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

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 () and Jia Zhao ()
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Yuxue Yue: Institute of Industrial Catalysis of Zhejiang University of Technology
Mingde Yu: Institute of Industrial Catalysis of Zhejiang University of Technology
Zhangyi Yao: University College London
Guangzong Fang: Dalian Institute of Chemical Physics Chinese Academy of Science
Bolin Wang: Northeast Electric Power University
Saisai Wang: Institute of Industrial Catalysis of Zhejiang University of Technology
Chunxiao Jin: Institute of Industrial Catalysis of Zhejiang University of Technology
Renqin Chang: Zhejiang University of Technology Hangzhou
Tulai Sun: Institute of Industrial Catalysis of Zhejiang University of Technology
Zhiyan Pan: Zhejiang University of Technology
Yihan Zhu: Institute of Industrial Catalysis of Zhejiang University of Technology
Feng Ryan Wang: University College London
Xiaonian Li: Institute of Industrial Catalysis of Zhejiang University of Technology
Jia Zhao: Institute of Industrial Catalysis of Zhejiang University of Technology

Nature Communications, 2025, vol. 16, issue 1, 1-15

Abstract: Abstract 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.

Date: 2025
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DOI: 10.1038/s41467-025-64639-w

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