| Download | - View accepted manuscript: Tuning the oxygen reduction reactivity of layered perovskites using the Jahn–Teller effect (PDF, 3.4 MiB)
- View supplementary information: Tuning the oxygen reduction reactivity of layered perovskites using the Jahn–Teller effect (PDF, 794 KiB)
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| DOI | Resolve DOI: https://doi.org/10.1021/acsami.4c01105 |
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| Author | Search for: Whittingham, Alexander W. H.1ORCID identifier: https://orcid.org/0000-0001-9752-6356; Search for: Boke, Marlyn; Search for: Smith, Rodney D. L.ORCID identifier: https://orcid.org/0000-0003-1209-9653 |
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| Affiliation | - National Research Council Canada. Clean Energy Innovation
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| Funder | Search for: Ontario Research Foundation; Search for: Natural Sciences and Engineering Research Council of Canada |
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| Format | Text, Article |
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| Subject | perovskite; oxygen reduction reaction; reaction mechanism; electrocatalysis; peroxide production; lattice distortions |
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| Abstract | Compositional tuning of layered perovskite oxidesprovides a means of systematically studying how local distortionsaffect fundamental aspects of electrochemical reaction pathways.Structural analysis of a family of samples La₁.₂Sr₀.₈Ni₁₋yCoyO₄ showsthat Ni-rich compositions have an expanded crystalline c axis, which isanisotropically compressed by systematic Co incorporation. Ramanspectra reveal the strong growth of a symmetry forbidden mode,which suggests that Co acts through localized distortions. Crystallo-graphic and spectroscopic parameters describing this structuraldistortion correlate to the measured Tafel slopes for the oxygenreduction reaction for all Ni-containing samples, which is attributedto the distortion of potential energy surfaces by the Jahn−Tellerexpansion of d⁷ Ni(III) cations. Incorporation of Co not only minimizes the distortion but alters the apparent selectivity of theoxygen reduction reaction away from H₂O₂ and toward H₂O. Rotating ring-disk electrochemical measurements, however, indicatethat the apparent change in selectivity is due to activation of a first-order chemical disproportionation of H₂O₂ that is activated byCo in the lattice. These outcomes will support efforts to design electrocatalysts and reactors for the electrochemical synthesis ofH₂O₂. |
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| Publication date | 2024-04-11 |
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| Publisher | American Chemical Society |
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| In | |
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| Language | English |
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| Peer reviewed | Yes |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | ae1e497c-0118-4c5c-bbdd-46a02121b9a2 |
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| Record created | 2024-05-15 |
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| Record modified | 2025-11-06 |
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