MOF-Derived CoNi Nanoalloy Particles Encapsulated in Nitrogen-Doped Carbon as Superdurable Bifunctional Oxygen Electrocatalyst

Carbon-encapsulated transition metal catalysts have caught the interest of researchers in the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) due to their distinctive architectures and highly tunable electronic structures. In this work, we synthesized N-doped carbon encapsulated with CoNi nanoalloy particles (CoNi@NC) as the electrocatalysts. The metal-organic skeleton ZIF-67 nanocubes were first synthesized, and then Ni2+ ions were inserted to generate CoNi-ZIF precursors by a simple ion-exchange route, which was followed by pyrolysis and with urea for the introduction of nitrogen (N) at a low temperature to synthesize CoNi@NC composites. The results reveal that ZIF-67 pyrolysis can dope more N atoms in the carbon skeleton and that the pyrolysis temperature influences the ORR and OER performances. The sample prepared by CoNi@NC pyrolysis at 650 °C has a high N content (9.70%) and a large specific surface area (167 m2 g-1), with a positive ORR onset potential (Eonset) of 0.89 V vs. RHE and half-wave potential (E1/2) of 0.81 V vs. RHE in 0.1 M KOH, and the overpotential of the OER measured in 1 M KOH was only 286 mV at 10 mA cm-2. The highly efficient bifunctional ORR/OER electrocatalysts synthesized by this method can offer some insights into the design and synthesis of complex metal-organic frameworks (MOFs) hybrid structures and their derivatives as functional materials in energy storage.