Probing adsorbates on La_1−x Sr _x NiO_3−δ surfaces under humid conditions: implications for the oxygen evolution reaction

Abstract Earth-abundant nickel-containing perovskite oxides (ANiO3) are highly active materials for the oxygen evolution reaction (OER). The strong nickel-oxygen (Ni–O) covalency, tunable by A-site chemical substitution, contributes to both bulk and surface material properties like the formation of oxygen vacancies (v •• O ) and OER activity. Here we quantify the coverage of OER relevant adsorbates on a series of La1−x Sr x NiO3−δ (LSNO, 0 ⩽ x ⩽ 0.5) epitaxial thin films exposed to humid environments by ambient pressure x-ray photoelectron spectroscopy. While all LSNO film compositions investigated here have comparable hydroxide coverages at the relative humidities (RHs) probed (1.5 × 10−5 – 0.2%RH), the amount of under-coordinated surface oxygen increases notably with Sr content. We interpret differences in the free energy of adsorption (ΔG ads,i ) of these OER intermediates, inferred from adsorption isotherms, in the context of proposed v •• O -mediated OER mechanisms, consistent with the pH-dependent OER activity observed here for LSNO. We find that Sr incorporation enhances the affinity of LSNO surfaces for these under-coordinated oxygen species, in line with calculations in the literature.