Oxygen Reduction Reaction at Penta-Coordinated Co Phthalocyanines

From the early 60s, Co complexes, especially Co phthalocyanines (CoPc) have been extensively studied as electrocatalysts for the oxygen reduction reaction (ORR). Generally, they promote the 2-electron reduction of O₂ to give peroxide whereas the 4-electron reduction is preferred for fuel cell applications. Still, Co complexes are of interest because depending on the chemical environment of the Co metal centers either promote the 2-electron transfer process or the 4-electron transfer. In this study, we synthetized 3 different Co catalysts where Co is coordinated to 5 N atoms using CoN4 phthalocyanines with a pyridine axial linker anchored to carbon nanotubes. We tested complexes with electro-withdrawing or electro-donating residues on the N4 phthalocyanine ligand. The catalysts were characterized by EPR and XPS spectroscopy. Ab initio calculations, Koutecky-Levich extrapolation and Tafel plots confirm that the pyridine back ligand increases the Co-O₂ binding energy, and therefore promotes the 4-electron reduction of O₂. But the presence of electron withdrawing residues, in the plane of the tetra N atoms coordinating the Co, does not further increase the activity of the compounds because of pull-push electronic effects.