Correlating Surface Crystal Orientation and Gas Kinetics in Perovskite Oxide Electrodes

Solid-gas interactions at electrode surfaces determine the efficiency of solid-oxide fuel cells and electrolyzers. Here, the correlation between surface-gas kinetics and the crystal orientation of perovskite electrodes is studied in the model system La_0.8 Sr_0.2 Co_0.2 Fe_0.8 O₃ . The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.e., La_0.8 Sr_0.2 Co_0.2 Fe_0.8 O₃ /La_0.9 Sr_0.1 Ga_0.95 Mg_0.05 O_3-δ /SrRuO₃ /SrTiO₃ (001), (110), and (111)]. Electrochemical impedance spectroscopy and electrical conductivity relaxation measurements reveal a strong surface-orientation dependency of the gas-exchange kinetics, wherein (111)-oriented surfaces exhibit an activity >3-times higher as compared to (001)-oriented surfaces. Oxygen partial pressure ( $$ )-dependent electrochemical impedance spectroscopy studies reveal that while the three surfaces have different gas-exchange kinetics, the reaction mechanisms and rate-limiting steps are the same (i.e., charge-transfer to the diatomic oxygen species). First-principles calculations suggest that the formation energy of vacancies and adsorption at the various surfaces is different and influenced by the surface polarity. Finally, synchrotron-based, ambient-pressure X-ray spectroscopies reveal distinct electronic changes and surface chemistry among the different surface orientations. Taken together, thin-film epitaxy provides an efficient approach to control and understand the electrode reactivity ultimately demonstrating that the (111)-surface exhibits a high density of active surface sites which leads to higher activity.