Effects of support material and electrolyte on a triphenylamine substituted cobalt porphyrin catalytic oxygen reduction reaction.

The interfacial charge transfer conditions are crucial for understanding the catalytic mechanism and thus developing high performing electrocatalysts. To justify the effects of support material and electrolyte on metalloporphyrin catalytic oxygen reduction reaction (ORR), we synthesize a symmetric triphenylamine (TPA) substituted cobalt porphyrin, nominated as s-TPA-CoP , and select carbon black and multi-walled carbon nanotubes as the supports to fabricate composite catalysts. The ORR performances are measured in both acidic and alkaline solutions. While the support material affects negligibly on reduction potentials, the stronger π-π stacking in s-TPA-CoP/CNT , as revealed by X-ray photoelectron spectroscopy measurements, leads to greater limiting current densities and larger electron transfer numbers as compared to s-TPA-CoP/XC in either electrolyte. Both composites perform better ORR activity but poorer 4-electron selectivity in base than in acid, whose origins are discussed from the aspects of interfacial charge states and inner- / outer-sphere electron transfer mechanisms. Strikingly, s-TPA-CoP/CNT exhibits an electron transfer number of 3.8 in acid, demonstrating the privilege of TPA as the substitution on monometallic cobalt porphyrins in chasing 4-electron transfer oxygen reduction. [Display omitted] • A triphenylamine substituted cobalt porphyrin is designed for ORR. • Carbon black and nanotubes are used as the support materials. • ORR activities are recorded in both acid and alkali electrolytes. • Stronger π-π stacking leads to greater ORR activity of the composites. • Both composites exhibit better ORR activity but poorer selectivity in base than in acid. [ABSTRACT FROM AUTHOR]