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

• Published in: Angewandte Chemie International Edition Vol. 63; no. 33; pp. e202407090 - n/a
• Main Authors: He, Qizhe, Li, Hongwei, Hu, Zhuofeng, Lei, Lei, Wang, Degao, Li, Ting‐Ting
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 12.08.2024
• Edition: International ed. in English
• Subjects: Carbon dioxide; Carbon nanotubes; Catalysts; CO2 Reduction; Copper; Copper oxides; Electrocatalysis; Electrowinning; Ethylene Production; Infrared spectroscopy; Nanoparticles; Porphyrin Frameworks; Porphyrins; Scaffolds; Synergetic-Tandem Strategy; CO2 reduction; Ethylene Production; Porphyrin Frameworks; electrocatalysis; Synergetic-Tandem Strategy
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202407090

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 (FEC2H4) 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. A synergetic‐tandem strategy was developed to construct a copper‐based composite catalyst by dispersing Cu2O nanoparticles on CuPOF‐Bpy@CNT comprising dual active sites for CO2 electroreduction. The synergetic interaction in dual active sites efficiently reduces CO2 to *CO with high concentration, which transferred to the nearby Cu2O sites for *CO dimerization to form *COCOH, affording an exceptional Faradaic efficiency of 71 % for C2H4 production.