Structure and reactivity of iron oxide surfaces

Epitaxial films of different iron oxide phases and of potassium iron oxide were grown onto Pt(111) substrates and used for studying structure-reactivity correlations. The film morphologies and their atomic surface structures were characterized by scanning tunneling microscopy and low energy electron diffraction including multiple scattering calculations. The adsorption of water, ethylbenzene, and styrene was investigated by temperature programmed desorption and photoelectron spectroscopy. A dissociative chemisorption of water and a molecular chemisorption of ethylbenzene and styrene is observed on all oxides that expose metal cations in their topmost layers, whereas purely oxygen-terminated FeO(111) monolayer films are chemically inert and only physisorption occurs. Regarding the technical styrene synthesis reaction, which is performed over iron oxide based catalysts, we find a decreasing chemisorption strength of the reaction product molecule styrene, if compared to ethylbenzene, when going from Fe3O4(111) over alpha-Fe2O3(0001) to KFe O-x(y)(111). Extrapolation of the adsorbate coverages to the technical styrene synthesis reaction conditions using the Langmuir isotherm for coadsorption suggests an increasing catalytic activity along the same direction. This result agrees with previous kinetic experiments performed at elevated gas pressures over the model systems studied here and over polycrystalline iron oxide catalyst samples. It indicates that the iron oxide surface chemistry does not change across the pressure gap and that the model systems simulate technical styrene synthesis catalysts in a realistic way.