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<p>Stabilizing metal oxides is a prerequisite for elucidating their intrinsic mechanistic roles and sustaining high electrocatalytic activity. Here, we synthesize a high-temperature-phase La<sub>2</sub>O<sub>3</sub>-socketed sub-2 nm δ-Bi<sub>2</sub>O<sub>3</sub> heterojunction (δ-Bi<sub>2</sub>O<sub>3</sub>/La<sub>2</sub>O<sub>3</sub>) that suppresses Bi<sup>3+</sup> reduction to metallic Bi, achieving ≥95% formate Faradaic efficiency for ~200 hours in industrial-level electrolyzers. Electronic structure analyses reveal that strong electrostatic interactions between δ-Bi<sub>2</sub>O<sub>3</sub> and La<sub>2</sub>O<sub>3</sub> drive oxygen migration to the interface, contracting δ-Bi<sub>2</sub>O<sub>3</sub> domains and enhancing La–Bi <i>d-p</i> orbital hybridization. This structural relaxation stabilizes interfacial Bi–O–La linkages and electron-deficient Bi<sub>2</sub>O<sub>3+x</sub> species under cathodic potentials, as confirmed by in situ X-ray absorption spectroscopy. Pourbaix diagrams and in situ infrared spectroscopy demonstrate that La<sub>2</sub>O<sub>3</sub> promotes water dissociation to form a hydroxylated δ-Bi<sub>2</sub>O<sub>3</sub> surface under working potentials, enhancing protonation propensity. Consequently, the energy barrier for the rate-determining step (*CO<sub>2</sub> → *HCOO) is lowered to +0.15 eV on δ-Bi<sub>2</sub>O<sub>3</sub>/La<sub>2</sub>O<sub>3</sub>, significantly lower than the +0.83 eV barrier on pristine δ-Bi<sub>2</sub>O<sub>3</sub>. This work establishes a sub-nanoscale oxide/oxide heterojunction strategy to stabilize high-valent metal sites, enabling sustainable electrochemical conversion.</p>

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Stabilizing sub-2 nm δ-Bi2O3 via strong lanthanide-oxide-support interaction for durable CO2 electroreduction to formate

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年4月24日

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  • Qianmin Wu,
  • Cui Li,
  • Yuxuan Wu,
  • Qing Liang,
  • Xuyu Lv,
  • Yanhong Li,
  • Chang Wang,
  • Mengjie Wu,
  • Lichun Kong,
  • Ji-Qing Lu,
  • Wei Zhang,
  • Zhengquan Li,
  • De-Li Chen,
  • Jing Zhou,
  • Fa Yang

摘要

Stabilizing metal oxides is a prerequisite for elucidating their intrinsic mechanistic roles and sustaining high electrocatalytic activity. Here, we synthesize a high-temperature-phase La2O3-socketed sub-2 nm δ-Bi2O3 heterojunction (δ-Bi2O3/La2O3) that suppresses Bi3+ reduction to metallic Bi, achieving ≥95% formate Faradaic efficiency for ~200 hours in industrial-level electrolyzers. Electronic structure analyses reveal that strong electrostatic interactions between δ-Bi2O3 and La2O3 drive oxygen migration to the interface, contracting δ-Bi2O3 domains and enhancing La–Bi d-p orbital hybridization. This structural relaxation stabilizes interfacial Bi–O–La linkages and electron-deficient Bi2O3+x species under cathodic potentials, as confirmed by in situ X-ray absorption spectroscopy. Pourbaix diagrams and in situ infrared spectroscopy demonstrate that La2O3 promotes water dissociation to form a hydroxylated δ-Bi2O3 surface under working potentials, enhancing protonation propensity. Consequently, the energy barrier for the rate-determining step (*CO2 → *HCOO) is lowered to +0.15 eV on δ-Bi2O3/La2O3, significantly lower than the +0.83 eV barrier on pristine δ-Bi2O3. This work establishes a sub-nanoscale oxide/oxide heterojunction strategy to stabilize high-valent metal sites, enabling sustainable electrochemical conversion.