Sulfur Doping versus Hierarchical Pore Structure: The Dominating Effect on the Fe–N–C Site Density, Activity, and Selectivity in Oxygen Reduction Reaction Electrocatalysis

[Image: see text] Nitrogen doping has been always regarded as one of the major factors responsible for the increased catalytic activity of Fe–N–C catalysts in the oxygen reduction reaction, and recently, sulfur has emerged as a co-doping element capable of increasing the catalytic activity even more because of electronic effects, which modify the d-band center of the Fe–N–C catalysts or because of its capability to increase the Fe–N(x) site density (SD). Herein, we investigate in detail the effect of sulfur doping of carbon support on the Fe–N(x) site formation and on the textural properties (micro- and mesopore surface area and volume) in the resulting Fe–N–C catalysts. The Fe–N–C catalysts were prepared from mesoporous carbon with tunable sulfur doping (0–16 wt %), which was achieved by the modulation of the relative amount of sucrose/dibenzothiophene precursors. The carbon with the highest sulfur content was also activated through steam treatment at 800 °C for different durations, which allowed us to modulate the carbon pore volume and surface area (1296–1726 m(2) g(–1)). The resulting catalysts were tested in O(2)-saturated 0.5 M H(2)SO(4) electrolyte, and the site density (SD) was determined using the NO-stripping technique. Here, we demonstrate that sulfur doping has a porogenic effect increasing the microporosity of the carbon support, and it also facilitates the nitrogen fixation on the carbon support as well as the formation of Fe–N(x) sites. It was found that the Fe–N–C catalytic activity [E(1/2) ranges between 0.609 and 0.731 V vs reversible hydrogen electrode (RHE)] does not directly depend on sulfur content, but rather on the microporous surface and therefore any electronic effect appears not to be determinant as confirmed by X-ray photoemission spectroscopy (XPS). The graph reporting Fe–N(x) SD versus sulfur content assumes a volcano-like shape, where the maximum value is obtained for a sulfur/iron ratio close to 18, i.e., a too high or too low sulfur doping has a detrimental effect on Fe–N(x) formation. However, it was highlighted that the increase of Fe–N(x) SD is a necessary but not sufficient condition for increasing the catalytic activity of the material, unless the textural properties are also optimized, i.e., there must be an optimized hierarchical porosity that facilitates the mass transport to the active sites.