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The correlation between ex situ electronic conductivity, oxygen vacancy content, flat-band potential (Efb), and the oxygen evolution reaction (OER) activity for a wide range of perovskite compositions are investigated experimentally and theoretically. It is found that all of these parameters can affect the OER activity; however, none of them alone play a crucial role in determining the electrocatalytic activity. The correlation of one single physicochemical property with the OER activity always presents deviation points, indicating that a limitation does exist for such 2-dimensional correlations. Nevertheless, these deviations can be explained considering other physicochemical properties and their correlation with the OER activity. Hence, this work aims in simultaneously linking the OER activity with several physicochemical materials properties. The concept of the OER/multidescriptor relationship represents a significant advancement in the search and design of highly active oxygen evolution catalysts, in the quest for efficient anodes in water electrolyzers.

It is shown that producing PrBaCo2O5 and Ba0.5Sr0.5Co0.8Fe0.2O3 nanoparticle by a scalable synthesis method leads to high mass activities for the oxygen evolution reaction with outstanding improvements by 10 and 50 times, respectively, compared to those prepared via the state of the art synthesis method. Here, detailed comparisons at both laboratory and industrial scales show that Ba0.5Sr0.5Co0.8Fe0.2O3 appears to be the most active and stable perovskite catalyst under alkaline conditions, while PrBaCo2O6 reveals thermodynamic instability described by the density functional theory based Pourbaix diagrams highlighting cation dissolution under oxygen evolution conditions. Operando Xray absorption spectroscopy is used in parallel to monitor electronic and structural changes of the catalysts during oxygen evolution reaction. The exceptional BSCF functional stability can be correlated to its thermodynamic metastability under oxygen evolution conditions as highlighted by Pourbaix diagram analysis. BSCF is able to dynamically self reconstruct its surface, leading to formation of Co based oxyhydroxide layers while retaining its structural stability. Differently, PBCO demonstrates a high initial oxygen evolution reaction activity while it undergoes a degradation process considering its thermodynamic instability under oxygen evolution conditions as anticipated by its Pourbaix diagram. Overall, this work demonstrates a synergetic approach of using both experimental and theoretical studies to understand the behavior of perovskite catalysts.

Mixed oxides derived from the perovskite structure by combination of A- and B-site elements and by partial substitution of oxygen provide an immense playground of physico-chemical properties. Here, we account for own research conducted at the Paul Scherrer Institute on perovskite-type oxides and oxynitrides used in electrochemical, photo(electro)chemical and catalytic processes aiming at facing energy relevant issues.

Multilayered heterostructures of Ce0.85Sm0.15O2-delta and Y0.16Zr0.92O2-delta of a high crystallographic quality were fabricated on (001) - oriented MgO single crystal substrates. Keeping the total thickness of the heterostructures constant, the number of ceria-zirconia bilayers was increased while reducing the thickness of each layer. At each interface Ce was found primarily in the reduced, 3+ oxidation state in a layer extending about 2 nm from the interface. Concurrently, the conductivity decreased as the thickness of the layers was reduced suggesting a progressive confinement of the charge transport along the YSZ layers. The comparative analysis of the in-plane electrical characterization suggests that the contribution to the total electrical conductivity of these interfacial regions is negligible. For the smallest layer thickness of 2 nm the doped ceria layers are electrically insulating and the ionic transport only occurs through the zirconia layers. This is explained in terms of a reduced mobility of the oxygen vacancies in the highly reduced ceria.

The size of the band gap and the energy position of the band edges make several oxynitride semiconductors promising candidates for efficient hydrogen and oxygen production under solar light illumination. The intense research efforts dedicated to oxynitride materials have unveiled the majority of their most important properties. However, two crucial aspects have received much less attention. One is the critical issue of the compositional/structural surface modifications occurring during operation and how these affect the photoelectrochemical performance. The second concerns the relation between the electrochemical response and the crystallographic surface orientation of the oxynitride semiconductor. These are indeed topics of fundamental importance since it is exactly at the surface where the visible light-driven electrochemical reaction takes place. In contrast to conventional powder samples, thin films represent the best model system for these investigations. This study reviews current state-of-the-art of oxynitride thin film fabrication and characterization before focusing on LaTiO2N selected as representative photocatalyst. We report the investigation of the initial physicochemical evolution of the surface. Then we show that, after stabilization, the absorbed photon-to-current conversion efficiency of epitaxial thin films can differ by about 50% for different crystallographic surface orientations and be up to 5 times larger than for polycrystalline samples.