Correlating Surface Crystal Orientation and Gas Kinetics in Perovskite Oxide Electrodes

Ran Gao, Abel Fernandez, Tanmoy Chakraborty, Aileen Luo, David Pesquera, Sujit Das, Gabriel Velarde, Vincent Thoréton, John Kilner, Tatsumi Ishihara, Slavomír Nemšák, Ethan J. Crumlin, Elif Ertekin, Lane W. Martin

Research output: Contribution to journalArticlepeer-review


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 La0.8Sr0.2Co0.2Fe0.8O3. The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.e., La0.8Sr0.2Co0.2Fe0.8O3/La0.9Sr0.1Ga0.95Mg0.05O3−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 ((Formula presented.))-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.

Original languageEnglish (US)
Article number2100977
JournalAdvanced Materials
Issue number20
StatePublished - May 20 2021
Externally publishedYes


  • electrochemical reactions
  • epitaxial thin films
  • half-cells
  • perovskite oxides
  • surface engineering

ASJC Scopus subject areas

  • General Materials Science
  • Mechanics of Materials
  • Mechanical Engineering


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