Direct methanol fuel cell with enhanced oxygen reduction performance enabled by CoFe alloys embedded into N-doped carbon nanofiber and bamboo-like carbon nanotube

The exploration of cost-effective electrocatalysts with high catalytic activity and methanol tolerance to replace precious metal catalysts in the oxygen reduction reaction (ORR) is highly desirable for direct methanol fuel cells (DMFCs). Herein, we report a novel complex composed of a CoFe alloy with a modulated electronic structure confined to nitrogen-doped carbon nanofiber (NCNF) and bamboo-like carbon nanotube (BCNT) by tuning the molar ratio of Co and Fe (CoFe@NCNF/BCNT). The synthetized catalysts possess one-dimensional (1D) mesoporous structure, high specific surface area, and rich pyridinic-N content. Notably, the Co1Fe1@NCNF/BCNT and Co1Fe3@NCNF/BCNT (Co:Fe ≈ 1:1 and 1:3) exhibited enhanced oxygen reduction activity and methanol tolerance, compared to unmodified samples. In addition, alkaline DMFCs containing Co1Fe1@NCNF/BCNT and Co1Fe3@NCNF/BCNT presented high power density (29.10 and 31.11 mW cm-2), exceeding that of Pt/C-modified DMFC (27.23 mW cm-2). Furthermore, the Co1Fe1@NCNF/BCNT-catalyzed DMFC exhibited high stability. This improved catalytic activity can be attributed to the rich surface area, controllable alloy composition, optimized N configuration, and favorable electronic interaction. The as-developed CoFe@NCNF/BCNT with multifunctional components may open a new avenue for designing highly active cathode catalysts for various fuel cells.