Electrochemically produced films based on individual porphyrins and bimetallic composites: Morphology and electrocatalytic properties in the reaction of oxygen electroreduction

• Published in: Electrochimica acta 2024-04, Vol.484, p.144025, Article 144025
• Main Authors: Kuzmin, Sergey M., Chulovskaya, Svetlana A., Tesakova, Mariya V., Koifman, Oskar I., Parfenyuk, Vladimir I.
• Format: Article
• Language: English
• Subjects: Electrocatalysis; Electrochemical deposition; Morphology; Polyporphyrins
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2024.144025

•Individual Fe- and Mn- porphyrin films vs bimetallic composites.•Film deposition processes, composition and morphologies of the obtained catalysts.•From mixed 2- and 4-electron oxygen reduction to a predominantly 4-electron reaction. In this work, we obtained polyporphyrin films based on Fe(III)Cl-5,10,15,20-tetrakis(4-pyridyl)porphyrin and Mn(III)acetate-5,10,15,20-tetrakis(4-pyridyl)porphyrin and composite films on their basis by electrooxidation-induced electrochemical polymerization. The obtained films produced uniform coatings. Spectral analysis showed that the composite films were enriched with iron complexes. Comparative analysis of the prepared films demonstrated differences between the morphologies of the composite film and films of individual metal complexes. The oxygen electroreduction process on the obtained materials proceeded at more positive values than that on carbositall. The effective number of transferred electrons demonstrated that replacing catalysts based on individual porphyrins with the bimetallic composite changed the process mechanism: while the four-electron mechanism competed with subsequent two-electron reactions on the Fe(III)Cl-5,10,15,20-tetrakis(4-pyridyl)porphyrin and Mn(III)acetate-5,10,15,20-tetrakis(4-pyridyl)porphyrin films, on the bimetallic composite the process mainly represented a four-electron reaction. [Display omitted]