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Detection of high-valent iron species in alloyed oxidic cobaltates for catalysing the oxygen evolution reaction

Author

Listed:
  • Nancy Li

    (Harvard University)

  • Ryan G. Hadt

    (Argonne National Laboratory
    California Institute of Technology)

  • Dugan Hayes

    (Argonne National Laboratory
    University of Rhode Island)

  • Lin X. Chen

    (Argonne National Laboratory
    Northwestern University)

  • Daniel G. Nocera

    (Harvard University)

Abstract

Iron alloying of oxidic cobaltate catalysts results in catalytic activity for oxygen evolution on par with Ni-Fe oxides in base but at much higher alloying compositions. Zero-field 57Fe Mössbauer spectroscopy and X-ray absorption spectroscopy (XAS) are able to clearly identify Fe4+ in mixed-metal Co-Fe oxides. The highest Fe4+ population is obtained in the 40–60% Fe alloying range, and XAS identifies the ion residing in an octahedral oxide ligand field. The oxygen evolution reaction (OER) activity, as reflected in Tafel analysis of CoFeOx films in 1 M KOH, tracks the absolute concentration of Fe4+. The results reported herein suggest an important role for the formation of the Fe4+ redox state in activating cobaltate OER catalysts at high iron loadings.

Suggested Citation

  • Nancy Li & Ryan G. Hadt & Dugan Hayes & Lin X. Chen & Daniel G. Nocera, 2021. "Detection of high-valent iron species in alloyed oxidic cobaltates for catalysing the oxygen evolution reaction," Nature Communications, Nature, vol. 12(1), pages 1-6, December.
    • Handle: RePEc:nat:natcom:v:12:y:2021:i:1:d:10.1038_s41467-021-24453-6
    DOI: 10.1038/s41467-021-24453-6
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    Cited by:

    1. Shao, Yuewen & Guo, Mingzhu & Fan, Mengjiao & Sun, Kai & Gao, Guoming & Li, Chao & Kontchouo, Félix Mérimé Bkangmo & Zhang, Lijun & Zhang, Shu & Hu, Xun, 2023. "Importance of oxyphilic FeNi alloy in NiFeAl catalysts for selective conversion of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran," Renewable Energy, Elsevier, vol. 208(C), pages 105-118.
    2. Yuanmiao Sun & Jiarui Wang & Shibo Xi & Jingjing Shen & Songzhu Luo & Jingjie Ge & Shengnan Sun & Yubo Chen & John V. Hanna & Shuzhou Li & Xin Wang & Zhichuan J. Xu, 2023. "Navigating surface reconstruction of spinel oxides for electrochemical water oxidation," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    3. Yingqing Ou & Liam P. Twight & Bipasa Samanta & Lu Liu & Santu Biswas & Jessica L. Fehrs & Nicole A. Sagui & Javier Villalobos & Joaquín Morales-Santelices & Denis Antipin & Marcel Risch & Maytal Casp, 2023. "Cooperative Fe sites on transition metal (oxy)hydroxides drive high oxygen evolution activity in base," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    4. Agnes E. Thorarinsdottir & Samuel S. Veroneau & Daniel G. Nocera, 2022. "Self-healing oxygen evolution catalysts," Nature Communications, Nature, vol. 13(1), pages 1-10, December.

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