Journal
CRYSTAL GROWTH & DESIGN
Volume 15, Issue 9, Pages 4237-4247Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.5b00525
Keywords
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Funding
- ENS Lyon
- ANR [ANR-09-BLAN-0187-01]
- Fonds Europeen de Developpement Regional (FEDER)
- CNRS
- Region Nord Pas-de-Calais
- Ministere de l'Education Nationale de l'Enseignement Superieur et de la Recherche
- Conseil Regional du Nord-Pas de Calais
- European Regional Development Fund (ERDF)
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
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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 alpha-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 observed a systematic full ordering between Fe ions and vacancies (V-Fe) that denote unprecedented easy in-plane metal diffusion driven by the Fe2+/Fe3+ redox. Besides the discovery of a diversity of original depleted triangular infinity{Fe2/3+' O-2-x(6)} topologies, we propose a unified model correlating the x Fe-removal and the experimental Fe/V-Fe ordering into periodic one-dimensional motifs paving the layers, gaining insights into predictive crystal chemistry of complex low dimensional oxides. Increasing the x values led to a progressive change of the materials from 2D ferromagnets (Fe2+) to 2D ferrimagnets (Fe2/3+) to antiferromagnets for x = 2/3 (Fe3+).
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