Electrochemical stability of the reconstructed Fe3O4(001) surface

Abstract

Establishing the atomic-scale structure of metaloxide surfaces during electrochemical reactions is a key step to modeling this important class of electrocatalysts. Here, we demonstrate that the characteristic (p2p2)R458 surface reconstruction formed on (001)-oriented magnetite single crystals is maintained after immersion in 0.1 M NaOH at 0.20 V vs. Ag/AgCl and we investigate its dependence on the electrode potential. We follow the evolution of the surface using in situ and operando surface X-ray diffraction from the onset of hydrogen evolution, to potentials deep in the oxygen evolution reaction (OER) regime. The reconstruction remains stable for hours between 0.20 and 0.60 V and, surprisingly, is still present at anodic current densities of up to 10 mA cm2 and strongly affects the OER kinetics. We attribute this to a stabilization of the Fe3O4 bulk by the reconstructed surface. At more negative potentials, a gradual and largely irreversible lifting of the reconstruction is observed due to the onset of oxide reduction.