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@ARTICLE{Maity:278659,
author = {Maity, A. and Dutta, R. and Penkala, B. and Ceretti, M. and
Letrouit-Lebranchu, A. and Chernyshov, D. and Perichon, A.
and Piovano, A. and Bossak, A. and Meven, Martin and Paulus,
W.},
title = {{S}olid-state reactivity explored in situ by synchrotron
radiation on single crystals: from {S}r{F}e{O} 2.5 to
{S}r{F}e{O} 3 via electrochemical oxygen intercalation},
journal = {Journal of physics / D},
volume = {48},
number = {50},
issn = {1361-6463},
address = {Bristol},
publisher = {IOP Publ.},
reportid = {FZJ-2015-06984},
pages = {504004 -},
year = {2015},
note = {"final draft post referee" wird nicht zur Verfügung
gestellt.},
abstract = {In this study we demonstrate the feasibility of following
up a chemical reaction by single crystal x-ray (synchrotron)
diffraction under operando conditions, carried out in a
specially designed electrochemical cell mounted on the BM01A
at the European Synchrotron Radiation Facility (ESRF). We
investigated in detail the electrochemical oxidation of
SrFeO2.5 to SrFeO3 on a spherical single crystal of 70 μm
diameter by in situ diffraction at an ambient temperature.
Complete data sets were obtained by scanning the whole
reciprocal space using a 2M Pilatus detector, resulting in
3600 frames with a resolution of 0.1° per data set, each
obtained in 18 min. The crystal was mounted in a specially
designed electrochemical cell with 1N KOH used as the
electrolyte. During the electrochemical oxidation, the
reaction proceeds following the phase sequence
SrFeO2.5/SrFeO2.75/SrFeO2.875/SrFeO3, structurally
accompanied by establishing a complex series of long-range
oxygen vacancy ordering, which gets instantly organized at
ambient temperature. The topotactic reaction pathway is
discussed in terms of the evolution of the twin domain
structure. The formation of SrFeO2.875 is accompanied by the
formation of diffuse streaks along the [1 0 0]-direction of
the perovskite cell, reaching high d-spacings. The diffuse
streaks are discussed and are thought to originate from a
modified twin structure induced by the SrFeO2.75 to
SrFeO2.875 transition, and the associated changes in the
domain structure, developed during the oxygen intercalation.
We equally analysed and discussed in detail the twin
structure of all the title compounds. We confirm the ground
state of SrFeO2.5 is able to adopt the Imma space group
symmetry, showing stacking faults of the tetrahedral layers
along the stacking axis of the brownmillerite unit cell,
indicated by the 1D diffuse rods. We showed that in situ
single crystal diffraction has huge potential in the study
of nonstoichiometric compounds under operando conditions, in
order to obtain structural information i.e. about diffuse
scattering, and microstructural information related to
domain effects such as twinning—information far beyond
that which powder diffraction methods allow us to obtain.},
cin = {JCNS (München) ; Jülich Centre for Neutron Science JCNS
(München) ; JCNS-FRM-II / JCNS-2},
ddc = {530},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-2-20110106},
pnm = {6G15 - FRM II / MLZ (POF3-6G15) / 6G4 - Jülich Centre for
Neutron Research (JCNS) (POF3-623)},
pid = {G:(DE-HGF)POF3-6G15 / G:(DE-HGF)POF3-6G4},
experiment = {EXP:(DE-MLZ)NOSPEC-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000368443100006},
doi = {10.1088/0022-3727/48/50/504004},
url = {https://juser.fz-juelich.de/record/278659},
}