Electrocatalytic oxidation of methanol on NiZnsalenA modified glassy carbon electrode

Nickel and zinc salen complexes were simultaneously encapsulated in the supercages of the mesoporous zeolite A by using the flexible ligand method. This heterogeneous catalyst NiZnsalenA was characterized by X-ray diffraction, infrared spectroscopy, diffuse reflectance UV-vis spectroscopy, elemental analysis, and N2 adsorption/desorption experiments. The techniques of cyclic voltammetry (CV) and chronoamperometry (CA) were employed to investigate the electrochemical behavior and electrocatalytic activity toward the oxidation of methanol on NiZnsalenA glassy carbon electrode (GCE) in 0.1-M NaOH solution. The CV results presented a pair of redox peaks associated with the Ni2+(salen)(OH)2/Ni3+(salen)O(OH) redox couple. NiZnsalenA also showed the superior electrocatalytic activity to the oxidation of methanol than pure Ni-modified electrode, mainly due to a synergetic effect in NiZnsalenA. This synergetic effect may originate from the interaction of Ni(salen) and Zn(salen) and/or the formation of dinuclear salen complexes via the lattice oxygen of the zeolitic host. The effects of the scan rate, methanol concentration, and OH− concentration on methanol oxidation are investigated, and a possible mechanism is proposed that the oxidation of methanol is done by reaction with Ni3+(salen)O(OH) and also direct electrooxidation reaction. The kinetic parameters such as the electron transfer coefficient α and the rate constant ks of the electrode reaction were estimated to be 0.39 and 1.59 s−1, respectively. In both the CA and CC studies, the process of methanol oxidation followed a Cottrellian behavior, and the diffusion coefficients DCA and DCC of methanol represented the similar tendency, where an initial sharp drop was terminated to a very slow change as the concentration of methanol was approaching 0.7 M. The catalytic rate constant kcat increased rapidly until the concentration of methanol was increased above 0.7 M, and then the values of kcat remained almost constant.