A new endstation to perform operando chemical analysis at solid–liquid interfaces by means of ambient pressure x-ray photoelectron spectroscopy (APXPS) is presented. The endstation is located at the Swiss Light Source and can be attached to the soft x-ray in situ spectroscopy beamline (X07DB) for solid–gas type experiments and to a tender x-ray beamline (PHOENIX I) for solid–liquid interface experiments. The setup consists of three interconnected ultrahigh vacuum chambers: one for sample preparation using surface science techniques, the analysis chamber for APXPS experiments, and an entry-lock chamber for sample transfer across the two pressure regimes. The APXPS chamber is designed to study solid–liquid interfaces stabilized by the dip and pull method. Using a three-electrode setup, the potential difference across the solid-electrolyte interface can be controlled, as is demonstrated here using an Ir(001) electrode dipped and pulled from a 0.1M KOH electrolyte. The new endstation is successfully commissioned and will offer unique opportunities for fundamental studies of phenomena that take place at solid–liquid interfaces and that are relevant for fields such as electrochemistry, photochemistry, or biochemistry, to name a few.

Combining electrochemical measurements with in situ and ex situ photoelectron spectroscopy and simulations to detect the formation of cobalt oxyhydroxide during the oxygen evolution reaction.

The perovskite-type oxide Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) is known as a highly active and stable oxygen evolution reaction (OER) electrocatalyst composited out of non-noble metals. The possibility of using the scalable flame spray synthesis (FSS) technique for the production of BSCF nanoparticles intensified the interest in this material for a future application in an alkaline water electrolyzer. A possible scale-up would require the optimization of the synthesis parameters to maximize the production rate. To further understand the influence of the synthesis parameters of the tunable FSS on the OER activity of BSCF, a systematic study was carried out by producing BSCF with different total metal concentrations (C_TM), flow rates of the precursor solution (FR_PS) and of the dispersion gas (FR_DG). This study reveals that all three parameters have a direct impact on the OER activity of BSCF—measured in a rotating disc electrode (RDE) setup—due to the controllability of the initial Co and Fe oxidation state—indicated by X-ray absorption spectroscopy (XAS) measurements—and with that also of the oxygen vacancy concentration in the as-synthesized BSCF. This controllability enables the optimization of the OER activity of BSCF and emphasizes the importance of having Co in a lower initial oxidation state for reaching a high electrocatalytic performance.

O K-edge XAS measurements reveal a surface reconstruction in RBaCuFeO _{5+ δ} layered perovskites when δ > 0. Oxygen excess, together with some degree of A-site cation intermixing, appears to control the OER activity in these Co-free electrocatalysts.