Unveiling Low Temperature Assembly of Dense Fe‐N4 Active Sites via Hydrogenation in Advanced Oxygen Reduction Catalysts

The single-atom Fe-N-C is a prominent material with exceptional reactivity in areas of sustainable energy and catalysis research. It is challenging to obtain the dense Fe-N₄ site without the Fe nanoparticles (NPs) sintering during the Fe-N-C synthesis via high-temperature pyrolysis. Thus, a novel approach is devised for the Fe-N-C synthesis at low temperatures. Taking FeCl₂ as Fe source, a hydrogen environment can facilitate oxygen removal and dichlorination processes in the synthesis, efficiently favouring Fe-N₄ site formation without Fe NPs clustering at as low as 360 °C. We shed light on the reaction mechanism about hydrogen promoting Fe-N₄ formation in the synthesis. By adjusting the temperature and duration, the Fe-N₄ structural evolution and site density can be precisely tuned to directly influence the catalytic behaviour of the Fe-N-C material. The FeNC-H₂-360 catalyst demonstrates a remarkable Fe dispersion (8.3 wt %) and superior acid ORR activity with a half-wave potential of 0.85 V and a peak power density of 1.21 W cm^-2 in fuel cell. This method also generally facilitates the synthesis of various high-performance M-N-C materials (M=Fe, Co, Mn, Ni, Zn, Ru) with elevated single-atom loadings.