Quasi-double-star nickel and iron active sites for high-efficiency carbon dioxide electroreduction

Abstract

Although the Faraday efficiencies (FEs) obtained on most of the Ni based single-atom catalysts (Ni–N–C) are satisfactory (generally >90%) for the electrochemical transfer CO₂ to CO, their practical application is still limited by their high overpotentials (>600 mV vs. RHE), which implies a higher energy consumption to drive the CO₂ RR. In this work, we have prepared a quasi-double star catalyst composed of nearby Ni and Fe active sites via a simple pyrolysis of Ni and Fe co-doped Zn-based MOFs in order to achieve a high selectivity at a low overpotential during the CO₂ RR. Specifically, the optimized Ni/Fe–N–C catalyst shows an exclusive selectivity (a maximum FE(CO) of 98%) at a low overpotential of 390 mV vs. RHE, which is superior to both the single metal counterparts (Ni–N–C and Fe–N–C catalysts) and other state-of-the-art M–N–C catalysts. The DFT results further reveal that regulating the catalytic CO₂ RR performance via nearby Ni and Fe active sites can potentially break the activity benchmark of the single metal counterparts because the neighboring Ni and Fe active sites not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO* in comparison to their single metal counterparts, but also prevent the undesired hydrogen evolution reaction (HER). This work presents a quasi-double-star catalyst composed of two metal sites for high-efficiency CO₂ reduction, which paves the way for the rational design of bimetallic catalysts with separated active sites for other reactions.