Asymmetric Cu₁-N₃-P-C active centers for efficient acetylene hydrochlorination

We investigated the pivotal role of active center symmetry on the stability of reactant adsorption and the transition state dynamics within the context of acetylene hydrochlorination. Our innovative approach involved the integration of phosphorus into a nitrogen-doped carbon framework and introduced the single Cu center, culminating in the development of novel copper-nitrogen-phosphorus-carbon (Cu-NPC) catalysts. These catalysts are distinguished by their asymmetrical Cu₁-N₃-P-C chemical environment. Our kinetic studies shed light on the underlying mechanisms contributing to the superior performance of the Cu-NPC catalysts. These catalysts not only enhance the reaction rate by moderating the adsorption strength of reactants, thereby optimizing the reaction kinetics, but also demonstrate an outstanding ability to mitigate the risk of carbon deposition, a common challenge that compromises catalyst longevity and efficiency. This is evidenced by a notably low deactivation rate of 0.027 h⁻¹ at a high C₂H₂ weight hourly space velocity (WHSV) of 1.4 ${\text{g}}_{{\text{C}}_2{\text{H}}_2}\cdot {{\text{g}}_{\text{cat}}}^{-1}\cdot {\text{h}}^{-1}$. This research not only advances our understanding of the critical influence of active center symmetry on catalyst performance but also paves the way for the rational design of advanced catalysts tailored for specific industrial applications.