Intrinsic Defect-Rich Graphene Coupled Cobalt Phthalocyanine for Robust Electrochemical Reduction of Carbon Dioxide

Carbon-based matrix is known to exert a profound influence on the stability and activity of a supported molecular catalyst for electrochemical CO2 reduction reaction (eCO2RR), while regulating the interfacial π–π interaction by designing functional species on the carbon matrix has seldom been explored. Herein, promoted π electron transfer between a graphene substrate and cobalt phthalocyanine (CoPc) is achieved by introducing abundant intrinsic defects into graphene (DrGO), which not only generates more electrochemically active Co sites and leads to a positive shift of the Co2+/Co+ reduction potential but also enhances the CO2 chemical adsorption. Consequently, as compared to the defect-free counterpart rGO-CoPc, DrGO-CoPc could yield CO with a Faradaic efficiency (FECO) higher than 85% in a wide potential range from −0.53 to −0.88 V, and the largest FECO and partial CO current density (JCO) achieve 90.2% and 73.9 mA cm–2, respectively. More importantly, both FECO and JCO can be dramatically improved when conducting eCO2RR in an ionic liquid-based electrolyte, for which FECO is higher than 90.0% in a wide potential range of 600 mV, with the peak JCO of up to 113.6 mA cm–2 in an H-type cell. The excellent eCO2RR performance of DrGO-CoPc rates itself as one of the best immobilized molecular catalysts.