Correlating Surface Crystal Orientation and Gas Kinetics in Perovskite Oxide Electrodes
© 2021 Wiley-VCH GmbH..
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 La0.8 Sr0.2 Co0.2 Fe0.8 O3 . The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.e., La0.8 Sr0.2 Co0.2 Fe0.8 O3 /La0.9 Sr0.1 Ga0.95 Mg0.05 O3-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 ( p O 2 )-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.
Medienart: |
E-Artikel |
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Erscheinungsjahr: |
2021 |
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Erschienen: |
2021 |
Enthalten in: |
Zur Gesamtaufnahme - volume:33 |
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Enthalten in: |
Advanced materials (Deerfield Beach, Fla.) - 33(2021), 20 vom: 07. Mai, Seite e2100977 |
Sprache: |
Englisch |
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Beteiligte Personen: |
Gao, Ran [VerfasserIn] |
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Links: |
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Themen: |
Electrochemical reactions |
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Anmerkungen: |
Date Revised 20.05.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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doi: |
10.1002/adma.202100977 |
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funding: |
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Förderinstitution / Projekttitel: |
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PPN (Katalog-ID): |
NLM323848311 |
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520 | |a 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 La0.8 Sr0.2 Co0.2 Fe0.8 O3 . The gas-exchange kinetics are characterized by synthesizing epitaxial half-cell geometries where three single-variant surfaces are produced [i.e., La0.8 Sr0.2 Co0.2 Fe0.8 O3 /La0.9 Sr0.1 Ga0.95 Mg0.05 O3-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 ( p O 2 )-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 | ||
650 | 4 | |a Journal Article | |
650 | 4 | |a electrochemical reactions | |
650 | 4 | |a epitaxial thin films | |
650 | 4 | |a half-cells | |
650 | 4 | |a perovskite oxides | |
650 | 4 | |a surface engineering | |
700 | 1 | |a Fernandez, Abel |e verfasserin |4 aut | |
700 | 1 | |a Chakraborty, Tanmoy |e verfasserin |4 aut | |
700 | 1 | |a Luo, Aileen |e verfasserin |4 aut | |
700 | 1 | |a Pesquera, David |e verfasserin |4 aut | |
700 | 1 | |a Das, Sujit |e verfasserin |4 aut | |
700 | 1 | |a Velarde, Gabriel |e verfasserin |4 aut | |
700 | 1 | |a Thoréton, Vincent |e verfasserin |4 aut | |
700 | 1 | |a Kilner, John |e verfasserin |4 aut | |
700 | 1 | |a Ishihara, Tatsumi |e verfasserin |4 aut | |
700 | 1 | |a Nemšák, Slavomír |e verfasserin |4 aut | |
700 | 1 | |a Crumlin, Ethan J |e verfasserin |4 aut | |
700 | 1 | |a Ertekin, Elif |e verfasserin |4 aut | |
700 | 1 | |a Martin, Lane W |e verfasserin |4 aut | |
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