期刊
CHEMISTRY OF MATERIALS
卷 35, 期 15, 页码 5895-5902出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.3c00693
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The synthesis and structural properties of Sr0.4Ba0.6Mn0.94Ti0.06O3-δ with polycrystalline cubic and hexagonal structures were investigated using in situ neutron diffraction and thermogravimetric analysis. The experiments replicated and explained the key synthesis processes involved in switching between different reducing and oxidizing atmospheres, transforming a hexagonal phase into an oxygen-deficient cubic perovskite phase. The partial substitution of large Ba ions at the Sr sites enhanced strains and created wide channels, facilitating rapid oxidation of the oxygen-deficient cubic phase, resulting in phase separation between oxygen-rich and oxygen-poor phases.
The synthesis and structural properties of polycrystallinecubicand hexagonal Sr0.4Ba0.6Mn0.94Ti0.06O3-& delta; have been investigated usinga combination of in situ neutron diffraction and thermogravimetricanalysis. The experiments were conceived to replicate and explainkey synthesis processes involving switching between different reducingand oxidizing atmospheres designed to transform a hexagonal phaseinto an oxygen-deficient cubic perovskite phase in which Mn ions arein their trivalent oxidation state. Hydrogen reduction of the hexagonalphase first produces a heavily oxygen-deficient hexagonal phase precedingto full decomposition of the material. Remarkable reversible propertiesof the parent hexagonal structure are observed with the phase recoveredwithin minutes by reoxidation of the material after it was decomposedin hydrogen-containing atmospheres. The partial substitution of largeBa ions at the Sr sites enhances the strains and creates wide channels,enabling the rapid oxidation of the oxygen-deficient cubic phase.The fast oxygen intake results in a phase separation between oxygen-richand oxygen-poor phases with no evidence for any vacancy-ordered superstructuresas those previously seen in the parent Ba- and Ti-free SrMnO3-& delta; system.
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