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

Abstract

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)degrees' redox potential of the complexes with a slope (dE degrees/dlogi)(E) close to +0.120 V dec(-1), showing that the catalytic activity increases with the shift of E-Cu(II)/Cu(I)degrees' 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 (Delta mu) of the reactive species follow a similar trend with the E-Cu(II)/Cu(I)degrees' where a positive shift of this parameter is related with a higher Delta mu 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.