Fourteen-Membered Macrocyclic Fe Complexes Inspired by FeN 4 -Center-Embedded Graphene for Oxygen Reduction Catalysis

For the broad application of polymer electrolyte fuel cells (PEFCs), the development of nonprecious-metal (NPM) catalysts for oxygen reduction is extremely important. To date, many NPM catalysts have been synthesized by pyrolyzing Fe-, N-, and C-containing precursors; however, they suffer from low density and uncertain chemical structure of their active sites. This study reports a novel 14-membered macrocyclic Fe complex, which was inspired by FeN4 centers in pyrolyzed catalysts, unlike typical macrocyclic MN4 complexes that have 16-membered rings. This 14-membered macrocycle possesses strong Fe–N bonds with an average bond distance of 1.90 Å, as evidenced by single-crystal X-ray diffraction (XRD), which are markedly shorter than those in porphyrin (2.0 Å). This complex demonstrates high electrocatalytic activity for oxygen reduction in both acidic and basic media.