Effects of the induced micro- and meso-porosity on the single site density and turn over frequency of Fe-N-C carbon electrodes for the oxygen reduction reaction.

[Display omitted] • A controlled evolution of micro and mesopores improves the Fe-N x site density. • NO-stripping showed the improvement of both site density and TOF. • The % of active iron increases in samples showing higher mesopores content. • Micro and meso pore are important either in site formation or site accessibility. Fe-N-C have emerged as one of the best non-PGM alternatives to Pt/C catalysts for the electrochemical reduction of O 2 in fuel cells. In this work, we explore the effect of steam and CO 2 treatments at high temperatures on the nanometric porous structure of a commercial carbon black. Using those support materials, we synthesize different Fe-N-C catalysts to achieve a better understanding on the role of micro- and mesopores of the support towards catalytic site formation and site activity. Different time and temperature of treatments result in an almost linear increment of surface area and microporous volume, which allows better nitrogen functionalization. Site density evaluation, performed using a recently described NO-stripping technique, showed an increase in site density and TOF which correlates well with the morphology variation. The percentage of active iron increases from 2.65 % to 14.74 % in activated catalysts confirming a better access of electrolyte to the iron sites. [ABSTRACT FROM AUTHOR]