• 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.
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