Facile and Reproducible Synthesis of Nanostructured Colloidal ZnO Nanoparticles from Zinc Acetylacetonate: Effect of Experimental Parameters and Mechanistic Investigations

A facile and reproducible route to nanostructured colloidal ZnO nanoparticles was developed by controlled hydrolysis and condensation of zinc acetylacetonate in alkaline conditions. By reaction of an ethanolic solution of Zn(acac)(2) with NaOH in a 1:2 molar ratio, after reflux, ZnO spherical nanoparticles were obtained that displayed a homogeneous size distribution; particle diameters ranged from 6 to 10 run, as evidenced by transmission electron microscopy (TEM) analysis. The same reaction was carried out also in water, glycerol and 1,2-propanediol, to investigate the effect of the solvent viscosity and dielectric constant on the final features of the obtained material. Irrespective of the nature of the solvent, X-ray diffraction (XRD) analysis shows the formation of hexagonal ZnO, whereas the presence of residual unreacted Zn(acac)(2) could be ruled out. Indeed, different particle sizes and very different morphologies were obtained. Also the reflux step was shown to be a key factor in avoiding the fast precipitation of a floc and achieving a pure compound, which was isolated and thoroughly characterised. The composition of the obtained ZnO was determined by elemental analysis, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), showing the formation of pure ZnO. IR spectroscopy evidenced the presence of adsorbed organic ligands on the colloid surfaces. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) revealed the presence of medium- to high-strength acidic sites on the ZnO surface. To gain a deeper insight into the formation mechanisms of these nanostructures, time-resolved UV/Vis and XAS studies were performed on the ethanol solution used for the synthesis of the oxide and also on the solid specimen, obtained after the refluxing step. No remarkable changes could be evidenced in the solution after the addition of an understoichiometric amount of NaOH, but the growth of the ZnO nanoparticles could be followed by UV/Vis spectra. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)