Stability of the Fe3O4 (√2 x √2)R 45° Surface in 0.1 M NaOH Investigated by High-Energy Surface X-Ray Diffraction
Authors: Bunge Jonas , Grumelli Doris , Fehrs Jan Ole , Fuchs Timo , Jacobse Leon , Stettner Jochim , Stierle Andreas , Magnussen Olaf M. 
Published: February 2024

Transition metal oxides, especially Fe, Co, and Ni oxides, are of great interest as electrocatalysts for the oxygen evolution reaction (OER) in alkaline solution. However, detailed data on the atomic-scale oxide-electrolyte interface structure of these systems are rare. We present studies of a model oxide electrocatalyst, -reconstructed Fe3O4(001). This oxide surface has been extensively investigated under ultrahigh vacuum (UHV) conditions, leading to a detailed understanding of its atomic structure [2]. In previous in situ surface X-ray diffraction studies, we demonstrated that the reconstructed surface can survive transfer into electrochemical environment and determined the stability of the reconstruction as a function of potential [2]. Specifically, we showed that the ()R45° reconstructed Fe3O4(001) surface can be transferred into 0.1 M NaOH at 0.2 V vs. Ag/AgCl while maintaining surface structure and that the reconstruction is irreversibly lifted at sufficiently negative potentials.
Here, we present more detailed in situ studies of this system, using the novel technique of High-Energy Surface X-Ray Diffraction (HESXRD) [3,4]. This technique enabled us to measure rapidly a huge reciprocal space volume, which allows to obtain very large sets of crystal truncation rods (CTRs) that can be analysed by surface crystallographic methods. These data provide detailed insights into the temporal stability of the surface at fixed potentials as well as potential-dependent changes in surface structure.
In the experiments the Fe3O4(001) single crystal samples were prepared by sputtering and annealing in UHV, followed by sample transfer into the hanging-meniscus cell employed for the HESXRD studies. A new experimental procedure allowed to reduce the time of sample transfer and establishment of potential control to below one minute.
The in situ HESXRD measurements were performed at beamline P21.2 of PETRA III at DESY. 7 symmetrically independent CTRs and 2 ()R45° fractional order rods could be measured. These data enabled detailed comparison of the oxide-electrolyte interface with the surface structure under UHV conditions [1]. The potential-dependent data indicate clear structural changes when applying more positive or more negative potentials than 0.2 V vs. Ag/AgCl, as illustrated in part A and B of Fig. 1. However, all surface structures were stable at constant potential over several hours, as indicated in part C of Fig. 1. The quality of the obtained results allows to determine quantitative analysis of the interface structure. First results of this analysis will be presented.
We gratefully acknowledge financial support by the German ministry of Science and Education (BMBF) via projects 05K19FK3 and 05K22FK1.

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Figure 1