We report a new production pathway for a variety of metal oxide nanocrystallites via submerged illumination in water: submerged photosynthesis of crystallites (SPSC). Similar to the growth of green plants by photosynthesis, nanocrystallites shaped as nanoflowers and nanorods are hereby shown to grow at the protruded surfaces via illumination in pure, neutral water. The process is photocatalytic, accompanied with hydroxyl radical generation via water splitting; hydrogen gas is generated in some cases, which indicates potential for application in green technologies. Together with the aid of ab initio calculation, it turns out that the nanobumped surface, as well as aqueous ambience and illumination are essential for the SPSC method. Therefore, SPSC is a surfactant-free, low-temperature technique for metal oxide nanocrystallites fabrication.

When applied in optoelectronic devices, a ZnO semiconductor dominantly absorbs or emits ultraviolet light because of its direct electron transition through a wide energy bandgap. On the contrary, crystal defects and nanostructure morphology are the chief key factors for indirect, interband transitions of ZnO optoelectronic devices in the visible light range. By ultraviolet illumination in ultrapure water, we demonstrate here a conceptually unique approach to tune the shape of ZnO nanorods from tapered to capped-end via apical surface morphology control. We show that oxygen vacancy point defects activated by excitonic effects near the tip-edge of a nanorod serve as an optoelectrical hotspot for the light-driven formation and tunability of the optoelectrical properties. A double increase of electron energy absorption on near band edge energy of ZnO was observed near the tip-edge of the tapered nanorod. The optoelectrical hotspot explanation rivals that of conventional electrostatics, impurity control, and alkaline pH control-associated mechanisms. Thus, it highlights a new perspective to understanding light-driven nanorod formation in pure neutral water.

We report the fabrication of flower-like CuO nanostructured surfaces via submerged photo-synthesis of crystallites (SPSC), which requires only UV illumination in neutral water. In this paper, we discuss the reaction mechanism of the photochemical formation of the SPSC-fabricated CuO nanostructures in detail based on surface microstructural analyses and a radiation-chemical consideration with additional gamma-ray irradiation. Since the SPSC method for surface nanostructural fabrication can work at low temperatures at atmospheric pressure without using harmful substances, it is a potential fabrication method for green nanotechnology applications. In this vein, the antibacterial activity of the nano-flowered CuO surfaces was tested against Gram-positive (Staphylococcus aureus) bacteria and Gram-negative (Escherichia coli K12) bacteria, and the results demonstrate that the nano-flowered CuO nanostructures act as an effective antimicrobial agent.

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Recently, metal oxide nanocrystallites have been synthesized through a new pathway, i.e., the submerged photosynthesis of crystallites (SPSC), and flower-like ZnO nanostructures have been successfully fabricated via this method. However, the photochemical reactions involved in the SPSC process and especially the role of light are still unclear. In the present work, we discuss the reaction mechanism for SPSC-fabricated ZnO nanostructures in detail and clarify the role of light in SPSC. The results show that both photoinduced reactions and hydrothermal reactions are involved in the SPSC process. The former produces OH radicals, which is the main source of OH− at the ZnO crystal tips, whereas the latter generates ZnO. Although ZnO nanocrystals can be obtained under both UV irradiation and dark conditions with the addition of thermal energy, light promotes ZnO growth and lowers the water pH to neutral, whereas thermal energy promotes ZnO corrosion and increases the water pH under dark conditions. The study concludes that the role of light in the submerged photosynthesis of crystallites process is to enhance ZnO apical growth at relatively lower temperature by preventing the pH of water from increasing, revealing the environmentally benign characteristics of the present process.