Enhanced cobalt porphyrin-catalytic oxygen reduction reactions by introducing benzoyloxy substitutes

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Vol. 476; p. 146575
• Main Authors: Wei, Yuqin, Zhao, Long, Liang, Yongdi, Yuan, Mingcai, Wu, Qijie, Xue, Zhaoli, Qiu, Xinping, Zhang, Jianming
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-11-2023
• Subjects: Benzoyloxy; Cobalt porphyrin; Electrocatalysis; Interfacial charge transfer; Oxygen reduction reactions; Electrocatalysis; Benzoyloxy; Cobalt porphyrin; Oxygen reduction reactions; Interfacial charge transfer
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2023.146575

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•Three cobalt porphyrins with different substituents are designed for ORRs.•Both carbon nanotubes and carbon black are used to construct composites.•The benzoyloxy-substituted porphyrin exhibited the best in both acid and base.•BA-TPACoP/CNT reaches similar ORR performance to Pt/C particular in base.•Possible origins are analyzed with assistance of theoretical calculations.
Three novel triphenylamine (TPA) cobalt porphyrins Ph-TPACoP, FP-TPACoP and BA-TPACoP are designed to explore their efficacy in electrocatalytic oxygen reduction reactions (ORRs). The porphyrins are coated on carbon nanotubes and carbon black to construct composites for ORRs in alkaline and acidic media. The BA-TPACoP-based composites, on either carbon support and in either electrolyte, exhibit the best ORR performance among the catalysts under the same conditions. Remarkably, BA-TPACoP/CNT attains comparable reduction potentials and response current densities to Pt/C in alkali, and it also exhibits an electron transfer number of 3.94 in acid, reaching close to the 4-electron oxygen reduction. This work demonstrates the efficacy of benzoyloxy substitutes for the ORR improvement and may provide an applicable protocol for engineering efficient metalloporphyrins as electrocatalysts.