Effects of tuning the structural symmetry of cobalt porphyrin on electrocatalytic oxygen reduction reactions.

Metalloporphyrins have attracted significant attention as highly promising alternatives to Pt-based electrocatalysts in the realm of oxygen reduction reactions (ORRs). While the structure of porphyrin is widely recognized as a pivotal factor influencing the ORR performance, the impact of molecular symmetry, which is one of the key properties of the molecular structure, has rarely been understood and its effects remain largely unexplored. Herein, we designed and synthesized two triphenylamine (TPA)-substituted cobalt porphyrins, the asymmetric aBz-TCoP and the symmetric Bz-2TCoP, which are doped onto carbon black to construct composite catalysts for ORRs. The electronic structures of both porphyrins are determined through density functional theory (DFT) calculations, and the morphology and electronic states of the composites are examined by spectroscopic techniques. A series of electrochemical measurements demonstrate the superior activity, selectivity and durability of Bz-2TCoP/C to aBz-TCoP/C in ORRs conducted in both acidic and alkaline electrolytes. The improved ORR properties of the symmetric porphyrin may stem from the steric properties rather than the electronic properties of the chemical structure. This work represents a preliminary study on the effects of porphyrin structural symmetry on electrocatalysis and provides a potential strategy for further structural modifications of metalloporphyrins, as non-noble metal electrocatalysts, to enhance the ORR performance.