Evaluation of the Specific Activity of M-N-Cs and the Intrinsic Activity of Tetrapyrrolic FeN Sites for the Oxygen Reduction Reaction.

M-N-C electrocatalysts are considered pivotal to replace expensive precious group metal-based materials in electrocatalytic conversions. However, their development is hampered by the limited availability of methods for the evaluation of the intrinsic activity of different active sites, like pyrrolic FeN sites within Fe-N-Cs. Currently, new synthetic procedures based on active-site imprinting followed by an ion exchange reaction, e.g. Zn-to-Fe, are producing single-site M-N-Cs with outstanding activity. Based on the same replacement principle, we employed a conservative iron extraction to partially remove the Fe ions from the N cavities in Fe-N-Cs. Having catalysts with the same morphological properties and Fe ligation that differ solely in Fe content allows for the facile determination of the decrease in density of active sites and their turn-over frequency. In this way, insight into the specific activity of M-N-Cs is obtained and for single-site catalysts the intrinsic activity of the site is accessible. This new approach surpasses limitations of methods that rely on probe molecules and, together with those techniques, offers a novel tool to unfold the complexity of Fe-N-C catalyst and M-N-Cs in general.