Subsurface Cation Vacancy Stabilization of the Magnetite (001) Surface

Abstract

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 (rt2xrt2)R45° 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 stoichiometric variation in this way, so such surface structures are likely commonplace.

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Cited by in corpus (40)

• Iron Oxide Surfaces
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• Single-Atom Catalysis: Insights from Model Systems
• Water Agglomerates on Fe3O4(001)
• An Atomic-Scale View of CO and H2 Oxidation on a Pt-Fe3O4 Model Catalyst
• A Multi-Technique Study of $C{O}_2$ Adsorption on $F{e}_3$$O_4$ Magnetite
• The role of surface defects in the adsorption of methanol on Fe3O4(001)
• CO oxidation by Pt2/Fe3O4: metastable dimer and support configurations facilitate lattice oxygen extraction
• Unusual Fe-H bonding associated with oxygen vacancies at the (001) surface of Fe3O4
• Cluster Catalysis with Lattice Oxygen: Tracing Oxygen Transport from a Magnetite(001) Support onto Small Pt Clusters
• An efficient way to model complex magnetite: assessment of SCC-DFTB against DFT
• Shaping Magnetite Nanoparticles from First-principles
• Ni modified Fe3O4(001) surface as a simple model system for understanding the Oxygen Evolution Reaction
• From Fe${}_3$O${}_4$/NiO bilayers to NiFe${}_2$O${}_4$-like thin films through Ni interdiffusion
• Self-limited Growth of an Oxyhydroxide Phase at the Fe3O4(001) Surface in Liquid and Ambient Pressure Water
• Adsorption of CO on the Fe3O4(001) Surface
• Rapid oxygen exchange between hematite and water vapor
• Electronic and magnetic structure of epitaxial NiO/Fe${}_3$O${}_4$(001) heterostructures grown on MgO(001) and Nb-doped SrTiO${}_3$(001)
• Influence of Local Defects on the Dynamics of O-H Bond Breaking and Formation on a Magnetite Surface
• Surface Reduction State Determines Stabilization and Incorporation of Rh on α-Fe2O3(1-102)
• Insight into the interface between Fe${}_3$O${}_4$(001) surface and water overlayers through multiscale molecular dynamics simulations
• Oxidation State Dynamics and Emerging Patterns in Magnetite
• Fe3O4(110)-(1x3) Revisited: Periodic (111) Nano-Facets
• Standardization of chemically selective atomic force microscopy for metal-oxide surfaces
• Cation- and lattice-site-selective magnetic depth profiles of ultrathin $\mathrm{F}{\mathrm{e}}_3{\mathrm{O}}_4$(001) films
• Parametrization of the Fe-Owater cross-interaction for a more accurate Fe3O4/water interface model and its application to a spherical Fe3O4 nanoparticle of realistic size
• Well-Ordered In Adatoms at the In${}_2$O${}_3$(111) Surface Created by Fe Deposition
• Dynamic atomic reconstruction: how Fe3O4 thin films evade polar catastrophe for epitaxy
• Atomic-scale studies of Fe3O4(001) and TiO2(110) surfaces following immersion in CO2-acidified water
• Oxygen-Terminated (1x1) Reconstruction of Reduced Magnetite Fe${}_3$O${}_4$(111)
• Structure and morphology of epitaxially grown Fe3O4/NiO bilayers on MgO(001)
• Mechanism of spin ordering in Fe${}_3$O${}_4$ nanoparticles by surface coating with organic acids
• ViPErLEED package I: Calculation of $I(V)$ curves and structural optimization
• Atomic Structure of Hematite ($\alpha$-Fe${}_2$O${}_3$) Nanocube Surface; Synchrotron X-ray Diffraction Study
• Application of murexide as a capping agent for fabrication of magnetite anodes for supercapacitors: experimental and first-principle studies
• Atomistic Simulations of Oxide-Water Interfaces using Machine Learning Potentials
• Impact of strain and morphology on magnetic properties of Fe${}_3$O${}_4$/NiO bilayers grown on Nb:SrTiO${}_3$(001) and MgO(001)
• A Multi-Technique Study of C2H4 Adsorption on a Model Single-Atom Rh1 Catalyst
• Structural and magnetic investigation of the interfaces of $\mathrm{F}{\mathrm{e}}_3{\mathrm{O}}_4/MgO(001)$ with and without NiO interlayer
• Atomistic modeling of functionalized magnetite surfaces with oxidation states