Creation of densely exposed and cavity-edged single Fe active sites for enhanced oxygen electroreduction

The performance of oxygen reduction reaction (ORR) on Fe-N-C single-atom catalysts (SACs) is still less satisfactory due to the rather low atomutilization of active sites. Here, a novel acetate thermolysis-assisted route is proposed to create hierarchical carbon nanocages of Fe-N-C SACs (FeSA-N/Cs-OAc) by selective cleavage of carbon layers, which features abundant edge-sited Fe-N-4 moieties in well-defined mesoporous channels. Benefiting from the ultra-high site density and utilization of Fe-N-4 moieties, the optimized FeSA-N/Cs-OAc catalyst demonstrates excellent ORR activities marked by extraordinarily high half-wave potentials (E-1/2) of 0.94 V and 0.82 V in alkaline and acidic electrolytes. Zn-air battery using FeSA-N/Cs-OAc as cathode delivers a power density of 165 mW cm(-2), and the maximum output power in H-2-O-2 fuel cell reaches 640 mW cm(-2). The abundant mesoporosity makes most Fe-N-4 sites accessible and simultaneously produces in-plane pore defects that reduced adsorption energy of *OH (-0.72 eV), finally presenting remarkably enhanced ORR performance.

Automated summary

Hierarchical carbon nanocages of Fe-N-C single-atom catalysts (FeSA-N/Cs-OAc) were created using a novel acetate thermolysis-assisted route, resulting in abundant edge-sited Fe-N-4 moieties in well-defined mesoporous channels. The optimized FeSA-N/Cs-OAc catalyst showed excellent oxygen reduction reaction (ORR) activities and demonstrated high performance in zinc-air batteries and fuel cells.