Issue 2, 2022

Crystal field-induced lattice expansion upon reversible oxygen uptake/release in YbMnxFe2−xO4

Abstract

We successfully form the solid solutions YbMnxFe2−xO4 for x = 0.25, 0.50, 0.75, and 1.0 in order to study the mechanism of oxygen release and uptake as a function of Mn substitution. High-resolution synchrotron X-ray diffraction (SXRD) reveals that YbMnxFe2−xO4 readily take up oxygen and undergo a structural transition from R[3 with combining macron]m to P[3 with combining macron] to become hyper-stoichiometric YbMnxFe2−xO4.5, which demonstrates their potential as oxygen storage materials. X-ray photoelectron spectroscopy (XPS) implies that Mn2+ and Fe2+ oxidize to Mn3+ and Fe3+ after the structural transition. Thermogravimetric analysis (TGA) and in situ SXRD measurements at elevated temperatures show that O2 uptake commences at 200 °C but the structural transition does not until 300 °C. The structural evolution under methane and air, monitored by in situ SXRD, implies promising reversibility and structural stability in this series. By performing structural refinements, we find that Mn substitution causes the lattice parameters, a and c, to evolve in a diametric fashion. Strong anisotropic expansion of the lattice occurs in all the reduced phases YbMnxFe2−xO4 (R[3 with combining macron]m) and oxidized phases YbMnxFe2−xO4.5 (P[3 with combining macron]). We propose that this phenomenon can be attributed to d-electron filling and crystal field effects for the Mn and Fe cations.

Graphical abstract: Crystal field-induced lattice expansion upon reversible oxygen uptake/release in YbMnxFe2−xO4

Supplementary files

Article information

Article type
Paper
Submitted
07 Sep 2021
Accepted
17 Nov 2021
First published
18 Nov 2021
This article is Open Access
Creative Commons BY-NC license

Mater. Adv., 2022,3, 1087-1100

Crystal field-induced lattice expansion upon reversible oxygen uptake/release in YbMnxFe2−xO4

T. Li, R. Jayathilake, L. Balisetty, Y. Zhang, B. Wilfong, T. J. Diethrich and E. E. Rodriguez, Mater. Adv., 2022, 3, 1087 DOI: 10.1039/D1MA00822F

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