Effect of thermal and mechano-chemical activation on the photocatalytic efficiency of ZnO for drugs degradation.

Over the past few years, pharmaceutical drugs have been considered as emerging pollutants due to their continuous input and persistence in the aquatic ecosystem even at low concentrations. They have been detected worldwide in environmental matrices, indicating their ineffective removal from water and wastewaters using conventional methods. In this study we present photocatalytic purification of water from Acetaminophen and Chloramphenicol by ZnO upon UV-light illumination. Commercial ZnO powders are activated thermally (annealed at different temperatures-100, 200, 300, 400 and 500 °C for 1 h) and mechanically (treated for 5, 15, 20, 30, 40 and 60 min). The mechonoactivation is performed varying the atmosphere in air, or in suspension of ethanol and methanol. The changes in the studied material (phase composition, structure and particle size of the samples) and morphology have been investigated by means of X-ray diffraction and Scanning electron microscopy. The ZnO powders annealed at 100 °C show highest photocatalytic efficiency and rate constant of dye degradation, which is due to the smaller size of nanocrystallites and their better developed surface. The degradation rate of Acetaminophen and Chloramphenicol increases with time of mechanical activation up to 30 min and then decreases. The optimal temperature and time of mechanoactivation are experimentally established.

CdS/ZnS nanocomposites: from mechanochemical synthesis to cytotoxicity issues.

CdS/ZnS nanocomposites have been prepared by a two-step solid-state mechanochemical synthesis. CdS has been prepared from cadmium acetate and sodium sulfide precursors in the first step. The obtained cubic CdS (hawleyite, JCPDS 00-010-0454) was then mixed in the second step with the cubic ZnS (sphalerite, JCPDS 00-005-0566) synthesized mechanochemically from the analogous precursors. The crystallite sizes of the new type CdS/ZnS nanocomposite, calculated based on the XRD data, were 3-4 nm for both phases. The synthesized nanoparticles have been further characterized by high-resolution transmission electron microscopy (HRTEM) and micro-photoluminescence (µPL) spectroscopy. The PL emission peaks in the PL spectra are attributed to the recombination of holes/electrons in the nanocomposites occurring in depth associated with Cd, Zn vacancies and S interstitials. Their photocatalytic activity was also measured. In the photocatalytic activity tests to decolorize Methyl Orange dye aqueous solution, the process is faster and its effectivity is higher when using CdS/ZnS nanocomposite, compared to single phase CdS. Very low cytotoxic activity (high viability) of the cancer cell lines (selected as models of living cells) has been evidenced for CdS/ZnS in comparison with CdS alone. This fact is in a close relationship with Cd(II) ions dissolution tested in a physiological solution. The concentration of cadmium dissolved from CdS/ZnS nanocomposites with variable Cd:Zn ratio was 2.5-5.0 µg.mL(-1), whereas the concentration for pure CdS was much higher - 53 µg.ml(-1). The presence of ZnS in the nanocrystalline composite strongly reduced the release of cadmium into the physiological solution, which simulated the environment in the human body. The obtained CdS/ZnS quantum dots can serve as labeling media and co-agents in future anti-cancer drugs, because of their potential in theranostic applications.