Atomic Structure of the Fe3O4/Fe2O3 Interface During Phase Transition from Hematite to Magnetite.

Phase transition between iron oxides practically defines their functionalities in both physical and chemical applications. Direct observation of the atomic rearrangement and a quantitative description of the dynamic behavior of the phase transition, however, are rare. Here, we monitored the structure evolution from a rod-shaped hematite nanoparticle to magnetite during H2 reduction at elevated temperatures. Environmental transmission electron microscopy observations, along with selected area electron diffraction experiments, identified that the reduction preferentially commenced with Fe3O4 nucleation on the surface defective sites, followed by laterally growing into a Fe3O4 film until fully covering the particle surface. The Fe3O4 phase then propagated toward the bulk particle via a Fe3O4/α-Fe2O3 interface with the relationship α-Fe2O3(0001)//Fe3O4(111) in an aligned orientation of [112]Fe3O4||[112̅0]α-Fe2O3. Upon this Fe3O4/α-Fe2O3 interface, the Fe-O octahedra in Fe3O4(111) (as layer A) matches that of α-Fe2O3(0001) at a rotation angle of 30°, and the reduction proceeds in such a pattern that two-thirds of the FeOh in the adjacent layer (layer B) is transformed into FeTe.

Geometrical Structure of the Gold-Iron(III) Oxide Interfacial Perimeter for CO Oxidation.

The geometrical structure of the Au-Fe2 O3 interfacial perimeter, which is generally considered as the active sites for low-temperature oxidation of CO, was examined. It was found that the activity of the Au/Fe2 O3 catalysts not only depends on the number of the gold atoms at the interfacial perimeter but also strongly depends on the geometrical structure of these gold atoms, which is determined by the size of the gold particle. Aberration-corrected scanning transmission electron microscopy images unambiguously suggested that the gold particles, transformed from a two-dimensional flat shape to a well-faceted truncated octahedron when the size slightly enlarged from 2.2 to 3.5 nm. Such a size-induced shape evolution altered the chemical bonding environments of the gold atoms at the interfacial perimeters and consequently their catalytic activity. For Au particles with a mean size of 2.2 nm, the interfacial perimeter gold atoms possessed a higher degree of unsaturated coordination environment while for Au particles with a mean size of 3.5 nm the perimeter gold atoms mainly followed the atomic arrangements of Au {111} and {100} facets. Kinetic study, with respect to the reaction rate and the turnover frequency on the interfacial perimeter gold atom, found that the low-coordinated perimeter gold atoms were intrinsically more active for CO oxidation. 18 O isotopic titration and Infrared spectroscopy experiments verified that CO oxidation at room temperature occurred at the Au-Fe2 O3 interfacial perimeter, involving the participation of the lattice oxygen of Fe2 O3 for activating O2 and the gold atoms for CO adsorption and activation.

Restructuring of the gold-carbide interface for low-temperature water-gas shift.

A passivated Au/α-MoC catalyst, containing 2-4 layered Au clusters of 1.6 nm, was re-activated by CH4/H2 at 590 °C, during which the structure of the gold-carbide interface changed considerably. The partially-oxidized surface Mo species were carburized to MoC, while the Au clusters dispersed into smaller ones, accompanied by the coating of carbide thin layers on Au. This restructuring promoted charge transfer from Au to MoC and extended the Au-MoC interfacial perimeter, which was largely responsible for the activity in the low-temperature water-gas shift reaction.