Sr3Fe2O7−δ has not only high structural stability under severe reduction conditions, but also high oxygen storage capacity due to topotactic oxygen intake/release.
The compounds of
SrFe1–x
Ti
x
O3−δ with a robust
perovskite structure are synthesized by Ti substitution for Fe sites
in SrFeO3−δ, and they display improved oxygen
storage properties and chemical stability in a CO2 atmosphere.
The oxygen storage rate of SrFe0.8Ti0.2O3−δ is over 5 times faster than that of SrFeO3−δ. Further, in the presence of CO2, SrFe1–x
Ti
x
O3−δ with x ≥
0.2 maintains its oxygen storage property, whereas, for x ≤ 0.1, the oxygen release rate drastically deteriorates due
to the formation of SrCO3. The perovskite structures (space
group I4/mmm) of SrFe1–x
TixO3−δ (x ≥ 0.2) are preserved even after reduction treatment
under a H2 atmosphere at 773 K. In contrast, the material
with x ≤ 0.1 undergoes a phase transformation
from perovskite (I4/mmm) to brownmillerite
structures (Ima2), and the latter easily reacts with
CO2 to form a large amount of SrCO3 on the surface.
Thus, the robust perovskite structure maintains its original framework
despite the reduction treatment, resulting in improved oxygen storage
rate as well as the CO2 resistance.
This study proves that a small amount of Pd loading (1 wt%) on SrFeO can dramatically enhance the oxygen-storage properties of SrFeO. The topotactic oxygen intake and release between SrFeO and SrFeO takes place in response to gas switching between an O flow and H flow, regardless of the presence or absence of Pd loading. The effect of Pd loading is significant for the oxygen-release process under H atmosphere; that is, highly dispersed Pd metal nanoparticles sized less than 1 nm formed on Pd/SrFeO to promote H dissociation, resulting in the improvement of the oxygen-release temperature and rate. Pd/SrFeO with a layered perovskite structure has a higher oxygen-release property at lower temperature than Pd/SrFeO with a perovskite phase without the layered structure. These facts indicate that the surface reaction as well as the crystal structure are responsible for the oxide ion mobility in perovskite structure, and also provide guidelines for designing novel oxygen-storage materials.
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