Surface structure of magnetite (111) under hydrated conditions by crystal truncation rod diffraction

X-ray crystal truncation rod (CTR) diffraction under hydrated conditions at circum-neutral pH was used to determine the surface structure of Fe3O4(111) following a wet chemical mechanical polishing (CMP) preparation method. The best-fit model to the CTR data shows the presence of two oxygen terminated domains that are chemically inequivalent and symmetrically distinct in the surface contribution ratio of 75% oxygen octahedral-iron (OOI) termination (aO2.61-aO1.00-oh1Fe2.55-bO1.00-bO3.00-td1Fe1.00-oh2Fe1.00-td2Fe1.00-R) to 25% oxygen mixed-iron (OMI) termination (bO1.00-bO3.00-td1Fe0-oh2Fe1.00-td2Fe1.00-aO3.00-aO1.00-oh1Fe3.00-R). An adsorbed water layer could not be constrained in the best-fit model. However, bond-valence analyses suggest that both of the surfaces are hydro-oxo terminated. Furthermore, the topmost iron layers of both domains are inferred to be occupied with the redox active Fe2+ and Fe3+ cations indicating that these irons are the principle irons involved in controlling the surface reactivity of magnetite in industrial and environmentally relevant conditions.