… such composites have been grown with a potentiostatic anodic/cathodic pulse-plating procedure and characterized by a multi-technique approach, combining a suite of in situ and ex situ spectroscopic methods with electrochemical measurements, in view of improving their electrocatalytic ORR activity and durability. In particular the pyrolysis process has been monitored in situ by micro-XPS: Mn, initially present in a core–shell structure with a metallic core and a Mn(II, III) shell, tends to oxidise achieving a final composition in which Mn(III) and Mn(IV) dominate; the partial decomposition of Mn/PPy results in a rearrangement of the chemical structure of PPy with the formation of novel Me–N bonds

and graphitic-N functionalities, that can be regarded as the active sites of this class of electrocatalysts. In terms of the same electrocatalytic figures of merit, our electrocatalyst outperforms MnOx supported on a range of carbons, such as C- powders, vulcan, and nanocarbon.