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<p>Preferential oxidation of CO (CO-PROX) is essential for H<sub>2</sub> purification in proton-exchange membrane fuel cells. Understanding the intrinsic electronic structural factors that influence catalytic performance is key to rational catalyst design. Using Pt single-atom catalysts supported on Fe<sub>2</sub>O<sub>3</sub> and Fe<sub>3</sub>O<sub>4</sub> as model systems, this work systematically investigates the relationship between structure and performance, focusing on the strength of selective orbital coupling and CO-PROX activity. On both supports, Pt single atoms are stabilized in an embedded form by substituting lattice Fe sites (Pt<sub>1</sub>@FeO<sub><i>x</i></sub>). Furthermore, CO and H<sub>2</sub> are preferentially activated at Pt-lattice O bridge sites, while O<sub>2</sub> activation occurs at Pt sites. Compared to the Pt<sub>1</sub>@Fe<sub>3</sub>O<sub>4</sub> system, the Pt<sub>1</sub>@Fe<sub>2</sub>O<sub>3</sub> system exhibits higher theoretical activity and selectivity, with energy barriers of 0.28&#xa0;eV for CO oxidation and 0.87&#xa0;eV for H<sub>2</sub> oxidation. The enhanced performance of Pt<sub>1</sub>@Fe<sub>2</sub>O<sub>3</sub> stems from its higher lattice O redox activity and an optimal selective orbital coupling strength, measured by the descriptor Σ|Δ<i>ε</i>| (the absolute value sum of band‑center shifts for the dominant interacting orbitals). This creates a clear energetic preference for activating CO over H<sub>2</sub>. This study establishes a semiquantitative structure–activity relationship linking electronic structure, adsorption strength, and catalytic performance, providing concrete theoretical guidance for experimental design of high-performance CO-PROX catalysts.</p>

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Theoretical Study on the Regulation of CO Preferential Oxidation Performance of Pt1@FeOx Single-Atom Catalysts by Selective Orbital Coupling

  • 期刊论文

  • 发表日期：

    2026年6月16日

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  • Xiuhui Zheng,
  • Yaqian Li,
  • Jianlin Cao,
  • Sheng Wei,
  • Defu Yin,
  • Hao Yan,
  • Yongxiao Tuo,
  • Xiang Feng,
  • Chaohe Yang,
  • De Chen

摘要

Preferential oxidation of CO (CO-PROX) is essential for H2 purification in proton-exchange membrane fuel cells. Understanding the intrinsic electronic structural factors that influence catalytic performance is key to rational catalyst design. Using Pt single-atom catalysts supported on Fe2O3 and Fe3O4 as model systems, this work systematically investigates the relationship between structure and performance, focusing on the strength of selective orbital coupling and CO-PROX activity. On both supports, Pt single atoms are stabilized in an embedded form by substituting lattice Fe sites (Pt1@FeOx). Furthermore, CO and H2 are preferentially activated at Pt-lattice O bridge sites, while O2 activation occurs at Pt sites. Compared to the Pt1@Fe3O4 system, the Pt1@Fe2O3 system exhibits higher theoretical activity and selectivity, with energy barriers of 0.28 eV for CO oxidation and 0.87 eV for H2 oxidation. The enhanced performance of Pt1@Fe2O3 stems from its higher lattice O redox activity and an optimal selective orbital coupling strength, measured by the descriptor Σ|Δε| (the absolute value sum of band‑center shifts for the dominant interacting orbitals). This creates a clear energetic preference for activating CO over H2. This study establishes a semiquantitative structure–activity relationship linking electronic structure, adsorption strength, and catalytic performance, providing concrete theoretical guidance for experimental design of high-performance CO-PROX catalysts.