Fe,Cu-codoped metal-nitrogen-carbon catalysts with high selectivity and stability for the oxygen reduction reaction

Metal-nitrogen-carbon materials (M-N-C) are non-noble-metal-based alternatives to platinum-based catalysts and have attracted tremendous attention due to their low-cost, high abundance, and efficient catalytic performance towards the oxygen reduction reaction (ORR). Among them, Fe-based materials show remarkable ORR activity, but they are limited by low selectivity and low stability. To address these issues, herein, we have synthesized FeCu-based M-N-C catalysts, inspired by the bimetal center of cytochrome c oxidase (CcO). In acidic media, the selectivity was notably improved compared with Fe-based materials, with peroxide yields less than 1.2% (<1/3 of the hydrogen peroxide yields of Fe-N-C catalysts). In addition to Cu-N-C catalysts which can catalytically reduce hydrogen peroxide, the reduction current of hydrogen peroxide using FeCu-N-C-20 exceeded that of Fe-N-C by about 6% when the potential was greater than 0.4 V. Furthermore, FeCu-based M-N-C catalysts suffered from only a 15 mV attenuation in their half-wave potentials after 10,000 cycles of accelerated degradation tests (ADT), while there was a 30 mV negative shift for Fe-N-C. Therefore, we propose that the H₂O₂ released from Fe-N_x sites or N-doped carbon sites would be reduced by adjacent Cu-N_x sites, resulting in low H₂O₂ yields and high stability.