Highly Efficient Oxygen Reduction Reaction Electrocatalysts Synthesized under Nanospace Confinement of Metal–Organic Framework

The output energy capacity of green electrochemical devices, e.g., fuel cells, depends strongly on the sluggish oxygen reduction reaction (ORR), which requires catalysts. One of the desired features for highly efficient ORR electrocatalytic materials is the richness of well-defined activate sites. Herein, we developed a facile approach to prepare highly efficient nonprecious metal and nitrogen-doped carbon-based ORR catalysts based on covalent organic polymers (COPs) synthesized in situ in the nanoconfined space of highly ordered metal organic frameworks (MOFs). The MOF templet ensured the developed electrocatalysts possess a high surface area with homogeneously distributed small metal/nitrogen active sites, as confirmed by X-ray absorption fine structure measurements and first-principles calculations, leading to highly efficient ORR electrocatalytic activity. Notably, the developed COP-TPP(Fe)@MOF-900 exhibits a 16 mV positive half-wave potential compared with the benchmarked Pt/C.