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

Abstract 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.