standard formation enthalpy of oxygen vacancies within the Ca2CoO3 moiety was much lower than that for a site within the CoO2 layer, in agreement with the presented experimental data. © 2014, American Chemical Society.en_AU
dc.identifier.citationSchrade, M., Casolo, S., Graham, P. J., Ulrich, C., Li, S., Løvvik, O. M., Finstaf, T. G., & Norby, T. (2014). Oxygen nonstoichiometry in (Ca2CoO3)0.62(CoO2): a combined experimental and computational study. The Journal of Physical Chemistry C, 118(33), 18899-18907. doi:10.1021/jp5048437en_AU
dc.identifier.govdoc7424en_AU
dc.identifier.issn1932-7455en_AU
dc.identifier.issue33en_AU
dc.identifier.journaltitleThe Journal of Physical Chemistry Cen_AU
dc.identifier.pagination18899-18907en_AU
dc.identifier.urihttp://dx.doi.org/10.1021/jp5048437en_AU
dc.identifier.urihttp://apo.ansto.gov.au/dspace/handle/10238/7902en_AU
dc.identifier.volume118en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectOxygenen_AU
dc.subjectOxidationen_AU
dc.subjectCalorimetryen_AU
dc.subjectRaman spectroscopyen_AU
dc.subjectDataen_AU
dc.subjectTemperature rangeen_AU
dc.titleOxygen nonstoichiometry in (Ca2CoO3)0.62(CoO2): a combined experimental and computational studyen_AU
dc.typeJournal Articleen_AU
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