Insight into the Growth Mechanism and Photocatalytic Behavior of Tubular Hierarchical ZnO Structures: An Integrated Experimental and Theoretical Approach

The hydrothermal synthesis of zinc oxide (ZnO) particles from zinc acetylacetonate monohydrate in pure aqueous solution and in aqueous NaOH solution at 90 degrees C is reported. The structural and morphological properties of ZnO particles were investigated by powder Xray 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 center dot center dot center dot O hydrogen bonds as controlling elements. The calculated values of the E-O center dot center dot center dot H interaction indicate a stronger interaction via O-H center dot center dot center dot O hydrogen bonds in pure aqueous media (E-O center dot center dot center dot H = -11.73 kcal mol(-1)) compared to those obtained in aqueous NaOH solution (E-O center dot center dot center dot H = -8.41 kcal mol(-1)). The specific structural motif of the (ZnO-H2O)(12) dodecamers with calculated negative Delta G* 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 (Delta G*(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.

Automated summary

Hydrothermal synthesis of ZnO particles was carried out in pure aqueous solution and aqueous NaOH solution. The presence of NaOH affected the growth mechanism and photocatalytic performance of ZnO structures. The formation of ZnO nanostructures was influenced by the interaction through O-H hydrogen bonds in different solutions.