Morphological and microstructural engineering of Mn-N-C with strengthened Mn-N bond for efficient electrochemical oxygen reduction reaction

Revealing the correlation between the micro–macro structures and active sites of transition metal-nitrogen-carbon (M−N−C) for electrochemical oxygen reduction reaction (ORR) is essential to develop non-precious metal catalyzed fuel cells and metal-air batteries. Herein, Mn-N-C catalysts with various morphologies and microstructures were prepared using Mn2+ coordinated bis(imino)-pyridine-based polymer with N-rich content as a new platform of precursor, which was synthesized via a condensation reaction of 1H-1, 2, 4-Triazole-3, 5-Diamine and 2, 6-Diacetylpyridine. Results demonstrate that morphologies and fine structures (pore structure, N dopants, surface area, and atomic Mn-N bond length, etc.) of Mn-N-C catalysts are strongly dependent on the growth of the specific precursor with and without NaCl as a template and the secondary calcination temperature can further optimize the bond length of Mn-Nx moieties, resulting in significant activity differences between correspondingly derived Mn-N-C catalysts for ORR. Compared to Mn-N-C derived from the synthesized precursor without NaCl, Mn-N-C obtained by the precursor grown directly on NaCl features an ultra-thin nanosheet-like structure with a hierarchical pore distribution and a shorter Mn-N bond, presenting high ORR performance with a half-wave potential of 0.88 V in 0.1 M KOH and a tiny potential loss of 11 mV after 30 K cycles, which is also proved by high-performance practical single Zn-Air battery (139 mW·cm−2) and proton exchange membrane fuel cell (400 mW·cm−2). This work provides a new understanding of the critical role of morphology and Mn-N bonding length of M−N−C for enhancing ORR and a new route of developing non-Fe/Co-based M−N−C catalysts for electrocatalysis.