A novel Ni-complex nanocatalyst for efficient electrochemical oxidation of alcohol in alkaline medium: Mechanism and DFT study

Abstract

A novel catalyst based on nanoparticles of Ni(II) complex was developed to enhance the activity toward alcohol oxidation and hence its possible application in direct alcohol fuel cells (DAFCs). The [NiII(ABP)2] complex was formed in a molar ratio 1(Ni):2(ABP), where (ABP) was synthesized based on 4-(Dimethylamino)benzaldehyde (DMBA), 4-Aminoantipyrine (AAP) and 2-aminophenol (AP) through two condensation steps. Several characterization techniques were used to evaluate the structure of the synthesized compounds, such as elemental analysis, mass, FTIR, UV–Vis, 1HNMR , magnetic, molar conductance and XRD. Transmission and scanning electron microscope (TEM and SEM) images of separated [NiII(ABP)2] complex revealed particles with a size lower than 26 nm. SEM for [NiII(ABP)2]/GCE before and after ethanol oxidation was performed along with EDX and mapping techniques. The computational DFT (density functional theory) calculations supported the octahedral geometry shape of the prepared [NiII(ABP)2] chelate. Several octahedral structures involved in a purposed mechanism were studied using DFT to show the expected optimized shapes formed during ethanol oxidation. Also, the alcohol adsorption simulation was performed using Dmol3 numerical DFT modules to calculate the adsorption energy of alcohols on nickel complex surface. Additionally, the activity toward oxidation of alcohols with different sizes and stereochemistry (methanol, ethanol, propanol, and isopropanol) was investigated in an alkaline medium. The electrode activity was represented for each alcohol as a function of anodic oxidation current. Whereas the electrode achieved 14, 26, 6, and 4 mA cm−2 for methanol, ethanol, propanol, and isopropanol, respectively. Moreover, several parameters were calculated to judge the electrode performance, like diffusion coefficient, catalytic rate constant, stability, Tafel slope, and charge transfer resistance. The theoretical calculations and the experimental findings strongly correlate with each other, where Ni-complex showed the greatest catalytic activity toward ethanol oxidation.