Journal
SCIENCE
Volume 346, Issue 6214, Pages 1215-1218Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1260556
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Funding
- Austrian Science Fund [P24925-N20, SFB-F41 ViCoM]
- Austrian Science Fund doctoral college SOLIDS4FUN [W1243]
- Vienna University of Technology
- European Research Council advanced grant OxideSurfaces
- Austrian Science Fund (FWF) [P24925, W1243] Funding Source: Austrian Science Fund (FWF)
- Austrian Science Fund (FWF) [P 24925] Funding Source: researchfish
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Iron oxides play an increasingly prominent role in heterogeneous catalysis, hydrogen production, spintronics, and drug delivery. The surface or material interface can be performance-limiting in these applications, so it is vital to determine accurate atomic-scale structures for iron oxides and understand why they form. Using a combination of quantitative low-energy electron diffraction, scanning tunneling microscopy, and density functional theory calculations, we show that an ordered array of subsurface iron vacancies and interstitials underlies the well-known (root 2 x root 2)R45 degrees reconstruction of Fe3O4(001). This hitherto unobserved stabilization mechanism occurs because the iron oxides prefer to redistribute cations in the lattice in response to oxidizing or reducing environments. Many other metal oxides also achieve stoichiometry variation in this way, so such surface structures are likely commonplace.
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