Boosting C2+ Selectivity in CO₂ Electroreduction on Cu Nanoparticles via Molecular Dispersion of Cobalt Phthalocyanine

Abstract Cu‐based tandem catalysts have been widely studied due to their excellent performance in electrocatalytic reduction of carbon dioxide (CO 2 RR) to produce C 2+ products. However, during the CO 2 RR process, Cu atoms face the issue of dynamic restructuring, resulting in relatively poor stability and single‐product selectivity. Herein, cobalt phthalocyanine (CoPc) was integrated with Cu nanoparticles (NPs) to prepare a tandem catalyst (Cu/CoPc x ) by in‐situ growth method, significantly enhancing the selectivity of Cu‐based catalysts for C 2+ products. The optimal material, Cu/CoPc 0.004 , achieved a Faradaic efficiency (FE) of 73.17% for C 2+ products, with a C 2+ product current density exceeding 377 mA/cm 2 . More importantly, tandem catalyst Cu/CoPc 0.004 exhibits high selectivity for ethylene, achieving a FE of 52.35% at −1.26 V (versus reversible hydrogen electrode) with a high ethylene current density (270 mA/cm 2 ). The experimental results indicate that the interaction between CoPc and Cu NPs introduces numerous oxygen vacancies and stabilizes the presence of Cu + . Moreover, the unique structure of the cascade catalyst enables CoPc to provide a large amount of CO intermediates for Cu active sites, thus, promoting C─C coupling and facilitating the formation of C 2+ products.