4 research outputs found
Chlorine Insertion Promoting Iron Reduction in BaāFe Hexagonal Perovskites: Effect on the Structural and Magnetic Properties
BaFeCl<sub>0.13(2)</sub>O<sub>2.48(2)</sub> has been synthesized and studied. A proper tuning of the synthetic
route has been designed to stabilize this compound as a single phase.
The thermal stability and evolution, along with the magnetic and structural
properties are reported here. The crystal structure has been refined
from neutron powder diffraction data, and it is of the type (hhchc)<sub>2</sub>-10H. It is stable up to a temperature of 900 Ā°C, where
the composition reads BaFeCl<sub>0.13(2)</sub>O<sub>2.34(2)</sub>.
The study by electron microscopy shows that the crystal structure
suffers no changes in the whole BaFeCl<sub>0.13(1)</sub>O<sub>3ā<i>y</i></sub> (2.34 ā¤ 3 ā <i>y</i> ā¤
2.48) compositional range. Refinement of the magnetic structure shows
that the Fe is antiferromagneticaly ordered, with the magnetic moment
parallel to the <i>ab</i> plane of the hexagonal structure.
At higher temperature, a nonreversible phase transition into a (hchc)-4H
structure type takes place with overall composition BaFeCl<sub>0.13(1)</sub>O<sub>2.26(1)</sub>. Microstructural characterization shows that,
in some crystals, this phase intergrows with a seemingly cubic related
phase. Differences between these two crystalline phases reside in
the chlorine content, which keeps constant through the phase transition
for the former and disappears for the latter
Direct Atomic Observation in Powdered 4H-Ba<sub>0.8</sub>Sr<sub>0.2</sub>Mn<sub>0.4</sub>Fe<sub>0.6</sub>O<sub>2.7</sub>
A new hexagonal polytype in the BaMn<sub>1ā<i>x</i></sub>Fe<sub><i>x</i></sub>O<sub>3āĪ“</sub> system has been stabilized. Powdered Ba<sub>0.8</sub>Sr<sub>0.2</sub>Mn<sup>IV</sup><sub>0.4</sub>Fe<sup>III</sup><sub>0.6</sub>O<sub>2.70</sub> crystallizes in the 4H hexagonal polytype (space group <i>P</i>6<sub>3</sub>/<i>mmc</i>) according to X-ray
diffraction. HAADF images and chemical maps with atomic resolution
have been obtained by combining Cs-corrected electron microscopy and
EELS spectroscopy. The structure is formed by dimers of face-sharing
octahedra linked by corners. EELS data show a random distribution
of the transition metals ions identified by Fe and Mn-L2,3 chemical
maps. A systematic difference in contrast observed in the OāK
signal mapping suggests that anion deficiency is randomly located
along the hexagonal layers in agreement with ND data. The magnetic
structure consists of ferromagnetic sheets with the magnetic moments
aligned along the <i>x</i>-axis and coupled antiferromagnetically
along the <i>c</i>-axis
SrMnO<sub>3</sub> Thermochromic Behavior Governed by Size-Dependent Structural Distortions
The influence of particle size in
both the structure and thermochromic
behavior of 4H-SrMnO<sub>3</sub> related perovskite is described.
Microsized SrMnO<sub>3</sub> suffers a structural transition from
hexagonal (<i>P</i>6<sub>3</sub>/<i>mmc</i>) to
orthorhombic (<i>C</i>222<sub>1</sub>) symmetry at temperature
close to 340 K. The orthorhombic distortion is due to the tilting
of the corner-sharing Mn<sub>2</sub>O<sub>9</sub> units building the
4H structural type. When temperature decreases, the distortion becomes
sharper reaching its maximal degree at ā¼125 K. These structural
changes promote the modification of the electronic structure of orthorhombic
SrMnO<sub>3</sub> phase originating the observed color change. nano-SrMnO<sub>3</sub> adopts the ideal 4H hexagonal structure at room temperature,
the orthorhombic distortion being only detected at temperature below
170 K. A decrease in the orthorhombic distortion degree, compared
to that observed in the microsample, may be the reason why a color
change is not observed at low temperature (77 K)
Critical Influence of Redox Pretreatments on the CO Oxidation Activity of BaFeO<sub>3āĪ“</sub> Perovskites: An in-Depth Atomic-Scale Analysis by Aberration-Corrected and in Situ Diffraction Techniques
A BaFeO<sub>3āĪ“</sub> (Ī“ ā 0.22) perovskite
was prepared by a solāgel method and essayed as a catalyst
in the CO oxidation reaction. BaFeO<sub>3āĪ“</sub> (0.22
ā¤ Ī“ ā¤ 0.42) depicts a 6H perovskite hexagonal
structural type with Fe in both III and IV oxidation states and oxygen
stoichiometry accommodated by a random distribution of anionic vacancies.
The perovskite with the highest oxygen content, BaFeO<sub>2.78</sub>, proved to be more active than its lanthanide-based counterparts,
LnFeO<sub>3</sub> (Ln = La, Sm, Nd). Removal of the lattice oxygen
detected in both temperature-programmed oxidation (TPO) and reduction
(TPR) experiments at around 500 K and which leads to the complete
reduction of Fe<sup>4+</sup> to Fe<sup>3+</sup>, i.e. to BeFeO<sub>2.5</sub>, significantly decreases the catalytic activity, especially
in the low-temperature range. The analysis of thermogravimetric experiments
performed under oxygen and of TPR studies run under CO clearly support
the involvement of lattice oxygen in the CO oxidation on these Ba-Fe
perovskites, even at the lowest temperatures. Atomically resolved
images and chemical maps obtained using different aberration-corrected
scanning transmission electron microscopy techniques, as well as some
in situ type experiments, have provided a clear picture of the accommodation
of oxygen nonstoichiometry in these materials. This atomic-scale view
has revealed details of both the cation and anion sublattices of the
different perovskites that have allowed us to identify the structural
origin of the oxygen species most likely responsible for the low-temperature
CO oxidation activity