The role of chalcogen doping in Fe–N–C catalysts for hydrogen-air polymer electrolyte fuel cells: Selenium doped Fe–N–C.

A spectrum of selenium-doped Fe–N–C catalysts is prepared and scrutinized for acidic oxygen reduction reactions to understand the impact of the presence and amount of chalcogen dopants on the catalytic performance as cathode catalyst layers (CCLs) for H 2 –O 2 and H 2 –air polymer electrolyte membrane fuel cells (PEMFCs). While for a high initial content of Se, all available iron is bonded into iron selenides, a low amount of Se doping yields Fe–N–C catalysts of extensive microporosity, increased nitrogen content, and iron occurring predominantly in the Fe-N x coordination state. The chemistry of the iron-carbon-selenium (Fe–C–Se) system is studied in detail to elucidate the impact of Se on Fe–N–C catalyst formation during pyrolysis. The performance of the Se-doped platinum group metal-free Fe–N–C catalysts in PEMFCs is compared with their commercially available counterpart. The effect of the catalysts' morphology alternation by ball-milling on their performance is also studied. It is concluded that chalcogen doping (either S or Se doping) indirectly impacts Fe–N–C catalyst activity by controlling carbon scaffold properties, while the idea of a direct impact of chalcogen atoms on the Fe-N x catalytic centers is challenged. [Display omitted] • Se-doped Fe–N–C catalysts are studied as CCLs in H 2 –O 2 and H 2 –air PEMFCs. • Se-content is varied in a wide range, yielding a large family of Se-doped Fe–N–C. • Se doping grants enhanced microporosity and formation of Fe–N x sites. • Common characteristics of chalcogen-doped Fe–N–C catalysts are identified. • Ball-milling alters catalysts' morphology, thus improving their activity. [ABSTRACT FROM AUTHOR]