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<p>Oxidation states underpin the understanding of active states, reaction mechanisms and catalytic performance of electrocatalysts. However, determining them at complex solid–liquid interfaces is challenging. Here we use multimodal spectroscopy to investigate polarized iridium oxide (IrO<sub><i>x</i></sub>) electrodes, a model water oxidation catalyst, to identify potential-dependent iridium and oxygen oxidation states. By integrating multiple operando spectroscopies (optical (ultraviolet–visible), Ir L-edge and O K-edge X-ray absorption spectroscopy) with electrochemistry mass spectrometry and density functional theory calculations, we identify the sequential depletion of electron densities from the Ir5<i>d</i> band (corresponding to Ir<sup>3+</sup>→Ir<sup>4+</sup>→Ir<sup>5+</sup>), followed by electron removal from the O2<i>p</i> band, forming electrophilic oxygen species (O<sup>−1</sup>) due to enhanced Ir–O covalency and electronic state overlap. Time-resolved measurements reveal distinct lifetimes for Ir<sup>5+</sup> and O<sup>−1</sup> states under water oxidation conditions, Ir<sup>5+</sup> remains unreactive whereas O<sup>−1</sup> is consumed at a time constant commensurate with the reaction rate, indicating that O<sup>−1</sup> drives the oxygen evolution reaction. These findings demonstrate the necessity of using multiple operando techniques to gain a unified understanding of the evolution of oxidation states and active sites with potential for water oxidation on oxide catalysts.</p>

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Key role of oxidizing species driving water oxidation revealed by time-resolved optical and X-ray spectroscopies

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月26日

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  • Caiwu Liang,
  • Lucas Garcia Verga,
  • Benjamin Moss,
  • Santosh Kumar,
  • Soren B. Scott,
  • Mark A. Turner,
  • Pilar Ferrer,
  • Veronica Celorrio,
  • Dave C. Grinter,
  • Yemin Tao,
  • Sid Halder,
  • Yifeng Wang,
  • Cindy Tseng,
  • Guangmeimei Yang,
  • Georg Held,
  • Sarah J. Haigh,
  • Aron Walsh,
  • Ifan E. L. Stephens,
  • James R. Durrant,
  • Reshma R. Rao

摘要

Oxidation states underpin the understanding of active states, reaction mechanisms and catalytic performance of electrocatalysts. However, determining them at complex solid–liquid interfaces is challenging. Here we use multimodal spectroscopy to investigate polarized iridium oxide (IrOx) electrodes, a model water oxidation catalyst, to identify potential-dependent iridium and oxygen oxidation states. By integrating multiple operando spectroscopies (optical (ultraviolet–visible), Ir L-edge and O K-edge X-ray absorption spectroscopy) with electrochemistry mass spectrometry and density functional theory calculations, we identify the sequential depletion of electron densities from the Ir5d band (corresponding to Ir3+→Ir4+→Ir5+), followed by electron removal from the O2p band, forming electrophilic oxygen species (O−1) due to enhanced Ir–O covalency and electronic state overlap. Time-resolved measurements reveal distinct lifetimes for Ir5+ and O−1 states under water oxidation conditions, Ir5+ remains unreactive whereas O−1 is consumed at a time constant commensurate with the reaction rate, indicating that O−1 drives the oxygen evolution reaction. These findings demonstrate the necessity of using multiple operando techniques to gain a unified understanding of the evolution of oxidation states and active sites with potential for water oxidation on oxide catalysts.