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Title: An investigation of the Fe and Mo oxidation states in Sr[subscript 2]Fe[subscript 2]Mo[subscript x]O[subscript 6] (0.25 [less than] x [less than] 1.0) double perovskites by X-ray absorption spectroscopy

Abstract

Sr{sub 2}FeMoO{sub 6} double perovskite systems are widely studied because of their interesting and technologically relevant physical properties. Sr{sub 2}FeMoO{sub 6} is just a single composition in the Sr{sub 2}Fe{sub 2-x}Mo{sub x}O{sub 6} solid-solution, and it is important to understand how the composition impacts the transition-metal valence states. Variations in the lattice parameters of these materials were studied using powder X-ray diffraction and it was found that a large change in the lattice constant occurs between Sr{sub 2}Fe{sub 1.50}Mo{sub 0.50}O{sub 6} and Sr{sub 2}Fe{sub 1.35}Mo{sub 0.65}O{sub 6} that likely coincides with a transition from a cubic to a tetragonal unit cell, in agreement with previous studies. Fe K- and Mo K-edge X-ray absorption near-edge spectra were also collected to investigate how the oxidation state and coordination environment change with composition. When the Mo content is low, Fe adopts a 3+ oxidation state and Mo adopts a 6+ oxidation state. As the Mo content is increased, the Fe and Mo cations are both partially reduced, resulting in a mixture of Fe{sup 3+} and Fe{sup 2+} and Mo{sup 5+} and Mo{sup 6+}. The reduction of the metal centers apparently drives the change in unit cell. The influence of preparation method on themore » oxidation states of Fe and Mo was also investigated by annealing the materials under vacuum. The results reported here show that the oxidation states of Fe and Mo are strongly impacted by both composition and preparation method, which may account for the wide variety of oxidation state and magnetic properties that have been reported previously.« less

Authors:
;  [1]
  1. (Saskatchewan)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1048966
Resource Type:
Journal Article
Journal Name:
J. Alloy Comp.
Additional Journal Information:
Journal Volume: 537; Journal Issue: 10, 2012; Journal ID: ISSN 0925-8388
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; ABSORPTION; ABSORPTION SPECTROSCOPY; ANNEALING; CATIONS; LATTICE PARAMETERS; MAGNETIC PROPERTIES; MIXTURES; PEROVSKITE; PEROVSKITES; PHYSICAL PROPERTIES; SPECTRA; VALENCE; X-RAY DIFFRACTION

Citation Formats

Hayes, John R., and Grosvenor, Andrew P. An investigation of the Fe and Mo oxidation states in Sr[subscript 2]Fe[subscript 2]Mo[subscript x]O[subscript 6] (0.25 [less than] x [less than] 1.0) double perovskites by X-ray absorption spectroscopy. United States: N. p., 2012. Web. doi:10.1016/j.jallcom.2012.05.056.
Hayes, John R., & Grosvenor, Andrew P. An investigation of the Fe and Mo oxidation states in Sr[subscript 2]Fe[subscript 2]Mo[subscript x]O[subscript 6] (0.25 [less than] x [less than] 1.0) double perovskites by X-ray absorption spectroscopy. United States. doi:10.1016/j.jallcom.2012.05.056.
Hayes, John R., and Grosvenor, Andrew P. Thu . "An investigation of the Fe and Mo oxidation states in Sr[subscript 2]Fe[subscript 2]Mo[subscript x]O[subscript 6] (0.25 [less than] x [less than] 1.0) double perovskites by X-ray absorption spectroscopy". United States. doi:10.1016/j.jallcom.2012.05.056.
@article{osti_1048966,
title = {An investigation of the Fe and Mo oxidation states in Sr[subscript 2]Fe[subscript 2]Mo[subscript x]O[subscript 6] (0.25 [less than] x [less than] 1.0) double perovskites by X-ray absorption spectroscopy},
author = {Hayes, John R. and Grosvenor, Andrew P.},
abstractNote = {Sr{sub 2}FeMoO{sub 6} double perovskite systems are widely studied because of their interesting and technologically relevant physical properties. Sr{sub 2}FeMoO{sub 6} is just a single composition in the Sr{sub 2}Fe{sub 2-x}Mo{sub x}O{sub 6} solid-solution, and it is important to understand how the composition impacts the transition-metal valence states. Variations in the lattice parameters of these materials were studied using powder X-ray diffraction and it was found that a large change in the lattice constant occurs between Sr{sub 2}Fe{sub 1.50}Mo{sub 0.50}O{sub 6} and Sr{sub 2}Fe{sub 1.35}Mo{sub 0.65}O{sub 6} that likely coincides with a transition from a cubic to a tetragonal unit cell, in agreement with previous studies. Fe K- and Mo K-edge X-ray absorption near-edge spectra were also collected to investigate how the oxidation state and coordination environment change with composition. When the Mo content is low, Fe adopts a 3+ oxidation state and Mo adopts a 6+ oxidation state. As the Mo content is increased, the Fe and Mo cations are both partially reduced, resulting in a mixture of Fe{sup 3+} and Fe{sup 2+} and Mo{sup 5+} and Mo{sup 6+}. The reduction of the metal centers apparently drives the change in unit cell. The influence of preparation method on the oxidation states of Fe and Mo was also investigated by annealing the materials under vacuum. The results reported here show that the oxidation states of Fe and Mo are strongly impacted by both composition and preparation method, which may account for the wide variety of oxidation state and magnetic properties that have been reported previously.},
doi = {10.1016/j.jallcom.2012.05.056},
journal = {J. Alloy Comp.},
issn = {0925-8388},
number = 10, 2012,
volume = 537,
place = {United States},
year = {2012},
month = {10}
}