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
- Saskatchewan
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.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Organization:
- FOREIGN
- OSTI ID:
- 1048966
- Journal Information:
- J. Alloy Comp., Vol. 537, Issue 10, 2012; ISSN 0925-8388
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Double perovskite Sr{sub 2}FeMoO{sub 6-x}N{sub x} (x=0.3, 1.0) oxynitrides with anionic ordering
Sr3Fe5/4Mo3/4O6.9, an n = 2 Ruddlesen-Popper Phase: Synthesis and Properties