Nowadays, great focus is given to the contamination of surface and groundwater because of the extensive usage of pesticides in agriculture. The improvements of commercial catalyst TiO2 activity using different Au nanoparticles were investigated for mesotrione photocatalytic degradation under simulated sunlight. The selected system was 2.43 × 10−3% Au–S–CH2–CH2–OH/TiO2 (0.5 g/L) that was studied by transmission electron microscopy and ultraviolet-visible (UV-Vis) spectroscopy. It was found that TiO2 particles size was ~20 nm and ~50 nm, respectively. The Au nanoparticles were below 10 nm and were well distributed within the framework of TiO2. For 2.43 × 10−3% Au–S–CH2–CH2–OH/TiO2 (0.5 g/L), band gap energy was 2.45 eV. In comparison to the pure TiO2, addition of Au nanoparticles generally enhanced photocatalytic removal of mesotrione. By examining the degree of mineralization, it was found that 2.43 × 10−3% Au–S–CH2–CH2–OH/TiO2 (0.5 g/L) system was the most efficient for the removal of the mesotrione and intermediates. The effect of tert-butanol, NaF and ethylenediaminetetraacetic acid disodium salt on the transformation rate suggested that the relative contribution of various reactive species changed in following order: h+ > ●OHads > ●OHbulk. Finally, several intermediates that were formed during the photocatalytic treatment of mesotrione were identified.
Polluting the natural water resources is a serious global issue, which is confirmed by the fact that today at least 2 billion people consume water from contaminated sources. The conventional wastewater treatment methods cannot effectively remove the persistent pollutants (e.g., drugs, organic dyes, pesticides) from the aqueous environment. Heterogeneous photocatalysis is a promising and sustainable alternative for water remediation. It is based on the interaction between light irradiation and the semiconductors (e.g., TiO2, ZnO) as photocatalysts, but these compounds, unfortunately, have some disadvantages. Hence, great attention has been paid to the nanotechnology as a possible way of improvement. Nanomaterials have extraordinary properties; however, their conventional synthesis is often difficult and requires a significant amount of dangerous chemicals. This concise topical review gives recent updates and trends in development of sustainable and green pathways in the synthesis of nanomaterials, as well as in their application for water remediation. In our review we put emphasis on the eco-friendly, mostly plant extract-based materials. The importance of this topic, including this study as well, is proved by the growing number of publications since 2018. Due to the current serious environmental issues (e.g., global warming, shortage of pure and quality water), it is necessary for the traditional TiO2 and ZnO semiconductors to be replaced with the harmless, non-toxic, and more powerful nanocomposites as photocatalysts. Not only because of their higher efficiency as compared to the bulk semiconductors, but also because of the presence of biomolecules that can add up to the pollutant removal efficiency, which has been already confirmed in many researches. However, despite the fact that the application of heterogeneous photocatalysis together with green nanotechnology is absolutely the future in water purification, there are some challenges which have to be overcome. The exact effects of the biomolecules obtained from plants in the synthesis of nanoparticles, as well as in the photocatalytic processes, are not exactly known and require further investigation. Furthermore, heterogeneous photocatalysis is a well-known and commonly examined process; however, its practical use outside the laboratory is expensive and difficult. Thus, it has to be simplified and improved in order to be available for everyone. The aim of our review is to suggest and prove that using these bio-inspired compounds it is possible to reduce human footprint in the nature.
Pure water scarcity is an emerging, all-around problem that globally affects both the life quality and the world’s economy. Heterogeneous photocatalysis under solar irradiation is a promising technique for the organic pollutants (e.g., pesticides, drugs) removal from an aqueous environment. Furthermore, the drawbacks of commercially available photocatalysts can be successfully overcome by using innovative nanoparticles, such as ZrO2/Fe3O4. Four ZrO2/Fe3O4 nanopowders with a different mass ratio of ZrO2 and Fe3O4 were synthesized using the chemical co-precipitation method. XRD analysis showed the presence of magnetite and hematite Fe-oxide phases in all samples. The content of the magnetite phase increased with the addition of 19% ZrO2. The efficiency of the newly synthesized ZrO2/Fe3O4 nanoparticles was investigated in the rapid removal of selected pollutants under various experimental conditions. Nevertheless, the influence of the water matrix on photocatalytic degradation was also examined. The obtained data showed that using ZrO2/Fe3O4 nanosystems, an appropriate removal rate of the selected pesticides and pharmaceuticals can be reached after 120 min of solar irradiation. Further, the total organic carbon measurements proved the mineralization of the target emerging pollutants. ZrO2/Fe3O4 nanoparticles are economically feasible, as their removal from the suspension can be easily achieved using affordable, environmentally-friendly magnetic separation.
A new titanium/molybdenum/mixed-oxides (TMO) contact-type heterojunction photocatalyst was prepared by a simple, low-cost, and environmentally-friendly mixing-calcination solid-state method. A microstructural investigation by scanning electron microscopy (SEM) showsirregularly shaped agglomerated morphology of TMO that consists of firmly connected globular TiO2 and rod-like MoO3 particles. The detailed structure and optical bandgap investigation by X-ray diffraction, Raman, and UV-Vis spectroscopy revealed the TMO’s composition of ~37 wt.% rutile TiO2, ~25 wt.% of anatase TiO2, and ~38 wt.% of molybdite MoO3 phase and an absorption threshold of around 380 nm, which implies more probability of desirable higher visible light absorption. The removal efficiency of pesticides quinmerac (QUI) and tembotrione (TEM), and pharmaceuticals metoprolol (MET), amitriptyline (AMI), ciprofloxacin (CIP),and ceftriaxone (CEF) from water in the presence of starting pure TiO2, MoO3, and prepared TMO were investigated under different pH values and UV irradiation/simulated sunlight (SS). Each starting metal-oxide precursors and prepared TMO showed a different affinity for adsorption of tested pesticides and pharmaceuticals, and, in general, better photocatalytic degradation efficiency under UV irradiation than under simulated sunlight. The highest photocatalytic degradation efficiency under UV irradiation was 81.6% for TEM using TMO; using TiO2 was 65.0% for AMI, and using MoO3 was 79.3% for CEF after 135 min. However, TMO showed a very high synergic adsorption/photocatalytic under-SS efficiency in the removal of CIP of almost 80% and under UV irradiation of 90% CIP removal after 75 min. The toxicity of catalysts, starting compounds, and their intermediates formed during the removal process was assessed using a rat hepatoma cell line (H-4-II-E). The highest hepatotoxic effects were obtained by using UV irradiated QUI and MET suspension with TMO for up to 60 min.
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