Highly Selective CO2 Electroreduction to C2H4 Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu2O Nanoparticles via a Synergetic‐Tandem Strategy

Abstract Low *CO coverage on the active sites is a major hurdle in the tandem electrocatalysis, resulting in unsatisfied C 2 H 4 production efficiencies. In this work, we developed a synergetic‐tandem strategy to construct a copper‐based composite catalyst for the electroreduction of CO 2 to C 2 H 4 , which was constructed via the template‐directed polymerization of ultrathin Cu(II) porphyrin organic framework incorporating atomically isolated Cu(II) porphyrin and Cu(II) bipyridine sites on a carbon nanotube (CNT) scaffold, and then Cu 2 O nanoparticles were uniformly dispersed on the CNT scaffold. The presence of dual active sites within the Cu(II) porphyrin organic framework create a synergetic effect, leading to an increase in local *CO availability to enhance the C−C coupling step implemented on the adjacent Cu 2 O nanoparticles for further C 2 H 4 production. Accordingly, the resultant catalyst affords an exceptional CO 2 ‐to‐C 2 H 4 Faradaic efficiency (FE C2H4 ) of 71.0 % at −1.1 V vs reversible hydrogen electrode (RHE), making it one of the most effective copper‐based tandem catalysts reported to date. The superior performance of the catalyst is further confirmed through operando infrared spectroscopy and theoretic calculations.