One-step pyrolysis synthesis of nitrogen, manganese-codoped porous carbon encapsulated cobalt-iron nanoparticles with superior catalytic activity for oxygen reduction reaction

Replacing precious metal catalysts with low-price and abundant catalysts is one of urgent goals for green and sustainable energy development. It is imperative yet challenging to search low-cost, high-efficiency, and long-durability electrocatalysts for oxygen reduction reaction (ORR) in energy conversion devices. Herein, three-dimensional low-cost Co3Fe7 nanoparticles/nitrogen, manganese-codoped porous carbon (Co3Fe7/N, Mn-PC) was synthesized with the mixture of dicyandiamide, cobalt (II) tetramethoxyphenylporphyrin (Co(II)TMOPP), hemin, and manganese acetate by one-step pyrolysis and then acid etching. The resultant Co3Fe7/N, Mn-PC exhibited excellent durability and prominent ORR activity with more positive onset potential (Eonset, 0.98 V) and half-wave potential (E1/2, 0.87 V) in 0.1 M KOH electrolyte, coupled with strong methanol resistance. The pyrolysis temperature and optimal balance of graphite with pyridine-nitrogen are of significance for the ORR performance. The prepared Co3Fe7/N, Mn-PC displayed excellent ORR performance over commercial Pt/C in the identical environment. It was ascribed to the uniform 3D architecture, Mn- and N-doping effects by finely adjusting the electronic structures, coupled with the synergistic catalytic effects of multi-compositions and multi-active sites. This work provides some constructive guidelines for preparation of low-cost and high-efficiency ORR electrocatalysts.