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Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions

Author

Listed:
  • David N. Mueller

    (Stanford University)

  • Michael L. Machala

    (Stanford University)

  • Hendrik Bluhm

    (Lawrence Berkeley National Laboratory)

  • William C. Chueh

    (Stanford University
    Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory)

Abstract

Surface redox-active centres in transition-metal oxides play a key role in determining the efficacy of electrocatalysts. The extreme sensitivity of surface redox states to temperatures, to gas pressures and to electrochemical reaction conditions renders them difficult to investigate by conventional surface-science techniques. Here we report the direct observation of surface redox processes by surface-sensitive, operando X-ray absorption spectroscopy using thin-film iron and cobalt perovskite oxides as model electrodes for elevated-temperature oxygen incorporation and evolution reactions. In contrast to the conventional view that the transition metal cations are the dominant redox-active centres, we find that the oxygen anions near the surface are a significant redox partner to molecular oxygen due to the strong hybridization between oxygen 2p and transition metal 3d electronic states. We propose that a narrow electronic state of significant oxygen 2p character near the Fermi level exchanges electrons with the oxygen adsorbates. This result highlights the importance of surface anion-redox chemistry in oxygen-deficient transition-metal oxides.

Suggested Citation

  • David N. Mueller & Michael L. Machala & Hendrik Bluhm & William C. Chueh, 2015. "Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions," Nature Communications, Nature, vol. 6(1), pages 1-8, May.
    • Handle: RePEc:nat:natcom:v:6:y:2015:i:1:d:10.1038_ncomms7097
    DOI: 10.1038/ncomms7097
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    Cited by:

    1. Matthäus Siebenhofer & Andreas Nenning & Christoph Rameshan & Peter Blaha & Jürgen Fleig & Markus Kubicek, 2024. "Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    2. Fangqing Wang & Peichao Zou & Yangyang Zhang & Wenli Pan & Ying Li & Limin Liang & Cong Chen & Hui Liu & Shijian Zheng, 2023. "Activating lattice oxygen in high-entropy LDH for robust and durable water oxidation," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    3. Pengcheng Ye & Keqing Fang & Haiyan Wang & Yahao Wang & Hao Huang & Chenbin Mo & Jiqiang Ning & Yong Hu, 2024. "Lattice oxygen activation and local electric field enhancement by co-doping Fe and F in CoO nanoneedle arrays for industrial electrocatalytic water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-12, December.

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