Reversible Exsolution of Nanometric Fe2O3 Particles in BaFe2-x(PO4)2 (0 ≤ x ≤ 2/3):The Logic of Vacancy Ordering in Novel Metal-Depleted Two-Dimensional Lattices
- CNRS-UMR
We show here that the exsolution of Fe2+ ions out of two-dimensional (2D) honeycomb layers of BaFe2(PO4)2 into iron-deficient BaFe2–x(PO4)2 phases and nanometric α-Fe2O3 (typically 50 nm diameter at the grain surface) is efficient and reversible until x = 2/3 in mild oxidizing/reducing conditions. It corresponds to the renewable conversion of 12 wt % of the initial mass into iron oxide. After analyzing single crystal X-ray diffraction data of intermediate members x = 2/7, x = 1/3, x = 1/2 and the ultimate Fe-depleted x = 2/3 term, we then observed a systematic full ordering between Fe ions and vacancies (VFe) that denote unprecedented easy in-plane metal diffusion driven by the Fe2+/Fe3+ redox. Besides the discovery of a diversity of original depleted triangular ∞{Fe2/3+2–xO6} topologies, we propose a unified model correlating the x Fe-removal and the experimental Fe/VFe ordering into periodic one-dimensional motifs paving the layers, gaining insights into predictive crystahemistry of complex low dimensional oxides. When we increased the x values it led to a progressive change of the materials from 2D ferromagnets (Fe2+) to 2D ferrimagnets (Fe2/3+) to antiferromagnets for x = 2/3 (Fe3+).
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Organization:
- FOREIGNOTHER
- OSTI ID:
- 1225095
- Journal Information:
- Crystal Growth and Design, Vol. 15, Issue 9; ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- ENGLISH
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