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<p>The electrochemical urea oxidation reaction offers environmental benefits by enabling hydrogen generation and nitrogen recycling. However, catalyst instability caused by surface reconstruction remains a challenge. Here, we develop a heteronuclear vacancy-to-bond strategy that achieves both catalytic activation and structural preservation via atomic-level self-optimization. Using Fe-doped bimetallic frameworks, we construct a self-adaptive coordination microenvironment that dynamically generates controllable ligand vacancies while promoting metal dimerization, leading to shortened interatomic distances. The resulting ligand-vacancy-mediated stabilization delivers an low potential of 1.222 V @ 10 mA cm<sup>−2</sup> (188 mV lower than IrO<sub>2</sub>) with 87.7% Faradaic efficiency for nitrogen oxides. Spectroscopic analysis and theoretical calculations reveal that ligand-deficient structure reduces the C–N cleavage energy from 1.33 eV to 0.75 eV and shifts the rate-determining step from chemical C–N cleavage to potential-dependent *NO oxygenation, lowering the overall energy requirement. In industrial-scale electrolyzers, the catalyst sustains 1 A cm<sup>−2</sup> for 100 h with negligible degradation, achieving 13% energy savings over conventional water splitting. This work investigates a dynamic vacancy-to-bond conversion mechanism, offering insights into the design of adaptive electrocatalysts for sustainable energy applications.</p>

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Dynamic ligand-vacancy engineering drives metal dimerization for efficient urea electrooxidation

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月23日

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  • Mingjie Wu,
  • Jian Luo,
  • Xiaoya Zhan,
  • Junjie Zheng,
  • Xun Cui,
  • Yuanyuan Luo,
  • Yingkui Yang

摘要

The electrochemical urea oxidation reaction offers environmental benefits by enabling hydrogen generation and nitrogen recycling. However, catalyst instability caused by surface reconstruction remains a challenge. Here, we develop a heteronuclear vacancy-to-bond strategy that achieves both catalytic activation and structural preservation via atomic-level self-optimization. Using Fe-doped bimetallic frameworks, we construct a self-adaptive coordination microenvironment that dynamically generates controllable ligand vacancies while promoting metal dimerization, leading to shortened interatomic distances. The resulting ligand-vacancy-mediated stabilization delivers an low potential of 1.222 V @ 10 mA cm−2 (188 mV lower than IrO2) with 87.7% Faradaic efficiency for nitrogen oxides. Spectroscopic analysis and theoretical calculations reveal that ligand-deficient structure reduces the C–N cleavage energy from 1.33 eV to 0.75 eV and shifts the rate-determining step from chemical C–N cleavage to potential-dependent *NO oxygenation, lowering the overall energy requirement. In industrial-scale electrolyzers, the catalyst sustains 1 A cm−2 for 100 h with negligible degradation, achieving 13% energy savings over conventional water splitting. This work investigates a dynamic vacancy-to-bond conversion mechanism, offering insights into the design of adaptive electrocatalysts for sustainable energy applications.