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<p>Achieving specific orbital activation of C ≡ C by controlling the precise atomic architecture of supported metals is crucial for the selective transformation of alkynes. However, its physical mechanism remains a subject of debate. Herein, we construct a well-defined O-bridged CuN<sub>3</sub>-O-CuN<sub>3</sub> integrative catalytic pairs (Cu ICPs) based on Kirkendall effect. As a result, Cu ICPs with mixed Cu<sup>2+</sup>-Cu<sup>3+</sup> species demonstrate &gt;99% conversion and &gt;550 h stability in acetylene hydrochlorination (simulated industrial reaction conditions), showcasing unparalleled performance in the liquid-phase hydrochlorination of five alkynes as well. A combined experimental and theoretical analyses reveal selective coupling between the <i>d</i><sub>xz</sub>/<i>d</i><sub>yz</sub> orbitals of Cu ICPs and the <i>σ</i> orbitals of C ≡ C in C<sub>2</sub>H<sub>2</sub>, leading to the formation of highly reactive di-<i>σ</i>-HC = CH intermediate. Additionally, the presence of the bridged-O species promotes HCl dissociation, altering the addition pathway from the classical Eley-Rideal (E-R) mechanism to a Cl•-trigged Langmuir-Hinshelwood (L-H) mechanism, ultimately reducing the intrinsic energy barrier for addition, and breaking the universal standard electrode potential linear scaling relations.</p>

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Copper integrative catalytic pairs with mixed-valence Cu2+-Cu3+ Species for selective alkyne conversion

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年10月30日

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  • Yuxue Yue,
  • Mingde Yu,
  • Zhangyi Yao,
  • Guangzong Fang,
  • Bolin Wang,
  • Saisai Wang,
  • Chunxiao Jin,
  • Renqin Chang,
  • Tulai Sun,
  • Zhiyan Pan,
  • Yihan Zhu,
  • Feng Ryan Wang,
  • Xiaonian Li,
  • Jia Zhao

摘要

Achieving specific orbital activation of C ≡ C by controlling the precise atomic architecture of supported metals is crucial for the selective transformation of alkynes. However, its physical mechanism remains a subject of debate. Herein, we construct a well-defined O-bridged CuN3-O-CuN3 integrative catalytic pairs (Cu ICPs) based on Kirkendall effect. As a result, Cu ICPs with mixed Cu2+-Cu3+ species demonstrate >99% conversion and >550 h stability in acetylene hydrochlorination (simulated industrial reaction conditions), showcasing unparalleled performance in the liquid-phase hydrochlorination of five alkynes as well. A combined experimental and theoretical analyses reveal selective coupling between the dxz/dyz orbitals of Cu ICPs and the σ orbitals of C ≡ C in C2H2, leading to the formation of highly reactive di-σ-HC = CH intermediate. Additionally, the presence of the bridged-O species promotes HCl dissociation, altering the addition pathway from the classical Eley-Rideal (E-R) mechanism to a Cl•-trigged Langmuir-Hinshelwood (L-H) mechanism, ultimately reducing the intrinsic energy barrier for addition, and breaking the universal standard electrode potential linear scaling relations.