Promotion of Catalytic Oxygen Reduction Reactions: The Utility of Proton Management Substituents on Cobalt Porphyrins.

Three ABAB-type cobalt -tetraarylporphyrins with fluorine (), acetic acid (), and cyanoacetic acid () groups at the -positions of phenyl rings at the 10,20-positions are synthesized and evaluated as catalysts for oxygen reduction reactions (ORRs). In density functional theory calculations, the frontier molecular orbitals of these complexes were found to be stabilized relative to model complexes with electron-withdrawing atoms or moieties on the -aryl rings. Electrochemical measurements suggest that electrodes with ( exhibit the most positive ORR potential values and the highest limiting current density in both acidic and alkali electrolytes, while the electrocatalyst exhibits extremely low ORR performance. The electron transfer numbers for the electrocatalysts are more than 3.0, indicating that a mixture of 2- and 4-electron transfer pathways occurs. The results demonstrate that coupling the hydrogen bonding properties and electron-withdrawing abilities through rational design of the substituent at the -position is an efficient way to modify the ORR performance.