A Porphyrin/Graphene Framework: A Highly Efficient and Robust Electrocatalyst for Carbon Dioxide Reduction

Developing immobilized molecular complexes, which demonstrate high product efficiencies at low overpotential in the electrochemical reduction of CO 2 in aqueous media, is essential for the practical production of reduction products. In this work, a simple and facile self‐assembly method is demonstrated by electrostatic interaction and π–π stacking for the fabrication of a porphyrin/graphene framework (FePGF) composed of Fe(III) tetraphenyltrimethylammonium porphyrin and reduced liquid crystalline graphene oxide that can be utilized for the electrocatalytic reduction of CO 2 to CO on a glassy carbon electrode in aqueous electrolyte. The FePGF results in an outstanding robust catalytic performance for the production of CO with 97.0% faradaic efficiency at an overpotential of 480 mV and superior long‐term stability relative to other heterogeneous molecular complexes of over 24 h (cathodic energy efficiency: 58.1%). In addition, a high surface area carbon fiber paper is used as a substrate for FePGF catalyst, resulting in enhanced current density of 1.68 mA cm −2 with 98.7% CO faradaic efficiency at an overpotential of 430 mV for 10 h, corresponding to a turnover frequency of 2.9 s −1 and 104 400 turnover number. Furthermore, FePGF/CFP has one of the highest cathodic energy efficiencies (60.9%) reported for immobilized metal complex catalysts.