A manganese(iii) Schiff base complex immobilized on silica-coated magnetic nanoparticles showing enhanced electrochemical catalytic performance toward sulfide and alkene oxidation

Abstract

In this study, a novel Mn(III)–Schiff base complex was synthesized and characterized. The structure of this complex was determined to be a deformed octahedral coordination sphere by single-crystal X-ray diffraction analysis. The Mn(III)–Schiff base complex was supported on silica-coated iron magnetic nanoparticles via axial coordination by one-step complex anchoring to produce a heterogenized nanocatalyst. After this, the complex was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), and powder X-ray diffraction (XRD). Moreover, atomic absorption spectroscopy was used to determine the amount of the loaded metal. The heterogenized nanocatalyst effectively catalyzed the oxidation of a broad range of sulfides and alkenes with H₂O₂ in the presence of a glassy carbon electrode, applying voltage to the reaction mixture. The results showed that the application of a potential to the reaction mixture could significantly decrease the reaction time when compared with the case of similar chemical oxidation reactions. In addition, an excellent value of turnover frequency (17 750 h⁻¹) was achieved for the electrochemical oxidation of styrene. Moreover, the nanocatalyst showed good recoverability without significant loss of its activity within six successive runs in the electrochemical oxidation of methyl phenyl sulfide and cyclooctene. The electrochemical properties and stability of Fe₃O₄@SiO₂-[MnL(OAc)] were investigated by cyclic voltammetry measurements and chronoamperometry technique.