Carboxyl induced ultrahigh defects and boron/nitrogen active centers in cobalt-embedded hierarchically porous carbon nanofibers: The stable oxygen reduction reaction catalysis in acid.

Transition metal-nitrogen-carbon (MNC) type catalysts have been considered a promising alternative to noble metals for oxygen reduction reaction (ORR) electrocatalysis. Nevertheless, poor stabilities of MNC catalysts in acidic solutions limit their commercialization. In this study, we design and synthesize novel three-dimensional (3D) cobalt (Co) nanoparticles encapsulated in ultrahigh content of boron (B) and nitrogen (N) -doped hierarchically porous carbon nanofibers (denoted as Co@BN-PCNFs) by carbonizing the 3D acetic acid/cobalt nitrate/4-hydroxybenzeneboronic acid/polyvinylpyrrolidone precursor networks woven using electrospinning method under a nitrogen atmosphere. The optimal Co@BN-PCNFs-900 catalyst has abundant micro/mesopores and numerous topological defects and exhibits the largest surface area. Under the synergistic effect of oxygen-containing acetic acid molecules and the electrospinning technology, 5.87 at.% of B and 5.91 at.% of N atoms were doped into carbon nanofibers. Specifically, B/N electrocatalytic active centers (including BC, pyridinic-N/CoNC, pyrrolic-N, and graphitic-N) of approximately 8.70 at.% were successfully introduced into the skeletons of Co@BN-PCNFs-900. In 0.1 M KOH, the ORR onset potential (E) and half-wave potential (E) of Co@BN-PCNFs-900 were ∼ 64 and ∼ 63 mV, respectively, more positive than those of 20 wt% Pt/C. Additionally, in 0.5 M HSO, the ORR E and E values of Co@BN-PCNFs-900 were only ∼ 11 and ∼ 7 mV, respectively, more negative than those of 20 wt% Pt/C. As the 3D hierarchically porous architectures, topological carbon edges, BC, and partial NC/CoNC are relatively stable, the Co@BN-PCNFs-900 exhibits excellent stability toward ORR catalysis in both acidic and basic media. These favorable properties of Co@BN-PCNFs-900 nanofibers make them the best non-noble metal-based carbonaceous electrocatalysts for ORR in acidic electrolytes.