ABSTRACT
Replacing Pt-based catalysts with cost-effective, highly efficient, and durable platinum group metal-free catalysts for the oxygen reduction reaction (ORR) is crucial for commercializing hydrogen fuel cells. Herein, we present a highly active Fe-N-C electrocatalyst that contains both Fe nanoparticles and FeNx active sites derived from an Fe-doped carbonized zeolitic imidazolate framework (ZIF-8). It is found that adjusting the doping amount of Fe in the Fe-doped ZIF-8 precursor alters the morphology of the catalyst after heat treatment. The Fe-N-C-300 composite catalyst with the optimized Fe doping amount exhibits excellent activity, good stability, and remarkable methanol tolerance in the challenging acid environment. This study reveals that a suitable amount of Fe nanoparticles in the catalyst can alter the structure of the FeNx active moieties and increase three-phase boundaries to boost the mass transport, thus leading to improved fuel cell performance. This will have implications for using Fe-N-C catalysts in real applications, as the formation of Fe NPs during the synthesis and reaction is almost inevitable.
ABSTRACT
Combining the advantages of homogeneous and heterogeneous catalytic systems has emerged as a promising strategy for electrochemical CO2 reduction although developing robust, active, product-selective, and easily available, catalysts remains a major challenge. Herein, we report the electroreduction of CO2 catalyzed by cobalt and benzimidazole containing Vitamin B12 immobilized on the surface of reduced graphene oxide (rGO). This hybrid system with a naturally abundant molecular catalyst produces CO with high selectivity and a constant current density in an aqueous buffer solution (pH 7.2) for over 10 h. A Faradaic efficiency (FE) of 94.5% was obtained for converting CO2 to CO at an overpotential of 690 mV with a CO partial current density (jCO) of 6.24 mA cm-2 and a turnover frequency (TOF) of up to 28.6 s-1. A higher jCO (13.6 mA cm-2) and TOF (52.4 s-1) can be achieved with this system at a higher overpotential (790 mV) without affecting the product selectivity (â¼94%) for CO formation. Our experimental findings are corroborated with density functional theory (DFT) studies to understand the influence of the covalently attached and redox-active benzimidazole unit. To the best of our knowledge, this is the first example of naturally abundant vitamin being immobilized on a conductive surface for highly efficient CO2 electroreduction.
