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 C₂H₄ production efficiencies. In this work, we developed a synergetic-tandem strategy to construct a copper-based composite catalyst for the electroreduction of CO₂ to C₂H₄, 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 Cu₂O 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 Cu₂O nanoparticles for further C₂H₄ production. Accordingly, the resultant catalyst affords an exceptional CO₂-to-C₂H₄ 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.