UHV-based analytics with electrochemical oxygen activity control

The (electro)chemical properties of electrode materials in solid oxide cells or oxide-based redox catalysts are determined by the surface chemistry of these materials under operation conditions. Surface point defect concentrations strongly depend on the oxygen stoichiometry in the bulk and the gas phase's chemical composition (<i>e.g.</i>, oxygen activity). However, many chemically sensitive surface analysis techniques rely on UHV conditions, leading to a two-fold deviation from surfaces under operational conditions. On the one hand, adsorbed gas phase species are missing in UHV. On the other hand, transition metal oxidation states and the oxygen vacancy concentration at surfaces are connected to the oxygen stoichiometry in the bulk of the material, which is inevitably altered during cell transfer from electrochemical measurement to UHV-based analytics. To reduce this two-fold gap between analytical studies and typical operation conditions, we present a novel solid oxide cell design for electrochemical oxygen activity control of surfaces in UHV-based analytic tools. Its key feature is an oxygen-ion buffering counter electrode containing a Fe|FeO phase equilibrium with known oxygen activity. A defined voltage between this counter electrode and the oxide under investigation (used as working electrode) defines the oxygen activity of the relevant oxide surface. Moreover, simultaneous thin film coulometry allows the determination of the bulk oxygen deficiency in the respective oxides. As a proof of concept, we use UHV-based XPS to compare the bulk and surface reducibility of fluorite-type Gd-doped ceria and perovskite-type Fe-doped SrTiO₃ under electrochemical oxygen activity control. We show that the cell voltage can tune the transition metal oxidation states and oxygen vacancy concentration at the surface. These relate well to the actual solid oxide cell operation at the same temperature and <i>p</i>(O₂).