Multielement Activity Mapping and Potential Mapping in Solid Oxide Electrochemical Cells through the use of operando XPS

Spatially resolved ambient pressure X-ray photoelectron spectroscopy has been used to measure and visualize regions of electrochemical activity, local surface potential losses, overpotentials, and oxidation state changes on single sided ceria/yttria-stabilized zirconia (YSZ)/Pt solid oxide electrochemical cells. When hydrogen electro-oxidation (negative applied bias) or water electrolysis (positive applied bias) is promoted on the ceria electrocatalyst, the Ce3+/Ce4+ ratios shift away from equilibrium values and thereby demarcate electrochemically active regions on the ceria electrode. In addition to the ceria oxidation state shifts, inactive surface impurities with high photoelectron cross sections, such as Si, can provide local markers of activity through chemical and surface potential mappings under various electrochemical conditions. Localized removal of chemically active carbonaceous surface impurities also reveals regions of electrochemical oxidation activity on the ceria electrode. Finally, we show...