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<p>Nucleophilic oxidation reactions (NORs) are key for high-value organics in electrosynthesis, but limited by slow dehydrogenation kinetics and competing oxygen evolution reactions (OER). While low-coordinated Ni species exhibit enhanced activity in rate-determining electrochemical deprotonation, they suffer irreversible oxidation with rapid performance degradation. Herein, we develop a class of oxyanion-stabilized low-coordinated Ni catalysts for highly efficient and durable oxidation of diverse nucleophiles including urea, methanol, and biomass-derived 5-hydroxymethylfurfural. Bicarbonate ligands form an electrostatically repulsive microenvironment, suppressing parasitic OER and Ni over-oxidation via dynamic ligand-cation coordination. These mediators form bifunctional channels, linking Ni<sup>2-δ</sup>/Ni<sup>3-δ</sup> reversible transition-based deprotonation and nucleophilic H-transfer, boosting dehydrogenation. A prototype catalyst engineered with bicarbonate ligands via electrochemical pre-reduction achieves 500 mA cm<sup>−2</sup> at 1.42 V (versus reversible hydrogen electrode) for urea oxidation and sustains stability for 1100 hours at 100 mA cm<sup>−2</sup>. Scaling to 100 cm<sup>2</sup> anion-exchange membrane reactor yields H<sub>2</sub> and valorized organics, showing sustainable electrosynthesis potential.</p>

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Oxyanions stabilized low-coordinated nickel species for efficient and durable nucleophilic electrooxidation

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年12月18日

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  • Xiaokang Liu,
  • Chengxiang Shi,
  • Gong Zhang,
  • Ruijie Gao,
  • Lun Pan,
  • Xiangwen Zhang,
  • Zhen-Feng Huang,
  • Jinlong Gong,
  • Ji-Jun Zou

摘要

Nucleophilic oxidation reactions (NORs) are key for high-value organics in electrosynthesis, but limited by slow dehydrogenation kinetics and competing oxygen evolution reactions (OER). While low-coordinated Ni species exhibit enhanced activity in rate-determining electrochemical deprotonation, they suffer irreversible oxidation with rapid performance degradation. Herein, we develop a class of oxyanion-stabilized low-coordinated Ni catalysts for highly efficient and durable oxidation of diverse nucleophiles including urea, methanol, and biomass-derived 5-hydroxymethylfurfural. Bicarbonate ligands form an electrostatically repulsive microenvironment, suppressing parasitic OER and Ni over-oxidation via dynamic ligand-cation coordination. These mediators form bifunctional channels, linking Ni2-δ/Ni3-δ reversible transition-based deprotonation and nucleophilic H-transfer, boosting dehydrogenation. A prototype catalyst engineered with bicarbonate ligands via electrochemical pre-reduction achieves 500 mA cm−2 at 1.42 V (versus reversible hydrogen electrode) for urea oxidation and sustains stability for 1100 hours at 100 mA cm−2. Scaling to 100 cm2 anion-exchange membrane reactor yields H2 and valorized organics, showing sustainable electrosynthesis potential.