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

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.