RESUMEN
The main obstacle for the electrocatalytic production of "green hydrogen" is finding suitable electrocatalysts which operate highly efficiently over extended periods of time. The topic of this study is the oxygen evolution reaction (OER), one of the half-reactions of water splitting. It is complex and has intricate kinetics, which impairs the reaction efficiency. Transition metal oxides have shown potential as electrocatalysts for this reaction, but much remains unknown about the atomic scale processes. We have investigated structure-composition-reactivity correlations for Co3O4, CoFe2O4, and Fe3O4 epitaxial thin-film electrocatalysts exposing either the (001) or (111) surface facets. We found that for Co3O4, the (001) facet is more reactive, while for the other oxides, the (111) facet is more active. A Tafel-like evaluation reveals systematically smaller "Tafel" slopes for the (001) facets. Furthermore, the slopes are smaller for the iron-containing films. Additionally, we found that the oxyhydroxide skin layer which forms under OER reaction conditions is thicker on the cobalt oxides than on the other oxides, which we attribute to either a different density of surface defects or to iron hindering the growth of the skin layers. All studied skin layers were thinner than 1 nm.
RESUMEN
Water electrolysis to produce 'green H2' with renewable energy is a promising option for the upcoming green economy. However, the slow and complex oxygen evolution reaction at the anode limits the efficiency. Co3O4 with added iron is a capable catalyst for this reaction, but the role of iron is presently unclear. To investigate this topic, we compare epitaxial Co3O4(111), CoFe2O4(111), and Fe3O4(111) thin film model electrocatalysts, combining quasi in-situ preparation and characterization in ultra-high vacuum with electrochemistry experiments. The well-defined composition and structure of the thin epitaxial films permits the obtention of quantitatively comparable results. CoFe2O4(111) is found to be up to about four times more active than Co3O4(111) and about nine times more than Fe3O4(111), with the activity depending acutely on the Co/Fe concentration ratio. Under reaction conditions, all three oxides are covered by oxyhydroxide. For CoFe2O4(111), the oxyhydroxide's Fe/Co concentration ratio is stabilized by partial iron dissolution.
RESUMEN
In this paper a growth recipe for well-ordered iron sulfide films and the results of their characterisation are presented. The film was studied using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM). XRD data reveal that the film has a NiAs-like structure with Fe vacancies, similar to iron sulfides such as pyrrhotite and smythite, although no indication of any ordering of these vacancies was observed. LEED and STM results show that the film exhibits a 2 × 2 surface reconstruction. XPS data provide additional evidence for a large number of Fe vacancies, and the oxidation states of the Fe and S in the film are analysed.
