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.

Special Issue: Photocatalytic Materials for Environment Treatment and Energy Production.

Nowadays, given the major problems facing humanity, the increasing environmental pollution and the need for sustainable and cheap energy sources represent important research issues [...].

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).

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.

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.

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.

Pilot-plant evaluation of TiO2 and TiO2-based hybrid photocatalysts for solar treatment of polluted water.

Materials with photocatalytic and adsorption properties for advanced wastewater treatment targeting reuse were studied. Making use of TiO2 as a well-known photocatalyst, Cu2S as a Vis-active semiconductor, and fly ash as a good adsorbent, dispersed mixtures/composites were prepared to remove pollutants from wastewater. X-ray diffraction, scanning electron microscopy, energy-dispersive X-Ray spectroscopy, atomic force microscopy, band gap energy, point of zero charge (pHpzc) and BET porosity were used to characterize the substrates. Phenol, imidacloprid and dichloroacetic acid were used as pollutants for photocatalytic activity of the new photocatalysts. Experiments using the new dispersed powders were carried out at laboratory scale in two solar simulators and under natural solar irradiation at the Plataforma Solar de Almería, in a Compound Parabolic Collector (CPC) for a comparative analysis of pollutants removal and mineralization efficiencies, and to identify features that could facilitate photocatalyst separation and reuse. The results show that radiation intensity significantly affects the phenol degradation rate. The composite mixture of TiO2 and fly ash is 2-3 times less active than sol-gel TiO2. Photodegradation kinetic data on the highly active TiO2 are compared for pollutants elimination. Photodegradation of dichloroacetic acid was fast and complete after 90min in the CPC, while after 150min imidacloprid and phenol removal was 90% and 56% respectively.