Sustainable Green Nanotechnologies for Innovative Purifications of Water: Synthesis of the Nanoparticles from Renewable Sources

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.

Selective ligand removal to improve accessibility of active sites in hierarchical MOFs for heterogeneous photocatalysis

Metal-organic frameworks (MOFs) are commended as photocatalysts for H2 evolution and CO2 reduction as they combine light-harvesting and catalytic functions with excellent reactant adsorption capabilities. For dynamic processes in liquid phase, the accessibility of active sites becomes a critical parameter as reactant diffusion is limited by the inherently small micropores. Our strategy is to introduce additional mesopores by selectively removing one ligand in mixed-ligand MOFs via thermolysis. Here we report photoactive MOFs of the MIL-125-Ti family with two distinct mesopore architectures resembling either large cavities or branching fractures. The ligand removal is highly selective and follows a 2-step process tunable by temperature and time. The introduction of mesopores and the associated formation of new active sites have improved the HER rates of the MOFs by up to 500%. We envision that this strategy will allow the purposeful engineering of hierarchical MOFs and advance their applicability in environmental and energy technologies.

Advanced catalytic oxidation coupled to biological systems to treat pesticide-contaminated water: A review on technological trends and future challenges

This article had the one and only objective of consolidating the couplings of advanced oxidation processes and biological in the decontamination of wastewater with pesticide content reported in the Scopus and Web of Science databases, through a critical analysis of which have been the most used, what methodologies have been implemented to develop them, identify the objectives of each work, determine the success of the research and where the main niches of knowledge are, which can lead to the generation of new scientific knowledge as well as future trends. A co-occurrence analysis was carried out through the VOSViewer software, to determine the most associated key words with the treatment configurations described above. Fenton and Photo-Fenton processes, heterogeneous photocatalysis TiO2/UV, electrocatalysis, ozonization and a particular case of hydrodynamic-ozone cavitation as main advanced oxidation processes, together with advanced biological processes such as SBR, MBR, MBBR; biodegradability and toxicity tests with bacterial strains and surface wetlands, whose treatment philosophy is activated sludge. The main future trends are the reuse of treated wastewater, the analysis and control of costs towards the efficient use of resources and the primary study of the byproducts generated in advanced oxidation to improve the efficiencies in the coupling.

Impact of Reaction Parameters and Water Matrices on the Removal of Organic Pollutants by TiO2/LED and ZnO/LED Heterogeneous Photocatalysis Using 365 and 398 nm Radiation

In this work, the application of high-power LED365nm and commercial, low-price LED398nm for heterogeneous photocatalysis with TiO2 and ZnO photocatalysts are studied and compared, focusing on the effect of light intensity, photon energy, quantum yield, electrical energy consumption, and effect of matrices and inorganic components on radical formation. Coumarin (COU) and its hydroxylated product (7-HC) were used to investigate operating parameters on the •OH formation rate. In addition to COU, two neonicotinoids, imidacloprid and thiacloprid, were also used to study the effect of various LEDs, matrices, and inorganic ions. The transformation of COU was slower for LED398nm than for LED365nm, but r07-HC/r0COU ratio was significantly higher for LED398nm. The COU mineralization rate was the same for both photocatalysts using LED365nm, but a significant difference was observed using LED398nm. The impact of matrices and their main inorganic components Cl− and HCO3− were significantly different for ZnO and TiO2. The negative effect of HCO3− was evident, however, in the case of high-power LED365nm and TiO2, and the formation of CO3•− almost doubled the r07-HC and contributes to the conversion of neonicotinoids by altering the product distribution and mineralization rate.

Heterogeneous Photocatalysis of Metronidazole in Aquatic Samples

Metronidazole (MET) is a commonly detected contaminant in the environment. The compound is classified as poorly biodegradable and highly soluble in water. Heterogeneous photocatalysis is the most promoted water purification method due to the possibility of using sunlight and small amounts of a catalyst needed for the process. The aim of this study was to select conditions for photocatalytic removal of metronidazole from aquatic samples. The effect of catalyst type, mass, and irradiance intensity on the efficiency of metronidazole removal was determined. For this purpose, TiO2, ZnO, ZrO2, WO3, PbS, and their mixtures in a mass ratio of 1:1 were used. In this study, the transformation products formed were identified, and the mineralization degree of compound was determined. The efficiency of metronidazole removal depending on the type of catalyst was in the range of 50–95%. The highest MET conversion (95%) combined with a high degree of mineralization (70.3%) was obtained by using a mixture of 12.5 g TiO2–P25 + PbS (1:1; v/v) and running the process for 60 min at an irradiance of 1000 W m−2. Four MET degradation products were identified by untargeted analysis, formed by the rearrangement of the metronidazole and the C-C bond breaking.

Application of EPR Spectroscopy in TiO2 and Nb2O5 Photocatalysis

The interaction of light with semiconducting materials becomes the center of a wide range of technologies, such as photocatalysis. This technology has recently attracted increasing attention due to its prospective uses in green energy and environmental remediation. The characterization of the electronic structure of the semiconductors is essential to a deep understanding of the photocatalytic process since they influence and govern the photocatalytic activity by the formation of reactive radical species. Electron paramagnetic resonance (EPR) spectroscopy is a unique analytical tool that can be employed to monitor the photoinduced phenomena occurring in the solid and liquid phases and provides precise insights into the dynamic and reactivity of the photocatalyst under different experimental conditions. This review focus on the application of EPR in the observation of paramagnetic centers formed upon irradiation of titanium dioxide and niobium oxide photocatalysts. TiO2 and Nb2O5 are very well-known semiconductors that have been widely used for photocatalytic applications. A large number of experimental results on both materials offer a reliable platform to illustrate the contribution of the EPR studies on heterogeneous photocatalysis, particularly in monitoring the photogenerated charge carriers, trap states, and surface charge transfer steps. A detailed overview of EPR-spin trapping techniques in mechanistic studies to follow the nature of the photogenerated species in suspension during the photocatalytic process is presented. The role of the electron donors or the electron acceptors and their effect on the photocatalytic process in the solid or the liquid phase are highlighted.

Graphitic Carbon Nitride as a Sustainable Photocatalyst Material for Pollutants Removal. State-of-the Art, Preliminary Tests and Application Perspectives

Photocatalysis is an attractive strategy for emerging pollutants remediation. Research towards the development of new, efficient and effective catalytic materials with high activity under wide irradiation spectra is a highly active sector in material science. Various semiconductor materials have been employed as photocatalysts, including TiO2, SrTiO3, CdS, BiVO4, Ta3N5, TaON, Ag3PO4, and g-C3N4. The latter is a metal-free, low cost polymer, providing high adsorption and catalytic properties, shown to be promising for photocatalysis applications under visible light. Furthermore, g-C3N4 composites are among the most promising advanced photocatalytical materials that can be produced by green synthesis processes. In this paper, the state-of-the-art of g-C3N4 applications is reviewed, and application perspectives are discussed. Photocatalysis tests with g-C3N4 under Xenon irradiation were performed to gather first-hand information to improve photoreactor design. Xenon light spectrum appears to be a suitable radiation source to replace direct sunlight in engineered pollutants removal processes catalyzed by g-C3N4, in lieu of other currently used heterogeneous photocatalysis processes (e.g., TiO2-UV). LED sources are also very promising due to higher energy efficiency and customizable, catalyzer-specific irradiation spectra.