Cobalt(II) Schiff-Base Complexes with Substituents of Varying Electron‑Withdrawing Character: Synthesis, Characterization, DFT Calculations and Application as Electrocatalysts for Oxygen Reduction Reaction

Abstract

Developing new non-noble metal electrocatalysts for oxygen reduction reaction (ORR) is an essential challenge in electrochemical device research. Among these, we highlight the metal Schiff-base complexes, which can be used as modified carbon paste electrodes (CPE). Herein, we present a facile one-pot method for preparing a new family of cobalt(II) complexes with Schiffbase ligands obtained from glycine and para-substituted aldehydes. Complexes were characterized by different techniques, and the effects of para-substituents on the electronic properties of the complexes were confirmed by ultraviolet-visible spectroscopy and cyclic voltammetry (CV). The CV was also used to evaluate the ORR behavior of metal complex-modified CPE in an alkaline medium. The three complex-modified CPE were found to be highly effective for ORR, and the electron-withdrawing character of para-substituent affects the electrochemical reactivity. Density functional theory (DFT) calculations were used to complement the study and correlate the electrochemical activity, the redox potentials, and the Hammett parameter (σp) with the singly occupied molecular orbital (SOMO) energy of the complexes. DFT data were also able to shed light on the likely ORR mechanism. In summary, electronic tuning of the ligand affects the electronic properties of the metal center and allows for systematic oxygen reduction-catalytic control.