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<p>Single-atom catalysts (SACs) enable atomic-level control over active sites, but orbital-level manipulation to steer catalytic behavior remains challenging. Here, we address this issue through <i>d</i>-orbital engineering of Cu SACs, achieving simultaneous control over coordination geometry (Cu-N<sub>3</sub>) and high metal loading (33.2 wt%) for direct benzene-to-phenol oxidation with H<sub>2</sub>O<sub>2</sub>. The tri-coordinated Cu SAC (Cu-N<sub>3</sub>-33.2) exhibits the highest performance with 85.8% benzene conversion and a turnover frequency of 680.3 h<sup>−1</sup> at 60 <sup>o</sup>C, ranking it among the best metal-based catalysts. In-situ ATR-IR spectroscopy and DFT calculations reveal that dynamically formed Cu-O intermediates, driven by <i>p-d</i> orbital hybridization between Cu (<i>d</i> orbitals) and O (<i>p</i> orbitals), lower the H<sub>2</sub>O<sub>2</sub> activation barrier by 0.98 eV compared to Cu-N<sub>4</sub> sites. High-density atomic Cu sites prevent over-oxidation by consuming singlet oxygen (<sup>1</sup>O<sub>2</sub>). This work establishes a dual-parameter optimization paradigm, including orbital configuration and site density, redefining design principles for selective oxidation SACs.</p>

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Manipulating d-orbital of Cu single atom site by coordination engineering for selective oxidation of benzene

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年7月1日

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  • Shuchun Li,
  • Changsheng Cao,
  • Jiabin Chen,
  • Wen Wen,
  • Xuefei Zhang,
  • Longji Cui,
  • Yuke Li,
  • Xing Huang,
  • Yu Tang,
  • Zailai Xie

摘要

Single-atom catalysts (SACs) enable atomic-level control over active sites, but orbital-level manipulation to steer catalytic behavior remains challenging. Here, we address this issue through d-orbital engineering of Cu SACs, achieving simultaneous control over coordination geometry (Cu-N3) and high metal loading (33.2 wt%) for direct benzene-to-phenol oxidation with H2O2. The tri-coordinated Cu SAC (Cu-N3-33.2) exhibits the highest performance with 85.8% benzene conversion and a turnover frequency of 680.3 h−1 at 60 oC, ranking it among the best metal-based catalysts. In-situ ATR-IR spectroscopy and DFT calculations reveal that dynamically formed Cu-O intermediates, driven by p-d orbital hybridization between Cu (d orbitals) and O (p orbitals), lower the H2O2 activation barrier by 0.98 eV compared to Cu-N4 sites. High-density atomic Cu sites prevent over-oxidation by consuming singlet oxygen (1O2). This work establishes a dual-parameter optimization paradigm, including orbital configuration and site density, redefining design principles for selective oxidation SACs.