Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 118, Issue 34, Pages 19768-19777Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp5037603
Keywords
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Funding
- Divisions of Materials and Engineering Sciences [DE-AC04-94AL85000]
- Chemical Sciences, Geosciences, and Biosciences of the Office of Basic Energy Sciences, U.S. Department of Energy [DE-AC02-05CH11231]
- Spanish Ministry of Science and Innovation [MAT2012-38045-C04-01]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
- Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and Materials Sciences Division of the U.S. Department of Energy [DE-AC02-05CH11231]
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We study where and how hematite (alpha-Fe2O3) nucleates and grows during the oxidation of magnetite(100) single crystals. Hematite inclusions grow along < 110 > directions of the magnetite (Fe3O4), leading to a biaxial array of hematite slabs in an electrically conducting matrix of magnetite. The slab arrays form in both bulk single crystals and thin films of magnetite. Atomic force microscopy reveals that the surface growth of magnetite that accompanies hematite formation is faster adjacent to the hematite slabs. In situ X-ray photoelectron and X-ray absorption spectroscopies at 600 degrees C in an oxygen environment reveal that the conversion of the Fe2+ in magnetite to Fe3+ in hematite occurs without the formation of the metastable phase maghemite (gamma-Fe2O3). We offer an explanation of why Fe3O4(100) oxidizes faster than Fe3O4(111).
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