Tileli, VasilikiShen, Tzu-Hsien2022-04-012022-04-012022-04-01202210.5075/epfl-thesis-9072https://infoscience.epfl.ch/handle/20.500.14299/186803Water splitting is one of the cleanest ways to store energy. The production of hydrogen and oxygen gases can be utilized in fuel cells to generate electricity, power, and heat. In the water splitting process, the oxygen evolution reaction (OER), taking place at the anode, is the sluggish reaction limiting the efficiency. Electrocatalysts are used to reduce the kinetic barrier of OER. Development of high-performance and stable OER catalysts requires fundamental understanding of their electrocatalytic properties and, hence, their holistic characterization is indispensable. The objective of this thesis is to probe Co-based oxide catalysts for OER in an alkaline medium using advanced (scanning) transmission electron microscopy ((S)TEM) techniques. Starting with the surface characterization of a highly active OER oxide catalyst, Ba0.5Sr0.5Co0.8Fe0.2O3-d (BSCF), it is shown that the surfaces of the as-synthesized BSCF particles are Co/Fe rich and adopt a spinel-like structure with a reduced valence of Co ions. The Co/Fe spinel structure is further linked to the formation of the highly active Co(Fe)OOH at the BSCF surface. Further real-time probing of BSCF oxide catalysts using electrochemical liquid-cell TEM shows a switchable wetting behavior of Co-based oxide catalysts by analyzing the liquid movement around oxide particles. The interfacial interactions at the surface-electrolyte under potential cycling are correlated to electrowetting and hydrophilic surface transformation. Molecular oxygen evolution is detected qualitatively under OER conditions by identifying the O2 feature in electron energy-loss spectra. Quantification of the O2 using electron energy-loss spectroscopy is also demonstrated, pending further improvements. The work herein offers new insights into the characterization framework of oxide catalysts for OER using (S)TEM. The bulk to surface structure of the catalysts can be analyzed, and the interfacial interactions of single-particle catalysts can be probed in real-time. The findings aid in understanding the performance and stability of oxygen-evolving oxide catalysts with further prospects envisioned towards a complete quantitative probing of electrocatalytic reactions in real-time. Ultimately, quantitative characterization in electrochemical liquid-phase (S)TEM can provide understanding of surface-active sites and reaction kinetics of oxygen evolution catalysts.enoxygen evolution reactionelectrocatalystsCo-based oxides(scanning) transmission electron microscopyelectron energy-loss spectroscopyelectrochemical liquid-phase transmission electron microscopythesis::doctoral thesis