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Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems. 

Electrocatalytic reactions are known to take place at the catalyst/electrolyte interface. Whereas recent studies of size‐dependent activity in nanoparticles and thickness‐dependent activity of thin films imply that the sub‐surface layers of a catalyst can contribute to the catalytic activity as well, most of these studies consider actual modification of the surfaces. In this study, the role of catalytically active sub‐surface layers was investigated by employing atomic‐scale thickness control of the La_0.7Sr_0.3MnO₃(LSMO) films and heterostructures, without altering the catalyst/electrolyte interface. The activity toward the oxygen evolution reaction (OER) shows a non‐monotonic thickness dependence in the LSMO films and a continuous screening effect in LSMO/SrRuO₃heterostructures. The observation leads to the definition of an “electrochemically‐relevant depth” on the order of 10 unit cells. This study on the electrocatalytic activity of epitaxial heterostructures provides new insight in designing efficient electrocatalytic nanomaterials and core‐shell architectures.