Nanocasting SiO₂ into metal–organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts

Single-atom catalysts (SACs) have sparked broad interest recently while the low metal loading poses a big challenge for further applications. Herein, a dual protection strategy has been developed to give high-content SACs by nanocasting SiO₂ into porphyrinic metal–organic frameworks (MOFs). The pyrolysis of SiO₂@MOF composite affords single-atom Fe implanted N-doped porous carbon (Fe_SA–N–C) with high Fe loading (3.46 wt%). The spatial isolation of Fe atoms centered in porphyrin linkers of MOF sets the first protective barrier to inhibit the Fe agglomeration during pyrolysis. The SiO₂ in MOF provides additional protection by creating thermally stable FeN₄/SiO₂ interfaces. Thanks to the high-density Fe_SA sites, Fe_SA–N–C demonstrates excellent oxygen reduction performance in both alkaline and acidic medias. Meanwhile, Fe_SA–N–C also exhibits encouraging performance in proton exchange membrane fuel cell, demonstrating great potential for practical application. More far-reaching, this work grants a general synthetic methodology toward high-content SACs (such as Fe_SA, Co_SA, Ni_SA).