Kramm, U.I.; Herrmann-Geppert, I.; Fiechter, S.; Zehl, G.; Zizak, I.; Dorbandt, I.; Schmeißer, D.; Bogdanoff, P.: Effect of iron-carbide formation on the number of active sites in Fe–N–C catalysts for the oxygen reduction reaction in acidic media. Journal of Materials Chemistry A 2 (2014), p. 2663-2670

In this work Fe–N–C catalysts were prepared by the oxalate-supported pyrolysis of FeTMPPCl or H2TMPP either in the presence or absence of sulfur. The well-known enhancing effect of sulfur-addition on the oxygen reduction activity was confirmed for these porphyrin precursors. The pyrolysis process was monitored in situ by high-temperature X-ray diffraction under synchrotron radiation (HT-XRD) and thermogravimetry coupled with mass-spectroscopy (TG-MS). It was found that the beneficial effect of sulfur could be attributed to the prevention of iron-carbide formation during the heat-treatment process. In the case of pyrolysis of the sulfur-free precursors an excessive iron-carbide formation leads to disintegration of FeN4-centers, hence limiting the number of ORR active sites on the final catalyst. Physical characterization of the catalysts by bulk elemental analysis, X-ray diffraction (XRD), Raman and 57Fe M¨oßbauer spectroscopy confirmed the outcome from HT-XRD and TG-MS. It could be shown that the avoidance of carbide formation during pyrolysis represents a promising way to enhance the density of ORR active sites on those catalysts. This can be done either by sulfur-addition or the performance of an intermediate acid leaching. As iron carbide is often found as a by-product in the preparation of Fe– N–C catalysts this work gives some general strategies for enhancing the density of active sites enabling higher current densities.