Systematic trends of the 57Fe Mössbauer isomer shifts in (FeOn) and (FeFn) polyhedra. Evidence of a new correlation between the isomer shift and the inductive effect of the competing bond T-X (→ Fe) (where X is O or F and T any element with a formal positive charge)

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 α-Fe2O3(0001) to KFexOy(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.

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Structure and reactivity of iron oxide surfaces

The multipole moment is an established concept of electrons in solids. Entanglement of spin, orbital, and sublattice degrees of freedom is described by the multipole moment, and spontaneous multipole order is a ubiquitous phenomenon in strongly correlated electron systems. In this paper, we present group-theoretical classification theory of multipole order in solids. Intriguing duality between the real-space and momentum-space properties is revealed for odd-parity multipole order which spontaneously breaks inversion symmetry. Electromagnetic responses in odd-parity multipole states are clarified on the basis of the classification theory. A direct relation between the multipole moment and the magnetoelectric effect, Edelstein effect, magnetopiezoelectric effect, and dichromatic electron transport is demonstrated. More than 110 odd-parity magnetic multipole materials are identified by the group-theoretical analysis. Combining the list of materials with the classification tables of multipole order, we predict emergent responses of the candidate materials.

Group-theoretical classification of multipole order: Emergent responses and candidate materials

Well‐characterized catalyst model compounds of KAlO2 and KFeO2 are investigated by thermal desorption of potassium from the material. The desorbing fluxes of ions, atoms and highly excited states (field ionizable Rydberg states) were studied with surface and field ionization detectors in a vacuum apparatus. From the Arrhenius plots the activation energies for desorption of K and K+ were determined. The chemical state of potassium at the surfaces is concluded to be: ionic on KAlO2 (with the K desorption barrier of 1.76 eV) and covalent on KFeO2 (barrier of 2.73 eV). These results agree with the data obtained earlier for industrial catalysts for ammonia and styrene production. They are interpreted in terms of the Schottky cycle, which is completed for KAlO2 and fails for KFeO2. This failure indicates a non‐equilibrium desorption process. K Rydberg states are only found to desorb from KFeO2, in agreement with the suggestion that such states in some way are responsible for the catalytic activity.

Z. Tomkowicz

Papers

Crystal and magnetic structure of KFeO2