Heterogenized Molecular Electrocatalyst Based on a Hydroxo‐Bridged Binuclear Copper(II) Phenanthroline Compound for Selective Reduction of CO₂ to Ethylene

Molecular copper catalysts have emerged as promising candidates for the electrochemical reduction of CO₂. Notable features of such systems include the ability of Cu to generate C₂₊ products and the well‐defined active sites that allow for targeted structural tuning. However, the frequently observed in situ formation of Cu nanoclusters has undermined the advantages of the molecular frameworks. It is therefore desirable to develop Cu‐based catalysts that retain their molecular structures during electrolysis. In this context, a heterogenized binuclear hydroxo‐bridged phenanthroline Cu(II) compound with a short Cu···Cu distance is reported as a simple yet efficient catalyst for electrogeneration of ethylene and other C₂ products. In an aqueous electrolyte, the catalyst demonstrates remarkable performance, with excellent Faradaic efficiency for C₂ products (62%) and minimal H₂ evolution (8%). Furthermore, it exhibits high stability, manifested by no observable degradation during 15 h of continuous electrolysis. The preservation of the atomic distribution of the active sites throughout electrolysis is substantiated through comprehensive characterizations, including X‐ray photoelectron and absorption spectroscopy, scanning and transmission electron microscopy, UV–vis spectroscopy, as well as control experiments. These findings establish a solid foundation for further investigations into targeted structural tuning, opening new avenues for enhancing the catalytic performance of Cu‐based molecular electrocatalysts.