Efficient oxygen reduction electrocatalysis on Mn3O4 nanoparticles decorated N-doped carbon with hierarchical porosity and abundant active sites

Abstract

Transition metal on nitrogen-doped carbons (M-N-C, M = Fe, Co, Mn, etc.) are a group of promising sustainable electrocatalysts toward oxygen reduction reaction (ORR). Compared to its Fe, Co analogues, Mn–N–C possesses the advantage of being inert for catalyzing Fenton reaction, and thus is expected to offer higher durability, but its ORR activity needs essential improvement. Herein, an efficient Mn–N–C ORR catalyst composed of Mn3O4 nanoparticles supported on nitrogen-doped carbon was successfully synthesized by pyrolysis of cyanamide/Mn-incorporated polydopamine (PDA) film coated carbon black (CB), where the presence of N-rich cyanamide confers abundant Mn-Nx active sites and rich micropore/mesopores to the catalyst. In an alkaline medium, as-synthesized Mn–N–C electrocatalyst outperforms commercial Pt/C catalyst in terms of onset potential (0.98 V, vs. RHE), half-wave potential (0.868 V, vs. RHE), and limiting current density. Meanwhile, it exhibits excellent durability and resistance to methanol. In a Zinc-air primary battery, it demonstrates better performance as a cathodic catalyst than Pt/C.