Fabrication of ZnO/ZnAl₂O₄/Au Nanoarrays through DC Electrodeposition Utilizing Nanoporous Anodic Alumina Membranes for Environmental Application

Abstract

In this study, anodic aluminum oxide membranes (AAOMs) and Au-coated AAOMs (AAOM/Au) with pore diameters of 55 nm and inter-pore spacing of 100 nm are used to develop ZnO/AAOM and ZnO/ZnAl2O4/Au nanoarrays of different morphologies. The effects of the electrodeposition current, time, barrier layer, and Au coating on the morphology of the resultant nanostructures were investigated using field emission scanning electron microscopy. Energy dispersive X-ray and X-ray diffraction were used to analyze the structural parameters and elemental composition of the ZnO/ZnAl2O4/Au nanoarray, and the Kirkendall effect was confirmed. The developed ZnO/ZnAl2O4/Au electrode was applied to remove organic dyes from aqueous solutions, including methylene blue (MB) and methyl orange (MO). Using a 3 cm2 ZnO/ZnAl2O4/Au sample, the 100% dye removal for 20 ppm MB and MO dyes at pH 7 and 25 °C was achieved after approximately 50 and 180 min, respectively. According to the kinetics analysis, the pseudo-second-order model controls the dye adsorption onto the sample surface. AAOM/Au and ZnO/ZnAl2O4/Au nanoarrays are also used as pH sensor electrodes. The sensing capability of AAOM/Au showed Nernstian behavior with a sensitivity of 65.1 mV/pH (R2 = 0.99) in a wide pH range of 2–9 and a detection limit of pH 12.6, whereas the ZnO/ZnAl2O4/Au electrode showed a slope of 40.1 ± 1.6 mV/pH (R2 = 0.996) in a pH range of 2–6. The electrode’s behavior was more consistent with non-Nernstian behavior over the whole pH range under investigation. The sensitivity equation was given by V(mV) = 482.6 + 372.6 e−0.2095 pH at 25 °C with R2 = 1.0, which could be explained in terms of changes in the surface charge during protonation and deprotonation.

Keywords

• nanoporous alumina membranes
• ZnO
• dye removal
• pH sensor
• nanoarrays
• methylene blue and methyl orange