Encapsulated cementite enhances catalytic performance of carbon nanotubes for oxygen reduction reaction

The encapsulated cementite changed the electron distribution state of surface layer CNT, which enhanced the catalytic activity for oxygen reduction reaction. [Display omitted] •N-doped CNT with cementite encapsulated was synthesized as a catalyst for ORR.•Encapsulated cementite changed the electron distribution of surface layer CNT.•The E0 and E1/2 of Fe3C@CNT catalyzed ORR is 60 mV higher than that of Pt/C.•Equal-potential circle theory is proposed to explain catalytic mechanism for ORR. Nonprecious-metal-based materials show great potential to be highly efficient catalysts for oxygen reduction reaction (ORR). There is still room for improvement in the performances of nonprecious-metal-based catalysts for ORR. In this paper, we investigated the catalytic performances of N-doped carbon nanotubes (CNTs) with encapsulated cementite (Fe3C@CNT) for ORR. The encapsulation structure was confirmed by scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses. The catalytic performances of Fe3C@CNT for ORR were investigated by cyclic voltammetry, linear sweep voltammetry, Tafel analysis, rotating disk electrode, and rotating ring-disk electrode tests. The results showed that both the onset potential and half-wave potential of Fe3C@CNT-catalyzed ORR were 60 mV higher than those of 20 wt% Pt/C catalyst. Fe3C@CNT catalyzed ORR mainly happened through a four-electron pathway. The long-time running stability of the Fe3C@CNT was also superior to that of the 20 wt% Pt/C catalyst. The eutectic layers between the CNTs and cementite enhanced the electron transfer from the inner-layer CNT to the surface-layer N-doped CNT. Calculations revealed that the iron and carbon in the cementite were in positive and negative electronic states, respectively. The encapsulated cementite promoted the formation of equipotential circles on the surface-layer CNT, which greatly enhanced the catalytic performance of the Fe3C@CNT for ORR. N-doped CNTs with encapsulated cementite show great potential to be high-performance catalysts for ORR.