Stability and catalytic performance of reconstructed Fe3O4(001) and Fe3O4(110) surfaces during oxygen evolution reaction

M. Müllner, M. Riva, F. Kraushofer, M. Schmid, G. S. Parkinson, S. F. L. Mertens, U. Diebold

Institut für Angewandte Physik, Technische Universität Wien, 1040 Wien, Austria

J. Phys. Chem. C 123 (2019) 8304-8311

Earth-abundant oxides are promising candidates as effective and low-cost catalysts for the oxygen evolution reaction (OER) in alkaline media, which remains one of the bottlenecks in electrolysis and artificial photosynthesis. A fundamental understanding of the atomic-scale reaction mechanism during OER could drive further progress, but a stable model system has yet to be provided. Here we show that Fe3O4 single crystal surfaces, prepared in ultra high vacuum (UHV) are stable in alkaline electrolyte in the range pH 7-14 and under OER conditions in 1 M NaOH. Fe3O4(001) and (110) surfaces where studied with X-ray photoelectron spectroscopy, low-energy electron diffraction and scanning tunneling microscopy in UHV, and atomic force microscopy in air. Fe3O4(110) is found to be more reactive for oxidative water splitting than (001)-oriented magnetite samples. Magnetite is electrically conductive, the structure and properties of its major facets are well understood in UHV. With these newly obtained results we propose magnetite (Fe3O4) as a promising model system for further mechanistic studies of electrochemical reactions in alkaline media and highly oxidizing conditions.

Corresponding author: Gareth Parkinson (parkinson at iap_tuwien_ac_at).

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