Cu Single‐Atom Catalysts for High‐Selectivity Electrocatalytic Acetylene Semihydrogenation

Abstract The site isolation strategy has been employed in thermal catalytic acetylene semihydrogenation to inhibit overhydrogenation and C−C coupling. However, there is a dearth of analogous investigations in electrocatalytic systems. In this work, density functional theory (DFT) simulations demonstrate that isolated Cu metal sites have higher energy barriers on overhydrogenation and C−C coupling. Following this result, we develop Cu single‐atom catalysts highly dispersed on nitrogen‐doped carbon matrix, which exhibit high ethylene selectivity (>80 % Faradaic efficiency for ethylene, <1 % Faradaic efficiency for C 4 , and no ethane) at high concentrations of acetylene. The superior performance observed in the electrocatalytic selective hydrogenation of acetylene can be attributed to the weak adsorption of ethylene intermediates and highly energy barriers on C−C coupling at isolated sites, as confirmed by both DFT calculations and experimental results. This study provides a comprehensive understanding of the isolated sites inhibiting the side reactions of electrocatalytic acetylene semihydrogenation.