Insight into magnetite's redox catalysis from observing surface morphology during oxidation

8 pag, 6 figs. -- Supporting Information is available at Publisher's webWe study how the (100) surface of magnetite undergoes oxidation by monitoring its morphology during exposure to oxygen at ∼650 C. Low-energy electron microscopy reveals that magnetite's surface steps advance continuously. This growth of Fe3O4 crystal occurs by the formation of bulk Fe vacancies. Using Raman spectroscopy, we identify the sinks for these vacancies, inclusions of α-Fe2O3 (hematite). Since the surface remains magnetite during oxidation, it continues to dissociate oxygen readily. At steady state, over one-quarter of impinging oxygen molecules undergo dissociative adsorption and eventual incorporation into magnetite. From the independence of growth rate on local step density, we deduce that the first step of oxidation, dissociative oxygen adsorption, occurs uniformly over magnetite's terraces, not preferentially at its surface steps. Since we directly observe new magnetite forming when it incorporates oxygen, we suggest that catalytic redox cycles on magnetite involve growing and etching crystal. © 2013 American Chemical Society.Our research was supported by the Office of Basic Energy Sciences, Division of Materials and Engineering Sciences, U.S. Department of Energy under contract no. DE-AC04-94AL85000 and the Spanish Ministry of Science and Innovation through project no. MAT2009-14578-C03-01