Mn/Co co-doped porous carbon material derived from self-assembly of CoPc and ZIF-11 for oxygen reduction reaction

Developing low-cost, high-performance oxygen reduction reaction (ORR) electrocatalyst plays a key role in promoting the low-carbon green production. Herein, a Mn/Co co-doped carbon-based non-noble metal electrocatalyst (NNME) with enhanced ORR performance was prepared by simply pyrolyzing the self-assembly induced complex precursor of CoPc@Mn-ZIF-11. The obtained NNME demonstrates the half-wave potential of 0.864 V (vs. RHE) in 0.1 M KOH aq., which is comparable to that of the commercial 20% Pt/C and much better than the directly pyrolysis of mechanically blended CoPc and Mn-ZIF-11 without self-assembly method. Especially, our electrocatalyst shows superior durability during accelerated durability test and methanol tolerance to commercial Pt/C in alkaline medium. As evidenced by the physical characterizations, the enhanced ORR activity should have a close relationship with the self-assembly process, which allows the well encapsulation of CoPc into the nanocages of Mn-ZIF-11, thus leading to the uniform dispersion of Mn/Co–N–C species in the carbon matrix after pyrolysis. Besides, the higher content of defects and nitrogen of the synthesized electrocatalyst by self-assembly method should be another key reason for the higher ORR activity than that of the mechanically mixed sample. Graphical abstract Self-assembled CoPc with Mn-ZIF-11 derived electrocatalyst with enhanced ORR activity than the mechanically mixed method