AbstractThe removal of acetylene impurities remains important yet challenging to the ethylene downstream industry. Current thermocatalytic semihydrogenation processes require high temperature and excess hydrogen to guarantee complete acetylene conversion. For this reason, renewable electricity-based electrocatalytic semihydrogenation of acetylene over Cu-based catalysts is an attractive route compared to the energy-intensive thermocatalytic processes. However, active Cu electrocatalysts still face competition from side reactions and often require high overpotentials. Here, we present an undercoordinated Cu nanodots catalyst with an onset potential of −0.15 V versus reversible hydrogen electrode that can exclusively convert C₂H₂ to C₂H₄ with a maximum Faradaic efficiency of ~95.9% and high intrinsic activity in excess of −450 mA cm⁻² under pure C₂H₂ flow. Subsequently, we successfully demonstrate simulated crude ethylene purification, continuously producing polymer-grade C₂H₄ with <1 ppm C₂H₂ for 130 h at a space velocity of 1.35 × 10⁵ ml g_cat⁻¹ h⁻¹. Theoretical calculations and in situ spectroscopies reveal a lower energy barrier for acetylene semihydrogenation over undercoordinated Cu sites than nondefective Cu surface, resulting in the excellent C₂H₂-to-C₂H₄ catalytic activity of Cu nanodots.