Green bio-synthesis of Ni/montmorillonite nanocomposite using extract of Allium jesdianum as the nano-catalyst for electrocatalytic oxidation of methanol

In this work, synthesis of Ni nanoparticles was carried out successfully by water extract of Allium jesdianum as a biochemical reducing agent in the presence of montmorillonite clay (MMT) as a natural solid support for the first time. Then the electrochemical activity of the synthesized nanocomposite was investigated in methanol electrocatalytic oxidation. MMT with high cation exchange capacity and nano layer structure was exposed to ion exchange conditions in nickel solution. Then Ni²⁺ ion exchanged form was used in this process as a source of ions and also capping agent. Water extract of Allium jesdianum used as a reducing agent due to abundant availability of phenolic and flavonoid contents. The synthesized Ni/MMT nanocomposite was characterized using UV-Vis spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM) and Energy-dispersive X-ray spectroscopy (EDX). The surface of prepared modified electrode has been characterized using SEM to evaluate the morphology, showing uniform dispersion of Ni nanoparticles with mean diameter of 12 to 20 nm. The modified carbon paste electrode was then used in methanol electrocatalytic oxidation reaction. Methanol oxidation on the proposed modified electrode surface occurs at 0.6 V and 0.3 V in alkaline and acidic medium respectively. Also, the results showed the better performance of modified electrode toward methanol electrocatalytic oxidation in comparison with carbon paste electrode that is modified by ion exchanged MMT. Charge transfer coefficients and apparent charge transfer rate constant for the modified electrode in the absence of methanol in alkaline medium were respectively found as: α_a = 0.53, α_c = 0.37 and k_s = 1.6×10^-1 s^-1. Also, the average value of catalytic rate constant for the electrocatalytic oxidation of methanol by the prepared nano-catalyst was estimated to be about 0.9 L·mol^-1·s^-1 by chronoamperometry technique. The prepared electrode was also effective for electrocatalytic oxidation of ethanol and formaldehyde in alkaline medium.