Substituents and the induced partial charge effects on cobalt porphyrins catalytic oxygen reduction reactions in acidic medium.

Charge states at the catalytic interface can intensely alter the charge transfer mechanism and thus the oxygen reduction performance. Two symmetric cobalt porphyrins with electron deficient 2,1,3-benzothiadiazole (BTD) and electron-donating propeller-like triphenylamine (TPA) derivatives have been designed firstly, to rationally generate intramolecular partial charges, and secondly, to utilize the more exposed molecular orbitals on TPA for enhancing the charge transfer kinetics. The catalytic performance of the two electrocatalysts was examined for oxygen reduction reactions (ORR) in acidic electrolyte. It was found that BCP1/C with two BTD groups showed greater reduction potential but less limiting current density as compared to BCP2/C bearing BTD-TPA units. The reduced potential of BCP2/C was proposed to the introduction of the electron-donating ability of TPA, which may decrease the adsorption affinity of oxygen to the cobalt center. Both dipole-induced partial charge effect and the more exposed cation orbitals of the 3D structural TPA were proposed to contribute to the increased response current of BCP2/C. In addition, BCP2/C attained more than 80% of HO generation in acidic solution, which may also relate to the structural effect. These findings may provide new insight into the structural design of organic electrocatalysts and deep understanding on the interfacial charge transfer mechanism for ORR.