Issue 13, 2018

A structural study of Ruddlesden–Popper phases Sr3−xYx(Fe1.25Ni0.75)O7−δ with x ≤ 0.75 by neutron powder diffraction and EXAFS/XANES spectroscopy

Abstract

The structures of Ruddlesden–Popper n = 2 member phases Sr3−xYxFe1.25Ni0.75O7−δ with 0 ≤ x ≤ 0.75 have been investigated using neutron powder diffraction and K-edge Fe and Ni EXAFS/XANES spectroscopy in order to gain information about the evolution of the oxygen vacancy distribution and Fe/Ni oxidation state with x. Both samples prepared at 1300 °C under a flow of N2(g), with δ = 1.41–1.00, and samples subsequently annealed in air at 900 °C, with δ = 0.44–0.59, were characterized. The as-prepared x = 0.75 phase has δ = 1, the O1 atom site is vacant, and the Fe3+/Ni2+ ions have a square pyramidal coordination. With decreasing x the O3 occupancy decreases nearly linearly to 81% for x = 0, while the O1 occupancy increases from 0 for x = 0.4 to 33% for x = 0. The air-annealed x = 0.75 sample has a δ value of 0.59 and the Fe3+/Fe4+/Ni2+/Ni3+ ions have both square pyramidal and octahedral coordination. With decreasing x, the δ value decreases to 0.45 for x = 0, implying an increase in the oxidation states of Fe/Ni ions. EXAFS/XANES data show that for the as-prepared samples the coordination changes are predominantly for Ni2+ ions and that the air-annealed samples contain both Fe3+/Fe4+ and Ni2+/Ni3+ ions.

Graphical abstract: A structural study of Ruddlesden–Popper phases Sr3−xYx(Fe1.25Ni0.75)O7−δ with x ≤ 0.75 by neutron powder diffraction and EXAFS/XANES spectroscopy

Supplementary files

Article information

Article type
Paper
Submitted
11 अगस्त 2017
Accepted
29 सितम्बर 2017
First published
17 अक्तूबर 2017
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. A, 2018,6, 5313-5323

A structural study of Ruddlesden–Popper phases Sr3−xYx(Fe1.25Ni0.75)O7−δ with x ≤ 0.75 by neutron powder diffraction and EXAFS/XANES spectroscopy

J. Grins, D. Wardecki, K. Jansson, S. Carlson, J. J. Biendicho and G. Svensson, J. Mater. Chem. A, 2018, 6, 5313 DOI: 10.1039/C7TA07113B

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