Nanocasting SiO<sub>2</sub> into metal-organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts.

Jiao, Long; Zhang, Rui; Wan, Gang; Yang, Weijie; Wan, Xin; Zhou, Hua; Shui, Jianglan; Yu, Shu-Hong et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

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 SiO<sub>2</sub> into porphyrinic metal-organic frameworks (MOFs). The pyrolysis of SiO<sub>2</sub>@MOF composite affords single-atom Fe implanted N-doped porous carbon (Fe<sub>SA</sub>-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 SiO<sub>2</sub> in MOF provides additional protection by creating thermally stable FeN<sub>4</sub>/SiO<sub>2</sub> interfaces. Thanks to the high-density Fe<sub>SA</sub> sites, Fe<sub>SA</sub>-N-C demonstrates excellent oxygen reduction performance in both alkaline and acidic medias. Meanwhile, Fe<sub>SA</sub>-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<sub>SA</sub>, Co<sub>SA</sub>, Ni<sub>SA</sub>).