Fashedemi, Omobosede O.Ozoemena, Kenneth I.2014-06-192014-06-192013Fashedemi, OO & Ozoemena, KI 2013, 'Enhanced methanol oxidation and oxygen reduction reactions on palladium-decorated FeCo@Fe/C core–shell nanocatalysts in alkaline medium', Physical Chemistry Chemical Physics, vol. 15, 20982-20991.1359-734510.1039/c3cp52601ahttp://hdl.handle.net/2263/40292Palladium based nano-alloys are well known for their unique electrocatalytic properties. In this work, a palladium-decorated FeCo@Fe/C core–shell nanocatalyst has been prepared by a new method called microwave-induced top-down nanostructuring and decoration (MITNAD). This simple, yet efficient technique, resulted in the generation of sub-10 nm sized FeCo@Fe@Pd nanocatalysts (mainly 3–5 nm) from a micron-sized (0.21–1.5 mm) FeCo@Fe/C. The electrocatalytic activities of the core–shell nanocatalysts were explored for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline medium. A negative shift of 300 mV in the onset potential for MOR was observed, with a current thrice that of the Pd/C catalysts. A very low resistance to electron transfer (Rct) was observed while the ratio of forward-to-backward oxidation current (If/Ib) was doubled. The overpotential of ORR was significantly reduced with a positive shift of about 250 mV and twice the reduction current density was observed in comparison with Pd/C nanocatalysts with the same mass loading. The kinetic parameters (in terms of the Tafel slope (b) = 59.7 mV dec 1 (Temkin isotherm) and high exchange current density ( jo) = 1.26 10 2 mA cm 2) provide insights into the favorable electrocatalytic performance of the catalysts in ORR in alkaline media. Importantly, the core–shell nanocatalyst exhibited excellent resistance to possible methanol cross-over during ORR, which shows excellent promise for application in direct alkaline alcohol fuel cells (DAAFCs).en© the Owner Societies 2013Oxygen reductionAlkaline mediumMicrowave-induced top-down nanostructuring and decoration (MITNAD)FeCo@Fe@Pd nanocatalystsPalladiumDirect alkaline alcohol fuel cells (DAAFCs)Methanol oxidation reaction (MOR)Article