X-ray absorption spectroscopy study of parent misfit-layered cobalt oxide [Sr₂O₂]q}CoO₂
- Laboratory of Inorganic Chemistry, Department of Chemistry, Aalto University, P.O. Box 16100, FI-00076 Aalto (Finland)
- National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China)
Here we present a comprehensive X-ray absorption spectroscopy study carried out at Co-L₂,₃, Co-K, O-K and Sr-K edges for the parent misfit-layered cobalt oxide phase [Sr₂O₂]₀.₅₂CoO₂; comparison is made to another misfit-layered oxide [CoCa₂O₃]₀.₆₂CoO₂ and the perovskite oxide LaCoO₃. A high-quality sample of [Sr₂O₂]₀.₅₂CoO₂ was obtained through ultra-high-pressure synthesis using Sr₃Co₂O₆ and Sr(OH)₂∙8H₂O as starting materials. Different dosages of KClO₃ were mixed with the raw materials as an oxygen source and tested, but it was found that the window for the redox control of [Sr₂O₂]₀.₅₂CoO₂ is rather narrow. From Co-K and Co-L₂,₃ spectra a mixed III/IV valence state is revealed for cobalt in [Sr₂O₂]₀.₅₂}CoO₂, but the average valence value is a little lower than in [CoCa₂O₃]₀.₆₂CoO₂. Then, Sr-K spectrum indicates that the [Sr₂O₂] double-layer block in [Sr₂O₂]₀.₅₂CoO₂ clearly deviates from the cubic SrO rock-salt structure, suggesting a more complicated coordination environment for strontium. This together with a somewhat low Co-valence value and the fact that the phase formation of [Sr₂O₂]₀.₅₂CoO₂ required the presence of Sr(OH)₂∙8H₂O in the high-pressure synthesis suggest that the [Sr₂O₂] block contains ---OH groups, i.e. [Sr₂(O,OH)₂]₀.₅₂CoO₂. - Graphical abstract: [Sr₂O₂]₀.₅₂CoO₂ obtained through high-pressure synthesis is a parent of misfit-layered cobalt oxides, such as [CoCa₂O₃]₀.₆₂CoO₂ or [MmA₂O2+m]qCoO₂ in general. Our comprehensive X-ray absorption spectroscopy study shows that both [Sr₂O₂]₀.₅₂CoO₂ and [CoCa₂O₃]₀.₆₂CoO₂ possess mixed III/IV valence cobalt, but the average Co-valence is a little lower in the former. This is tentatively believed to be due to OH--- groups replacing part of O²⁻ ions in the [Sr₂O₂] layer block. Highlights: • [Sr₂O₂]₀.₅₂CoO₂ is a parent of misfit-layered cobalt oxides. • It is obtained by ultra-high-pressure synthesis from Sr₃Co₂O₆, Sr(OH)₂∙6H₂O and KClO₃. • Co-K and Co---L XANES spectra reveal lower than expected Co-valence value. • Sr-K XANES spectrum indicates that the [Sr₂O₂] block is not of simple rock-salt structure. • This block most probably contains ---OH--- groups, i.e. [Sr₂(O,OH)₂]₀.₅₂CoO₂.
- OSTI ID:
- 22306308
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. 202; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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