In‐Situ HF Forming Agents for Sustainable Manufacturing of Iron‐Based Oxygen Reduction Reaction Electrocatalysis Synthesized Through Sacrificial Support Method

Abstract Fe−N x −Cs being suitable to replace scarce and overpriced platinum group metals (PGMs) for cathodic oxygen reduction reaction (ORR) are gaining significant importance in the fuel cell arena. Although the typical sacrificial support method (SSM) ensures the superior electrocatalytic activity of derived Fe−N x −C, removing silica hard templates always remains a great challenge due to the hazardous use of highly toxic and not environmentally friendly hydrofluoric acid. Herein, strategic insight was given to modified SSM by exploiting the in‐situ formation of HF, deriving from the decomposition of NH 4 HF 2 and NaF, to dissolve silica templates, thus avoiding the direct use of HF. First, the suitable molar ratio between the etching agent and the silica was analyzed, revealing that NH 4 HF 2 efficiently dissolved silica even in a stoichiometric amount, whereas an excess of NaF was required. However, both etching agents exhibited conformal removal of silica while dispersed active moieties within the highly porous architecture of derived electrocatalysts were left behind. Moreover, NH 4 HF 2 ‐washed counterparts demonstrated relatively higher performance both in acidic and alkaline media. Notably, with NH 4 HF 2 ‐washed Fe−N x −C electrocatalyst, a remarkable onset potential of 970 mV (vs RHE) was achieved with nearly tetra‐electronic ORR as the peroxide yield remained less than 10 % in the alkaline medium.