Reactivity descriptors for Cu bis-phenanthroline catalysts for the hydrogen peroxide reduction reaction

• Published in: Electrochimica acta 2020-10, Vol.357, p.136881, Article 136881
• Main Authors: Muñoz-Becerra, Karina, Báez, Daniela F., Zagal, José H., Bollo, Soledad, Toro-Labbé, Alejandro, Venegas, Ricardo, Recio, F. Javier
• Format: Article
• Language: English
• Subjects: Aqueous solutions; Biosensors; Catalysts; Catalytic activity; Chemical reactions; Chemical reduction; Copper catalysts; Electrodes; Glassy carbon; Hydrogen peroxide; Hydrogen peroxide reduction reaction; Hydrogen peroxide sensor; Reactivity descriptors
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2020.136881

Following previous studies where the metal-centered redox potentials of MN4 complexes are proposed as a reactivity descriptor for different electrochemical reactions, in the present work we expand this idea to a series of substituted Cu(I)-phenanthrolines adsorbed on glassy carbon electrodes as catalysts for the hydrogen peroxide reduction reaction (HPRR) in aqueous media. As the foot of the wave for HPRR on Cu-based modified electrodes is closely related to the Cu(II)/Cu(I) formal potential, we have found a linear correlation between the catalytic activity expressed as (log i)E and the E°'Cu(II)/Cu(I) redox potential of the complexes with a slope (dE°/dlogi)E close to +0.120 V dec−1, showing that the catalytic activity increases with the shift of E°'Cu(II)/Cu(I) to more positive potentials as a result of the electron-withdrawing nature of the substituents on the ligands. Moreover, the theoretical differences in the calculated chemical potentials (Δμ) of the reactive species follow a similar trend with the E°'Cu(II)/Cu(I) where a positive shift of this parameter is related with a higher Δμ and in consequence, with high catalytic activity. Furthermore, this strategy can be used for the smart design of biosensors as it was shown by the electroanalytical results. [Display omitted]