Fluoride Adsorption from Aqueous Solution by Modified Zeolite-Kinetic and Isotherm Studies.

Fluorine is a very common element in the Earth's crust and is present in the air, food, and in natural waters. It never meets in the free state in nature due to its high reactivity, and it comes in the form of fluorides. Depending on the concentration of fluorine absorbed, it may be beneficial or harmful to human health. Similar to any trace element, fluoride ion is beneficial for the human body at low levels, but as soon as its concentration becomes too high, it is toxic, inducing dental and bone fluorosis. The lowering of fluoride concentrations that exceed the recommended standards in drinking water is practiced in various ways around the world. The adsorption process has been classified as one of the most efficient methods for the removal of fluoride from water as it is environmentally friendly, easy to operate, and cost-effective. The present study deals with fluoride ion adsorption on modified zeolite. There are several influential parameters, such as zeolite particle size, stirring rate, solution pH, initial concentration of fluoride, contact time, and solution temperature. The maximum removal efficiency of the modified zeolite adsorbent was 94% at 5 mg/L fluoride initial concentration, pH 6.3, and 0.5 g modified zeolite mass. The adsorption rate increases accordingly with increases in the stirring rate and pH value and decreases when the initial fluoride concentration is increased. The evaluation was enhanced by the study of adsorption isotherms using the Langmuir and Freundlich models. The Langmuir isotherm corresponds with the experimental results of the fluoride ions adsorption with a correlation value of 0.994. The kinetic analysis results of the fluoride ions adsorption on modified zeolite allowed us to demonstrate that the process primarily follows a pseudo-second-order and then, in the next step, follows a pseudo-first-order model. Thermodynamic parameters were calculated, and the ΔG° value is found to be in the range of -0.266 kJ/mol up to 1.613 kJ/mol amidst an increase in temperature from 298.2 to 331.7 K. The negative values of the free enthalpy ΔG° mean that the adsorption of fluoride ions on the modified zeolite is spontaneous, and the positive value of the enthalpy ∆H° shows that the adsorption process is endothermic. The ∆S° values of entropy indicate the fluoride adsorption randomness characteristics at the zeolite-solution interface.

Recent Developments in ZnS-Based Nanostructures Photocatalysts for Wastewater Treatment.

The continuous growth of the world population has led to the constant increase of environmental pollution, with serious consequences for human health. Toxic, non-biodegradable, and recalcitrant organic pollutants (e.g., dyes, pharmaceuticals, pesticides) are discharged into water resources from various industries, such as textiles, leather, pharmaceuticals, plastics, etc. Consequently, the treatment of industrial wastewater, via a sustainable technology, represents a great challenge for worldwide research. Photocatalytic technology, an innovative technique based on advanced oxidation process (AOP), is considered a green technology with promising prospects in the remediation of global environmental issues. In photocatalysis, a very important role is attributed to the photocatalyst, usually a semiconductor material with high solar light absorption capacity and conductivity for photogenerated-charge carriers. Zinc sulfide (ZnS), as n-type semiconductor with different morphologies and band gap energies (Eg = 3.2-3.71 eV), is recognized as a promising photocatalyst for the removal of organic pollutants from wastewater, especially under UV light irradiation. This review deals with the recent developments (the last five years) in ZnS nanostructures (0D, 1D, 3D) and ZnS-based heterojunctions (n-n, n-p, Z scheme) used as photocatalysts for organic pollutants' degradation under simulated (UV, Vis) and sunlight irradiation in wastewater treatment. The effects of different synthesis parameters (precursors' type and concentration, capping agents' dosages, reaction time and temperature, metal doping, ZnS concentration in heterostructures, etc.) and properties (particle size, morphology, band gap energy, and surface properties) on the photocatalytic performance of ZnS-based photocatalysts for various organic pollutants' degradation are extensively discussed.

Polymer Composite-Based Materials with Photocatalytic Applications in Wastewater Organic Pollutant Removal: A Mini Review.

The development of new technologies using nanomaterials has allowed scientists to design advanced processes with many applications in environmental protection, energy production and storage, and medicinal bio-mediated processes. Due to their significant potential applications in different branches of science, the development of new polymer composites represents a priority, especially for nano-technological processes. Interest in polymeric composites was outlined by the synthesis of a large number of nano- or mezzo-scale materials with targeted functional properties for polymer matrix hybridization. The present mini review explores some of the most representative and recent papers reporting the photocatalytic activity of polymer composites toward different organic compounds (dyes, pharmaceutically active molecules, phenol, etc.). The polymer composites were divided based on their composition and photocatalytic activity. TiO2- and ZnO-based polymeric composites have been described here in light of their photocatalytic activity toward different pollutants, such as rhodamine B, phenol, or methyl orange. Polymeric composites based on WO3, Fe2O3, or Bi2MoO6 were also described. The influence of different polymeric composites and photocatalytic parameters (light spectra and intensity, pollutant molecule and concentration, irradiation time, and photocatalyst dosage) on the overall photocatalytic efficiency indicates that semiconductor (TiO2, ZnO, etc.) insertion in the polymeric matrix can tune the photocatalytic activity without compromising the structural integrity. Future perspectives and limitations are outlined considering the systematic and targeted description of the reported results. Adopting green route synthesis and application can add economic and scientific value to the knowledgebase by promoting technological development based on photocatalytic designs.

UV-Vis Activated Cu2O/SnO2/WO3 Heterostructure for Photocatalytic Removal of Pesticides.

A three-steps sol-gel method was used to obtain a Cu2O/SnO2/WO3 heterostructure powder, deposited as film by spray pyrolysis. The porous morphology of the final heterostructure was constructed starting with fiber-like WO3 acting as substrate for SnO2 development. The SnO2/WO3 sample provide nucleation and grew sites for Cu2O formation. Diffraction evaluation indicated that all samples contained crystalline structures with crystallite size varying from 42.4 Å (Cu2O) to 81.8 Å (WO3). Elemental analysis confirmed that the samples were homogeneous in composition and had an oxygen excess due to the annealing treatments. Photocatalytic properties were tested in the presence of three pesticides-pirimicarb, S-metolachlor (S-MCh), and metalaxyl (MET)-chosen based on their resilience and toxicity. The photocatalytic activity of the Cu2O/SnO2/WO3 heterostructure was compared with WO3, SnO2, Cu2O, Cu2O/SnO2, Cu2O/WO3, and SnO2/WO3 samples. The results indicated that the three-component heterostructure had the highest photocatalytic efficiency toward all pesticides. The highest photocatalytic efficiency was obtained toward S-MCh (86%) using a Cu2O/SnO2/WO3 sample and the lowest correspond to MET (8.2%) removal using a Cu2O monocomponent sample. TOC analysis indicated that not all the removal efficiency could be attributed to mineralization, and by-product formation is possible. Cu2O/SnO2/WO3 is able to induce 81.3% mineralization of S-MCh, while Cu2O exhibited 5.7% mineralization of S-MCh. The three-run cyclic tests showed that Cu2O/SnO2/WO3, WO3, and SnO2/WO3 exhibited good photocatalytic stability without requiring additional procedures. The photocatalytic mechanism corresponds to a Z-scheme charge transfer based on a three-component structure, where Cu2O exhibits reduction potential responsible for O2 production and WO3 has oxidation potential responsible for HO· generation.

Opportunities for Recycling PV Glass and Coal Fly Ash into Zeolite Materials Used for Removal of Heavy Metals (Cd, Cu, Pb) from Wastewater.

This work shows the development and characterization of two zeolite structures by recycling PV glass and coal fly ash for the removal of cadmium, copper, and lead from synthetic solutions containing one or three cations. The materials were characterized in terms of crystalline structure (XRD), morphology (SEM, AFM), and specific surface. For increasing the heavy-metals removal efficiency, the adsorption conditions, such as substrate dosage, preliminary concentration, and contact time, were optimized. The pseudo-second-order kinetic model adsorption kinetics fit well to describe the activity of the zeolites ZFAGPV-A and ZFAGPV-S. The zeolite adsorption equilibrium data were expressed using Langmuir and Freundlich models. The highest adsorption capacities of the ZFAGPV-A zeolite are qmaxCd = 55.56 mg/g, qmaxCu = 60.11 mg/g, qmaxPb = 175.44 mg/g, and of ZFAGPV-S, are qmaxCd = 33.45 mg/g, qmaxCu = 54.95 mg/g, qmaxPb = 158.73 mg/g, respectively. This study demonstrated a new opportunity for waste recycling for applications in removing toxic heavy metals from wastewater.

Synthesis, Characterisation, Photocatalytic Activity, and Aquatic Toxicity Evaluation of TiO2 Nanoparticles.

Imidacloprid (IMD) is a toxic pesticide, and is one of the eight most widely used pesticides globally. Heterogeneous photocatalysis has often been investigated in recent years and can be successfully applied to remove imidacloprid from water. However, less investigated is the toxic effect of both the photocatalyst and the pesticide on aquatic life. Titanium dioxide (TiO2) remains the most effective photocatalyst, provided it is not toxic to the aquatic environment. This study investigated the TiO2 synthesis, characterisation, and photocatalytic activity on imidacloprid degradation and the toxicity of TiO2 nanoparticles and imidacloprid on the green algae Chlorella vulgaris. In the photodegradation process of IMD (initial concentration of 20 mg/L), electrons play an essential role; the degradation efficiency of IMD after 6 h increased from 69 to 90% under UV irradiation when holes (h+) scavengers were added, which allowed the electrons to react with the pollutant, resulting in lowering the recombination rate of electron-hole charge carriers. Growth inhibition of Chlorella vulgaris and effective concentration (EC50) were determined to study the toxic effect of TiO2 nanoparticles and imidacloprid. The EC50 increased from 289.338 mg/L in the first 24 h to 1126.75 mg/L after 96 h Chlorella vulgaris algal age, when the toxicant was TiO2. When IMD was the aquatic toxicant, a decrease in EC50 was observed from 22.8 mg/L (24 h) to 0.00777 mg/L (120 h), suggesting a long-term high toxicity level when pesticides in low concentrations are present in an aquatic environment.

Photocatalytic Activity of Cu2S/WO3 and Cu2S/SnO2 Heterostructures for Indoor Air Treatment.

Volatile organic compounds (VOCs) are commonly found in indoor spaces (e.g., homes or offices) and are often related to various illnesses, some of them with carcinogenic potential. The origins of VOC release in the indoor environment are in office products, building materials, electronics, cleaning products, furniture, and maintenance products. VOC removal can be done based on two types of technologies: adsorption in specific materials and decomposition via oxidative processes. The present article reports the development and photocatalytic activity of two heterostructures (Cu2S/WO3 and Cu2S/SnO2) used for indoor air decontamination. The acetaldehyde removal rate is discussed in correlation with the S-scheme mechanisms established between the heterostructure components but also comparatively with the bare catalysts' activity. Acetaldehyde was considered as a VOC reference because it was found by the International Agency for Research on Cancer to be one of the most frequent air toxins with potential carcinogenic effects. The samples contained monoclinic WO3, tetragonal SnO2, and orthorhombic Cu2S crystalline structures. The Cu2S crystallite size in the heterostructure varied from 75.9 to 82.4 Å, depending on the metal oxide substrate. The highest photocatalytic efficiency (75.7%) corresponded to Cu2S/SnO2, with a constant rate of 0.106 s-1 (which was three times faster than WO3 or SnO2 and seven and a half times faster than Cu2S).

Synergic Effect of TiO2 Filler on the Mechanical Properties of Polymer Nanocomposites.

Nanocomposites with polymer matrix offer excellent opportunities to explore new functionalities beyond those of conventional materials. TiO2, as a reinforcement agent in polymeric nanocomposites, is a viable strategy that significantly enhanced their mechanical properties. The size of the filler plays an essential role in determining the mechanical properties of the nanocomposite. A defining feature of polymer nanocomposites is that the small size of the fillers leads to an increase in the interfacial area compared to traditional composites. The interfacial area generates a significant volume fraction of interfacial polymer, with properties different from the bulk polymer even at low loadings of the nanofiller. This review aims to provide specific guidelines on the correlations between the structures of TiO2 nanocomposites with polymeric matrix and their mechanical properties. The correlations will be established and explained based on interfaces realized between the polymer matrix and inorganic filler. The paper focuses on the influence of the composition parameters (type of polymeric matrix, TiO2 filler with surface modified/unmodified, additives) and technological parameters (processing methods, temperature, time, pressure) on the mechanical strength of TiO2 nanocomposites with the polymeric matrix.

Tuned S-Scheme Cu2S_TiO2_WO3 Heterostructure Photocatalyst toward S-Metolachlor (S-MCh) Herbicide Removal.

A dual S-scheme Cu2S_TiO2_WO3 heterostructure was constructed by sol-gel method using a two-step procedure. Due to the synthesis parameters and annealing treatment the heterostructure is characterized by sulfur deficit and oxygen excess allowing the passivation of oxygen vacancies. The photocatalytic activity was evaluated under UV and UV-Vis irradiation scenarios using S-MCh as reference pollutant. The heterostructure is composed on orthorhombic Cu2S, anatase TiO2 and monoclinic WO3 with crystallite sizes varying from 65.2 Å for Cu2S to 97.1 Å for WO3. The heterostructure exhibit a dense morphology with pellets and particle-like morphology closely combined in a relatively compact assembly. The surface elemental composition indicate that the heterostructure maintain a similar atomic ratio as established during the synthesis with a slight sulfur deficit due to the annealing treatments. The results indicate that the three-component heterostructure have higher photocatalytic efficiency (61%) comparing with two-component heterostructure or bare components. Moreover, Cu2S_TiO2_WO3 exhibit a superior constant rate (0.114 s-1) due to the high concentration of photogenerated charge carriers, efficient charge separation and migration.

Photocatalytic Activity of S-Scheme Heterostructure for Hydrogen Production and Organic Pollutant Removal: A Mini-Review.

Finding new technologies and materials that provide real alternatives to the environmental and energy-related issues represents a key point on the future sustainability of the industrial activities and society development. The water contamination represents an important problem considering that the quantity and complexity of organic pollutant (such as dyes, pesticides, pharmaceutical active compounds, etc.) molecules can not be efficiently addressed by the traditional wastewater treatments. The use of fossil fuels presents two major disadvantages: (1) environmental pollution and (2) limited stock, which inevitably causes the energy shortage in various countries. A possible answer to the above issues is represented by the photocatalytic technology based on S-scheme heterostructures characterized by the use of light energy in order to degrade organic pollutants or to split the water molecule into its components. The present mini-review aims to outline the most recent achievements in the production and optimization of S-scheme heterostructures for photocatalytic applications. The paper focuses on the influence of heterostructure components and photocatalytic parameters (photocatalyst dosage, light spectra and intensity, irradiation time) on the pollutant removal efficiency and hydrogen evolution rate. Additionally, based on the systematic evaluation of the reported results, several perspectives regarding the future of S-scheme heterostructures were included.

Tandem Structures Semiconductors Based on TiO2_SnO2 and ZnO_SnO2 for Photocatalytic Organic Pollutant Removal.

The photocatalyst materials correlation with the radiation scenario and pollutant molecules can have a significant influence on the overall photocatalytic efficiency. This work aims to outline the significance of optimizing the components mass ratio into a tandem structure in order to increase the photocatalytic activity toward pollutant removal. ZnO_SnO2 and TiO2_SnO2 tandem structures were obtained by the doctor blade technique using different mass ratios between the components. The samples contain metal oxides with crystalline structures and the morphology is influenced by the main component. The photocatalytic activity was tested using three radiation scenarios (UV, UV-Vis, and Vis) and two pollutant molecules (tartrazine and acetamiprid). The results indicate that the photocatalytic activity of the tandem structures is influenced by the radiation wavelength and pollutant molecule. The TiO2_SnO2 exhibit 90% photocatalytic efficiency under UV radiation in the presence of tartrazine, while ZnO_SnO2 exhibit 73% photocatalytic efficiency in the same experimental conditions. The kinetic evaluation indicate that ZnO_SnO2 (2:1) have a higher reaction rate comparing with TiO2_SnO2 (1:2) under UV radiation in the presence of acetamiprid.

Black TiO2 Synthesis by Chemical Reduction Methods for Photocatalysis Applications.

Applications of TiO2 nanomaterials in photocatalysis, batteries, supercapacitors and solar cells, have seen widespread development in recent decades. Nowadays, black TiO2 have won attention due to enhancing the solar light absorption by the formation of oxygen vacancies and Ti3+ defects, to promote the separation of photo-generated charge carriers leading to the improvement of the photocatalytic performance in H2 production and pollutants degradation. The enhanced photocatalytic activity of black TiO2 is also due to a lattice disorder on the surface and the presence of oxygen vacancies, Ti3+ ions, Ti-OH and Ti-H groups. Enhancing the optical absorption characteristics of TiO2 and change of energy level and band-gap of materials have been successfully demonstrated to improve their photocatalytic activities, especially for black TiO2 nanoparticles, which promote visible light absorption. The current review focuses on the investigation of the chemical reduction synthetic route for black TiO2 nanomaterials, and their proposed association with green applications such as photodegradation of organic pollutants and photocatalytic water splitting. The synthesis methods of black TiO2 involves the changes from Ti4+ to Ti3+ state, into different strategies: (1) The use of highly active hydrogen species such as H2, H2/Ar or H2/N2 gases, and metal hydrides (NaBH4, CaH2), (2) the reduction by active metals such as aluminum, magnesium and zinc, and (3) organic molecules such as imidazole and ascorbic acid.

Enhancing the Photocatalytic Activity of SnO2-TiO2 and ZnO-TiO2 Tandem Structures Toward Indoor Air Decontamination.

ZnO-TiO2 and SnO2-TiO2 tandem structures were developed using the doctor blade technique. It was found that by employing organic hydrophilic and hydrophobic as additives into the precursor it is possible to tailor the film density and morphology with direct consequences on the photocatalytic activity of the tandem structures. The highest photocatalytic efficiency corresponds to ZnO-TiO2 and can reach 74.04% photocatalytic efficiency toward acetaldehyde when a hydrophilic additive is used and 70.93% when a hydrophobic additive is employed. The snO2-TiO2 tandem structure presents lower photocatalytic properties (61.35 % when the hydrophilic additive is used) with a constant rate reaction of 0.07771 min-1.

Volatile Organic Compounds (VOCs) Removal from Indoor Air by Heterostructures/Composites/Doped Photocatalysts: A Mini-Review.

The impact of volatile organic compounds (VOCs) on indoor air quality and, furthermore, on human health is still a subject of research investigations considering the large increase in forms of cancer and related diseases. VOCs can be 10 times higher in indoor air concentrations then that of the outdoors, as a consequence of emissions from electronics, building materials and consumer goods. Direct transformation of VOCs in mineralization products seems to be an alternative to reduce indoor air contaminants. The advantage of photocatalysis implementation in indoor air treatment is given by the absence of additional chemicals (such as H2O2) and waste. The present mini-review presents a comparative study on VOCs photocatalytic removal considering the photocatalyst composition, morphology and specific surface. The sheet-like morphology seems to provide a higher number of active sites which may contribute to oxidative reactions. The insertion of materials able to increase light absorbance or to mediate the charge carrier's transport will have a beneficial impact on the overall photocatalytic efficiency. Additionally, surface chemistry must be considered when developing photocatalysts for certain gas pollutants in order to favor molecule absorbance in the interfacial region. An energy consumption perspective is given based on the light intensity and irradiation period.

The Influence of Photoactive Heterostructures on the Photocatalytic Removal of Dyes and Pharmaceutical Active Compounds: A Mini-Review.

The diversification of pollutants type and concentration in wastewater has underlined the importance of finding new alternatives to traditional treatment methods. Advanced oxidation processes (AOPs), among others, are considered as promising candidate to efficiently remove organic pollutants such as dyes or pharmaceutical active compounds (PhACs). The present minireview resumes several recent achievements on the implementation and optimization of photoactive heterostructures used as photocatalysts for dyes and PhACs removal. The paper is focused on various methods of enhancing the heterostructure photocatalytic properties by optimizing parameters such as synthesis methods, composition, crystallinity, morphology, pollutant concentration and light irradiation.

Metal Oxides-Based Semiconductors for Biosensors Applications.

The present mini review contains a concessive overview on the recent achievement regarding the implementation of a metal oxide semiconductor (MOS) in biosensors used in biological and environmental systems. The paper explores the pathway of enhancing the sensing characteristics of metal oxides by optimizing various parameters such as synthesis methods, morphology, composition, and structure. Four representative metal oxides (TiO2, ZnO, SnO2, and WO3) are presented based on several aspects: synthesis method, morphology, functionalizing molecules, detection target, and limit of detection (LOD).

The Influence of Light Irradiation on the Photocatalytic Degradation of Organic Pollutants.

The design of a photocatalytic process must consider intrinsic and extrinsic parameters affecting its overall efficiency. This study aims to outline the importance of balancing several factors, such as radiation source, total irradiance, photon flux, catalyst substrate, and pollutant type in order to optimize the photocatalytic efficiency. Titanium oxide was deposed by the doctor blade technique on three substrates (microscopic glass (G), flour-doped tin oxide (FTO), and aluminum (Al)), and the photocatalytic properties of the samples were tested on two pollutants (tartrazine (Tr) and acetamiprid (Apd)). Seven irradiation scenarios were tested using different ratios of UV-A, UV-B + C, and Vis radiations. The results indicated that the presence of a conductive substrate and a suitable ratio of UV-A and Vis radiations could increase the photocatalytic efficiency of the samples. Higher efficiencies were obtained for the sample Ti_FTO (58.3% for Tr and 70.8% for Apd) and the sample Ti_Al (63.8% for Tr and 82.3% for Apd) using a mixture of three UV-A and one Vis sources (13.5 W/m2 and 41.85 µmol/(m2·s)). A kinetic evaluation revealed two different mechanisms of reaction: (a) a one-interval mechanism related to Apd removal by Ti_FTO, Ti_Al (scenarios 1, 4, 5, and 7), and Ti_G samples (scenario 7) and (b) a two-interval mechanism in all other cases.

Copper Sulfide Based Heterojunctions as Photocatalysts for Dyes Photodegradation.

The presence of toxic, non-biodegradable and harmful organic pollutants in soils, wastewater, and atmosphere has become an indisputable, and global fact as a significant environmental problem. The heterogeneous photocatalysis, an advanced oxidation process (AOP) using semiconductor materials as catalysts, is a topic of great interest considering the possibility of the pollutants removal from water. The photocatalytic degradation of organic contaminants (i.e., dyes, pesticides, phenolic compounds) present in water using semiconductor materials depends on a number of parameters such as: the bandgap energy, phase composition, crystallinity, morphology and surface area of catalyst, electron-hole recombination rate, intensity of light, and adsorption capacity of the dye on the photocatalyst surface. One of the important constraints related to the catalyst photocatalytic efficiency is the fast recombination of the photogenerated electrons and holes. Therefore, various strategies have been involved in promoting the charge separation, including the development of heterojunction between two semiconductor materials, by tailoring the photocatalysts properties. This mini-review deals with the recent developments on dyes photodegradation using as catalysts various heterojunctions based on copper sulfide nanostructures, such as copper sulfide/metal oxide, copper sulfide/metal sulfide, copper sulfide/graphene, copper sulfide/organic semiconductors etc. The effects of different parameters, such as synthesis parameters, particle size, bandgap energy, surface area, and morphology on the photocatalytic activity of copper sulfide heterojunctions for dyes degradation is also highlighted.