Oxygen reduction activity of Fe/Co/Ni doped MnOx @ graphene nanohybrid: A comparative study.

• Fe, Co, and Ni doped MnO x was grown on NG. • Doped catalysts show better ORR activity than the undoped one. • Doping can tune the Mn valence. • Enhanced activity for doped MnO x owing to increase in Mn valence on doping. We report the electrochemical activity of transition metal ion (Fe, Co and Ni) doped MnO x @ N -graphene (MnO x @NG) hybrid catalysts towards oxygen reduction reaction (ORR). The doped catalysts displayed significantly enhanced electrochemical performance than the undoped one. The Fe doped MnO x @NG exhibited highest positive shift in onset potential (0.93 V vs. RHE), highest electron transfer number (n) (3.87) and lowest peroxide yield (6.35 %) in 0.1 M KOH solution. The Co doped catalyst showed highest current density, which is comparable to that of benchmark 20 wt% Pt/C. The XRD analysis showed that the catalyst samples are poorly crystalline and the doping of either Fe or Co or Ni cation induces formation of Mn 2 O 3 , whereas the undoped catalyst consists of both Mn 2 O 3 and MnOOH. The STEM (scanning transmission electron microscope) micrographs revealed that in all the samples the MnO x nanostructures are well dispersed on NG and the elemental mapping of the doped catalysts showed uniform distribution of dopants. The X-ray photoelectron spectroscopy (XPS) studies revealed that doping of either cation results an increase in the average Mn valency of the host MnO x. The change in crystal structure and corresponding ORR activity has also been investigated with increase in dopant amount for Fe doped samples. [ABSTRACT FROM AUTHOR]