Highly Immobilized Bimetallic Fe/M‐N₄ (M‐ Mg or Zn) Conductive Metal–Organic Frameworks on Nitrogen‐Doped Porous Carbon for Efficient Electrocatalytic Hydrogen Evolution and Oxygen Reduction Reactions

Abstract

Herein, a simple method is proposed for developing bimetallic Fe/M‐N4/nitrogen‐doped porous carbon (NPC) (M‐Zn or Mg) conductive metal–organic framework (c‐MOF) composites because of their great potential in replacing conventional catalysts. The prepared composite MOF exhibits remarkable catalytic activity for both hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), surpassing the performance of the state‐of‐the‐art transition metal‐N4 cathode catalysts. These composites demonstrate excellent selectivity for a four‐electron transfer, facilitated by an associative reaction pathway that functions as the rate‐determining step. Therefore, they offer high half‐wave and onset potential values for ORR, i.e., 0.92 and 1.02 V for Fe/Mg‐N4‐NPC (hexaminobenzene (HAB)‐3@NPC) at a current density of 4.11 mA cm−2, and 0.89 and 0.99 V for Fe/Zn‐N4‐NPC (HAB‐2@NPC) at a current density of 3.8 mA cm−2, respectively. In addition, they provide low overpotentials of 21 and 64 mV at the current density of 10 mA cm−2 with Tafel slopes of 47.9 and 34.2 mV dec−1 for HER, respectively. Furthermore, when utilized as the cathode in bifunctional electrode assembly cells, they provide low cell voltages of 1.412 V at a current density of 20mA cm−2. In the membrane electrode assembly, the HAB‐3@NPC composite demonstrates an optimal power density of 0.861 Wcm−2, thus underscoring its potential in practical applications.