The hydrothermal synthesis of zinc oxide (ZnO) particles from zinc acetylacetonate monohydrate in “pure” aqueous solution and in aqueous NaOH solution at 90 °C is reported. The structural and morphological properties of ZnO particles were investigated by powder X-ray diffraction, X-ray absorption spectroscopy (XAS), field emission scanning electron microscopy, and transmission electron microscopy. The effect of NaOH on the growth mechanism and photocatalytic performance of hierarchical ZnO structures was investigated. The experimental findings, supported by results of quantum chemical calculations at the level of density functional theory, were used to propose the mechanism of nucleation and preferential growth of finely tuned hollow and nonhollow ZnO structures and their effects on the photocatalytic activity. The calculations indicate that the process of ZnO nucleation in “pure” aqueous solution mainly proceeds by the reaction of small monomers, while tetramers play a crucial role in aqueous NaOH solution. Both the preferred ZnO nanostructure and microstructure growth processes are driven by O–H···O hydrogen bonds as controlling elements. The calculated values of the E O···H interaction indicate a stronger interaction via O–H···O hydrogen bonds in “pure” aqueous media (E O···H = −11.73 kcal mol–1) compared to those obtained in aqueous NaOH solution (E O···H = −8.41 kcal mol–1). The specific structural motif of the (ZnO–H2O)12 dodecamers with calculated negative ΔG*INT free release energy indicates that the formation of anisotropic nanocrystalline ZnO with the c-axis as the primary growth direction is spontaneous and accelerated exclusively in “pure” aqueous solution, whereas it is an unfavorable endergonic process in aqueous NaOH solution (ΔG*INT > 0). Efforts have been made to determine the photocatalytic efficiency of the ZnO samples based on the XAS measurements. ZnO particles obtained in “pure” aqueous solution show the highest photocatalytic activity due to the presence of a larger amount of oxygen vacancies.

The existing setup for time-resolved quick-scanning X-ray absorption spectroscopy (QEXAFS) at beamline P64 at the PETRA III storage ring is complemented by new infrastructure suited for the collection of X-ray diffraction data simultaneously to the QEXAFS experiment. In particular, the sinusoidal periodic movements of the quick-EXAFS mono-chromator are modified in such a way, that an energy plateau with approximately constant energy over a certain time is created in the pre-edge region of the absorption edge of interest. By employing a properly defined trigger signal in this time, the exposure of a two-dimensional X-ray detector placed behind the sample is actuated, thus allowing to collect an X-ray diffraction pattern over a certain angular range as defined by the actual X-ray energy and the position of the 2D-detector. Details of the new setup as well as exemplary results obtained during the solvothermal synthesis of ZnO nanoparticles and the bcc-fcc phase transition of iron at elevated temperatures are presented.

No abstract

The formation of ZnO nanomaterials from different Zn acetylacetonate precursor solutions was studied in situ by employing simultaneous, time-resolved X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS) at the Zn K-edge. The precursor solutions were heated from room temperature to the desired reaction temperatures in a hermetically sealed cell dedicated to X-ray experiments. In general, the first indications for the formation of hexagonal ZnO were found for elevated temperatures of about 80 °C both by XRD and EXAFS, and the contributions increase with temperature and time. However, no reaction intermediates could be proved in addition to the Zn precursors and the formed hexagonal ZnO materials. Furthermore, the results show that the efficiency of the reaction, i.e., the conversion of the precursor material to the ZnO product, strongly depends on the solvent used and the reaction temperature. ZnO formation is accelerated by an increased temperature of 165 °C and the use of 1-octanol, with a conversion to ZnO of more than 80% after only a ca. 35 min reaction time according to a detailed analysis of the EXAFS data. For comparison, an identical concentration of Zn acetylacetonate in water or dilute alkaline NaOH solutions and a reaction temperature of around 90 °C leads to a smaller conversion of approximately 50% only, even after several hours of reaction. The particle size determined from XRD for different orientations shows a preferred orientation along the c-direction of the hexagonal crystal system, as well in accordance with scanning electron microscopy. The LaMer model explained this highly non-uniform growth of needle-like ZnO crystallites.

No abstract