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<p>The development of corrosion-resistant low-iridium anode catalysts is the key challenge in proton exchange membrane water electrolysis. However, the fundamental origin of anodic corrosion has been intensely debated over the years, mainly because of the limited mechanistic understanding of the complex proton-coupled electron transfer process. In this work, we employed femtosecond electrochemical transient absorption spectroscopy to probe the spatial–temporal synchronization of protons and electrons during the elementary proton-coupled electron transfer step at the femtosecond (10<sup>−15</sup> s) timescale. Here we show that anodic corrosion is initiated within 100 fs after polarization startup, driven by synchronized protons and electrons coupling at the electrode surface. By introducing a Lewis acid (CeO<sub>2</sub>) as a proton channel, the reaction dynamics of protons and electrons could be decoupled into temporal asynchrony to prevent the generation of soluble Ir<sup>6+</sup> species. Owing to this unique desynchronized proton–electron interaction, the CeO<sub>2</sub>–IrO<sub>2</sub> catalyst demonstrates outstanding stability for about 1,400 h of continuous operation.</p>

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Proton–electron temporal asynchrony on femtosecond timescales enables anti-corrosive low-iridium anodes for PEM electrolysers

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年2月27日

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  • Wei Shen,
  • Fei-Yue Gao,
  • Xiaogang Sun,
  • Haodian Xie,
  • Yang Hu,
  • Huiying Wu,
  • Mietek Jaroniec,
  • Yao Zheng,
  • Pinxian Xi,
  • Chun-Hua Yan,
  • Shi-Zhang Qiao

摘要

The development of corrosion-resistant low-iridium anode catalysts is the key challenge in proton exchange membrane water electrolysis. However, the fundamental origin of anodic corrosion has been intensely debated over the years, mainly because of the limited mechanistic understanding of the complex proton-coupled electron transfer process. In this work, we employed femtosecond electrochemical transient absorption spectroscopy to probe the spatial–temporal synchronization of protons and electrons during the elementary proton-coupled electron transfer step at the femtosecond (10−15 s) timescale. Here we show that anodic corrosion is initiated within 100 fs after polarization startup, driven by synchronized protons and electrons coupling at the electrode surface. By introducing a Lewis acid (CeO2) as a proton channel, the reaction dynamics of protons and electrons could be decoupled into temporal asynchrony to prevent the generation of soluble Ir6+ species. Owing to this unique desynchronized proton–electron interaction, the CeO2–IrO2 catalyst demonstrates outstanding stability for about 1,400 h of continuous operation.