One-pot gram-scale rapid synthesis of MN complexes with 14-membered ring macrocyclic ligand as a precursor for carbon-based ORR and CORR catalysts.

Herein, CoN, CuN, and NiN complexes with a 14-membered ring hexaazamacrocycle ligand HHAM were synthesised as precursors for ORR and CORR catalysts a one-pot, gram-scale synthesis procedure, which involved microwave heating for only 10 min. Detailed structures of the obtained 14MR-MN complex were revealed by single-crystal X-ray diffraction measurements.

High Durability of a 14-Membered Hexaaza Macrocyclic Fe Complex for an Acidic Oxygen Reduction Reaction Revealed by In Situ XAS Analysis.

Nonplatinum metal (NPM) catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) have been developed; however, NPM catalysts still need to be improved in terms of both their catalytic activity and durability. To overcome these problems, an Fe active site contained within a more compact ligand than conventional, porphyrinic, 16-membered ring ligands, or more specifically, a hexaaza macrocyclic ligand with a 14-membered ring (14MR), was developed. In this study, the durability of the Fe-14MR complex was compared to that of Fe phthalocyanine (FePc), which has a 16-membered ring ligand, using in situ X-ray absorption spectroscopy; demetalation of the Fe complexes was directly observed during electrochemical experiments performed under acidic ORR conditions.