Search

In recent years, scientific research has faced the numerous problems deriving from the presence of active ingredients in surface and groundwater. Traditional removal methods, such as adsorption and bioremediation, have several disadvantages; thus, in this work, membranes based on cellulose acetate loaded with Fe-N-TiO2, were tested for the photocatalytic degradation of Ceftriaxone Sodium from aqueous solution. The immobilization of the photocatalyst allows to overcome the limits of the photocatalytic process in suspension, which requires expensive and time-consuming post-treatments. Membranes were obtained by supercritical CO2 phase inversion process and were subjected to characterizations such as EDX, TGA, FT-IR, Raman spectroscopy and, subsequently, tested in adsorption tests in the dark and in the presence of visible light, to evaluate their photocatalytic activity. The variations in the concentration of the antibiotic, during the tests conducted, were monitored by HPLC chromatographic analysis. Samples with 10% and 30% by weight of Fe-N-TiO2 demonstrated relatively low adsorption efficiencies of the target contaminant, respectively equal to 22% and 18% in 180 minutes, for reasons related both to the morphology of the samples products, which changes from cellular to finger-like as the photocatalyst load increases, and to the quality of the dispersion. The membrane loaded with 20% by weight of Fe-N-TiO2 allowed a degradation of the model pollutant of 35% in 180 minutes; moreover, the reusability of the membranes was verified. The photocatalytic tests showed that the photocatalytic efficiency was highly correlated to the dispersion of the photocatalyst nanoparticles and to its loading in the polymeric membranes.

The global increase in energy demand requires a continuous search for renewable and clean alternative resources to fossil fuels. Hydrogen is emerging as a promising energy carrier for the future; its production via photocatalysis, driven by sunlight, can directly convert solar energy into a usable or storable energy resource. However, water splitting requires sacrificial agents or electron donors/hole scavengers, such as short-chain organic acids. This research explores the use of lactic acid as a source for photocatalytic hydrogen production, offering valuable alternatives for wastewater management and renewable energy production. This study employed the innovative supercritical antisolvent (SAS) technique to micronize the precursors of both the active phase (CeO2) and co-catalyst (CuO), ensuring rapid and complete solvent removal and size reduction of photocatalyst precursors. The prepared samples were characterized by field emission scanning electron microscopy (FESEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic light scattering (DLS) analysis, Brunauer-Emmett-Teller (BET) analysis and thermogravimetric analysis (TGA). This study has shown that the micronization process resulted in a notable improvement in CeO2 photocatalytic activity, attributed to the reduction of the dimensions of the powders. Hydrogen production was equal to 3989 μmol L−1 for the SAS-produced photocatalyst while using a commercial CeO2 sample resulted in H2 production of 2519 μmol L−1. The enhanced photoactivity of CeO2-CuO composites was found to be related to the presence of CuO. The optimal CuO amount was equal to 0.5 wt%, determining a hydrogen production of 9313 μmol L−1 after 4 h of UV irradiation time. A photocatalytic test carried out with deuterated water (D2O) instead of distilled H2O demonstrated that hydrogen was preferentially produced from water splitting reaction, whereas lactic acid acted as a sacrificial agent being oxidized from positive holes photogenerated in the valence band of CuO.

This work examined the influence of UV-A light modulation on the photocatalytic process coadjuvated with H2O2 to mineralize phenol in an aqueous solution. A fixed-bed batch photocatalytic reactor with a flat-plate geometry, irradiated by UV-A LEDs, was employed. The successful deposition of commercial TiO2 PC105 on a steel plate (SP) was achieved, and the structured photocatalyst was characterized using Raman spectroscopy, specific surface area (SSA) measurements, and UV–vis DRS analysis. These analyses confirmed the formation of a titania coating in the anatase phase with a bandgap energy of 3.25 eV. Various LED-dimming techniques, with both fixed and variable duty cycle values, were tested to evaluate the stability of the photocatalyst’s activity and the influence of operating parameters during the mineralization of 450 mL of a phenol solution. The optimal operating parameters were identified as an initial phenol concentration of 10 ppm, a hydrogen peroxide dosage of 0.208 g L−1, and triangular variable duty cycle light modulation. Under these conditions, the highest apparent phenol degradation kinetic constant (0.39 min−1) and the total mineralization were achieved. Finally, the energy consumption for mineralizing 90% phenol in one cubic meter of treated water was determined, showing the greatest energy savings with triangular light modulation.

Arsenic in drinking water is one of the most concerning problems nowadays due to its high toxicity. The aim of this work is the photocatalytic oxidation of As(III) to As(V) under visible light. This study is focused on the use of gadolinium-doped bismuth ferrite as a photocatalyst active under visible light. Different gadolinium amounts were evaluated (0, 0.5, 1, 2, 5, 10 mol%), and 2 mol% resulted in the best gadolinium amount to reach higher photocatalytic efficiency in terms of As(V) production. The samples were thoroughly characterized in their optical, structural, and morphological properties. The results allowed us to identify an optimal concentration of gadolinium equal to 2 mol%. The reactive oxygen species most responsible for the photocatalytic mechanism, evaluated through the addition of radical scavengers, were O2−● and e−. Finally, a photocatalytic test was performed with a drinking water sample polluted by As(III), showing photocatalytic performance similar to distilled water. Therefore, gadolinium-doped bismuth ferrite can be considered an efficient catalytic material for the oxidation of As(III) to As(V) under visible light.

Perchloroethylene (PCE) is a pollutant toxic to aquatic life and suspected of being a human carcinogen. It is also recalcitrant to degradation. Therefore remediation of PCE-contaminated groundwater is currently still a challenging task. In this work, the efficiency of a UV-assisted oxidation process exploiting a photocatalyst composed of zero-valent iron supported on commercial zinc sulfide (Fe/ZnS) and incorporated in a highly porous polymer, is investigated. The experimental studies were carried out, for about six months, on a pilot-scale photoreactor operating in continuous mode at the Solofra (Campania, Italy) wastewater plant, to evaluate the effectiveness and stability of the photocatalytic system. The results show that it is possible to reach a PCE degradation in natural groundwater in the range of 85–95%%. Furthermore, a kinetic model is developed and compared with collected experimental data. The mathematical model well describes the experimental data of the photocatalytic system operating both in batch and continuous mode and therefore it can be potentially used for further scale-up of photocatalytic systems devoted to PCE degradation, allowing to estimate the catalyst weight required for total PCE removal as a function of the liquid flow rate to be treated and inlet PCE concentration.

A polymeric composite consisting of Fe-N-codoped TiO2 (Fe-N-TiO2) dispersed into a monolithic syndiotactic polystyrene (sPS) aerogel (Fe-N-TiO2/sPS, 10/90 w/w) was used for the photocatalytic hydroxylation of benzene to phenol in presence of H2O2 to enhance the phenol selectivity and yield compared to Fe-N-TiO2 in powder form. Under UV light, Fe-N-TiO2/sPS composite aerogel showed selectivity to phenol of 43%, one order of magnitude more than the selectivity showed by Fe-N-TiO2 in powder form (4%). Under visible light irradiation Fe-N-TiO2 in powder form did not produce phenol, whereas selectivity to phenol of Fe-N-TiO2/sPS was 16%. The polymeric composite was recycled and reused up to five times without a significant decrease in photocatalytic oxidation activity in terms of benzene conversion and phenol yield, indicating the stability of the catalytic composite. Therefore, it was proved that the obtained photoreactive polymer composite could allow the development of innovative sustainable processes able to realize the selective oxidation reactions of aromatic hydrocarbons under mild conditions.

In this work, P-doped TiO2 (P-TiO2) photocatalyst was prepared by a modified sol-gel method at room temperature and then coated on corona discharge pre-treated polypropylene films (P-TiO2/PP). The obtained photoactive P-TiO2/PP was characterized with different techniques (XRD, SEM and SSA) and the photocatalytic effect under UV and visible light was analyzed in the degradation of methylene blue (MB), used as model organic pollutant. The photocatalytic tests were carried out in a batch photoreactor irradiated by a visible lamp (nominal power of 32 W and wavelength emission > 400 nm). The experimental results showed that the coating of P-TiO2 onto PP films allowed to achieve a MB discoloration of 63% after about 240 min of visible light irradiation.

Today, the increase in agricultural practices leads to pesticide pollution, which has become a threat to both water sources and humans. Various techniques to degrade pesticides have been used, but heterogeneous photocatalysis in presence of semiconductor nanoparticles has proven to be more efficient because it can degrade many persistent organic compounds. However, for practical and industrial applications, it is necessary to immobilize the photocatalyst on the surface or within macroscopic supports to avoid the post-treatment step to separate the photocatalyst in powder form from the treated water at the end of the process. In this work, monolithic polymer/photocatalyst composite aerogels based on syndiotactic polystyrene (sPS) and two different photocatalysts, N-doped TiO2 (NdT) and ZnO/NdT, were prepared to obtain easily recoverable materials for cost-saving processes. The aerogels were tested in the degradation of two target pesticides, atrazine (ATZ) and thiacloprid (THI), using a pilot-scale photoreactor. The experimental data showed a pollutant degradation higher than 90% after 180 min for ATZ and over 90% after 60 min of irradiation for THI. These results indicate that the heterogeneous photocatalytic process based on composite aerogels could be an efficient technology for pesticide degradation.

Heterogeneous photocatalysis is a promising technique for removing pollutants from water. In this work, supercritical antisolvent (SAS)-micronized ZnO (ZnOSAS) is coupled with commercial anatase TiO2 (PC50) to study the photocatalytic degradation of ceftriaxone under UV and visible light. Diffuse ultraviolet–visible reflectance (UV−vis DRS) measurement revealed that the presence of ZnO leads to a slight absorption in the visible region. Wide-angle X-ray diffraction (WAXD) analysis showed the presence of both ZnO wurtzite and TiO2 anatase crystalline phases in the composite. Photocatalytic tests proved that the activity of the ZnOSAS/PC50 composite is higher than that of commercial ZnO, SAS-micronized ZnO, and PC50, allowing complete ceftriaxone degradation under UV light after only 2 min of irradiation time. In contrast, about 90% of ceftriaxone degradation is achieved after 180 min of visible-light irradiation. The photocatalytic results for an experiment carried out in the presence of probe scavenger molecules for reactive oxygen species show that hydroxyl radicals and positive holes are both reactive species involved in the ceftriaxone photocatalytic degradation mechanism. Finally, reuse cycles of the ZnOsas/PC50 composite are performed, demonstrating the stability and recyclability of the photocatalyst.

In this work, photocatalytic materials constituted by Cr-doped TiO2 (Cr-TiO2) decorated with noble metals show high effectiveness in the mineralization of Acid Orange 7 (AO7) and in the disinfection of real river water. The materials were firstly obtained by sol-gel method to get Cr-TiO2 that was subsequently modified by photochemical deposition of Ag or Pd nanoparticles (Ag/Cr-TiO2, Pd/Cr-TiO2). Chemical-physical characterization results evidenced that the noble metals were homogeneously distributed on the Cr-TiO2 surface. By using Pd(0.25%)/Cr-TiO2, the AO7 discoloration efficiency was about 91.4% after only 60 min of visible irradiation, which can be due to the lowest band gap of this material. Moreover, nitrates, chlorides, total hardness, and coliform bacteria content significantly decreased after the treatment of real river water samples (that is contaminated by industrial and domestic effluents) under UV and visible light irradiation in the presence of TiCrOx decorated with noble metals. One hundred percent of elimination rate for E. coli, total coliforms, and other enterobacteriaceae (without regrowth) was achieved by using Ag/Cr-TiO2 as photocatalyst.

Emerging contaminants are a significant issue in the environment. Photocatalysis is proposed as a solution for the degradation of pollutants contained in wastewater. In this work, ZnO-based photocatalysts have been produced and tested for the photocatalytic degradation of an antibiotic; specifically, ceftriaxone has been used as a model contaminant. Moreover, there is particular interest in combining small-size ZnO particles and β-cyclodextrin (β-CD), creating a hybrid photocatalyst. Zinc acetate (ZnAc) (subsequently calcinated into ZnO) and β-CD particles with a mean diameter of 0.086 and 0.38 µm, respectively, were obtained using the supercritical antisolvent process (SAS). The produced photocatalysts include combinations of commercial and micronized particles of ZnO and β-CD and commercial and micronized ZnO. All the samples were characterized through UV–Vis diffuse reflectance spectroscopy (DRS), and the band gap values were calculated. Raman and FT-IR measurements confirmed the presence of ZnO and the existence of functional groups due to the β-cyclodextrin and ZnO combination in the hybrid photocatalysts. Wide-angle X-ray diffraction patterns proved that wurtzite is the main crystalline phase for all hybrid photocatalytic systems. In the photocatalytic degradation tests, it was observed that all the photocatalytic systems exhibited 100% removal efficiency within a few minutes. However, the commercial ZnO/micronized β-CD hybrid system is the photocatalyst that shows the best performance; in fact, when using this hybrid system, ceftriaxone was entirely degraded in 1 min.

Azo dyes are synthetic organic dyes used in the textile, leather, and paper industries. They pose environmental problems due to their toxic and persistent nature. The toxicity is due to the presence of azo groups in the dye molecule that can break down into aromatic amines, which are highly toxic to aquatic organisms and humans. Various treatment methods have been developed to remove azo dyes from wastewater. Conventional wastewater treatments have some drawbacks, such as high operating costs, long processing times, generation of sludge, and the formation of toxic by-products. For these reasons, a valid alternative is constituted by advanced oxidation processes. Good results have been obtained using heterogeneous photocatalysis and supercritical water oxidation. In the former method, a photocatalyst is in contact with wastewater, a suitable light activates the catalyst, and generated reactive oxygen species that react with pollutants through oxidative reactions to their complete mineralization; the latter involves pressurizing and heating wastewater to supercritical conditions in a reactor vessel, adding an oxidizing agent to the supercritical water, and allowing the mixture to react. In this review paper, works in the literature that deal with processing wastewater containing azo dyes through photocatalysts immobilized on macroscopic supports (structured photocatalysts) and the supercritical water oxidation technique have been critically analyzed. In particular, advancement in the formulation of structured photocatalysts for the degradation of azo dyes has been shown, underlying different important features, such as the type of support for the photoactive phase, reactor configuration, and photocatalytic efficiency in terms of dye degradation and photocatalyst stability. In the case of supercritical water oxidation, the main results regarding COD and TOC removal from wastewater containing azo dyes have been reported, taking into account the reactor type, operating pressure, and temperature, as well as the reaction time.

A reverse-micelle sol–gel method was chosen for the preparation of Fe-doped TiO2 samples that were employed in the photodegradation of the crystal violet dye under visible light irradiation in a batch reactor. The dopant amount was varied to assess the optimal photocatalyst composition towards the target dye degradation. The photocatalysts were characterized through a multi-technique approach, envisaging XRPD and QPA as obtained by Rietveld refinement, FE-SEM analysis, DR UV−vis spectroscopy, N2 adsorption/desorption isotherms measurement at −196 °C, ζ-potential measurement, and XPS analysis. The physical-chemical characterization showed that the adopted synthesis method allows obtaining NPs with uniform shape and size and promotes the introduction of Fe into the titania matrix, finally affecting the relative amounts of the three occurring polymorphs of TiO2 (anatase, rutile and brookite). By increasing the Fe content, the band gap energy decreases from 3.13 eV (with undoped TiO2) to 2.65 eV (with both 2.5 and 3.5 wt.% nominal Fe contents). At higher Fe content, surface Fe oxo-hydroxide species occur, as shown by DR UV-vis and XP spectroscopies. All the Fe-doped TiO2 photocatalysts were active in the degradation and mineralization of the target dye, showing a TOC removal higher than the undoped sample. The photoactivity under visible light was ascribed both to the band-gap reduction (as confirmed by phenol photodegradation) and to dye sensitization of the photocatalyst surface (as confirmed by photocatalytic tests carried out using different visible-emission spectra LEDs). The main reactive species involved in the dye degradation were determined to be positive holes.

In recent years, aromatic substances have become the focus of environmental pollution-related concern due to their high stability and mutagenicity. In this regard, researchers have focused their attention on the development of photocatalytic processes to convert nitroaromatic compounds into aniline. In this work, the photocatalytic conversion of nitrobenzene (NB) to aniline (AN) was studied. The photocatalytic reaction was performed using commercial TiO2 (P25) and a photocatalytic aerogel, based on P25 embedded in syndiotactic polystyrene (sPS) aerogel (sPS/P25 aerogel) as photocatalysts. Different alcohols were used as hydrogen sources during the photocatalytic experiments. At the optimized operating conditions (photocatalysts dosage: 0.5 mg/L and 50% (v/v) EtOH%), an AN yield of over 99% was achieved. According to the results, this work could open avenues toward effective production of AN from NB using mild reaction conditions with sPS/P25 aerogel—in view of a possible scale-up of the photocatalytic process.

FeN -co-doped TiO2 photocatalysts are prepared by sol–gel method using titanium tetraisopropoxide, urea and iron(II) acetylacetonate as precursors of titania, nitrogen and iron, respectively. The prepared samples are analysed from chemical-physical point of view by X-ray diffraction (XRD), Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS), specific surface area measurements and scanning electron microscopy (FESEM). UV–Vis DRS spectra evidence that the co-doping of TiO2 with N and Fe leads to the narrowing of the band gap value (2.7 eV) with respect to Fe-doped TiO2 (2.8 eV) and N-doped TiO2 (2.9–3 eV). XRD patterns show that photocatalysts are mainly in anatase phase and Fe and N ions are successfully incorporated into the TiO2 lattice. The average crystallite size of Fe-N co-doped TiO2 is slightly lower than the other samples and equal to about 7 nm and the specific surface area of the co-doped sample results to be 117 m2 g−1. Photocatalytic performances of all prepared samples are evaluated by analysing the degradation of Acid Orange 7 azo dye under visible light irradiation. Photocatalytic efficiency obtained using FeN co-doped TiO2 strongly increases compared to undoped TiO2, N-doped TiO2 and Fe-doped TiO2 photocatalysts. In detail, using the co-doped photocatalyst, dye discoloration and mineralization result equal to about 90 and 83% after 60 min of LEDs visible light irradiation, underlining the best performances of the FeN co-doped TiO2 photocatalyst both in terms of treatment time and electric energy consumption.

TiO2-loaded poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-coHFP) membranes were produced by supercritical CO2-assisted phase inversion. Three different TiO2 loadings were tested: 10, 20, and 30 wt% with respect to the polymer. Increasing the TiO2 amount from 10 wt% to 20 wt% in the starting solution, the transition from leafy-like to leafy-cellular morphology was observed in the section of the membrane. When 30 wt% TiO2 was used, the entire membrane section showed agglomerates of TiO2 nanoparticles. These polymeric membranes were tested to remove Sudan Blue II (SB) dye from aqueous solutions. The adsorption/photocatalytic processes revealed that membrane morphology and TiO2 cluster size were the parameters that mainly affected the dye removal efficiency. Moreover, after five cycles of exposure of these membranes to UV light, SB removal was higher than 85%.

N-doped TiO2 (N-TiO2) and N-doped ZnO (N-ZnO) were synthesized utilizing ammonia as a dopant source. The chemico-physical characteristics of synthesized samples were studied by Raman spectroscopy, X-ray diffraction, SEM analysis, N2 adsorption–desorption at −196 °C, and diffuse reflectance spectroscopy. Compared to undoped samples, the introduction of nitrogen in the semiconductor lattice resulted in a shift of band-gap energy to a lower value: 3.0 eV for N-ZnO and 2.35 eV for N-TiO2. The photocatalysts were tested for the degradation of Eriochrome Black T (EBT), which was selected as a model azo dye. Both N-doped semiconductors evidenced an improvement in photocatalytic activity under visible light irradiation (62% and 20% EBT discoloration for N-TiO2 and N-ZnO, respectively) in comparison with the undoped samples, which were inactive in the presence of visible light. Different behavior was observed under UV irradiation. Whereas N-TiO2 was more photoactive than commercial undoped TiO2, the introduction of nitrogen in ZnO wurtzite resulted in a drastic reduction in photocatalytic activity, with only 45% EBT discoloration compared to total color removal obtained with the commercial ZnO sample, suggesting intrinsic limitations for doping of this class of semiconductors.

Waterborne pathogens represent one of the most widespread environmental concerns. Conventional disinfection methods, including chlorination and UV, pose several operational and environmental problems; namely, formation of potentially hazardous disinfection by-products (DBPs) and high energy consumption. Therefore, there is high demand for effective, low-cost disinfection treatments. Among advanced oxidation processes, the photocatalytic process, a form of green technology, is becoming increasingly attractive. A systematic review was carried out on the synthesis, characterization, toxicity, and antimicrobial performance of innovative engineered photocatalysts. In recent decades, various engineered photocatalysts have been developed to overcome the limits of conventional photocatalysts using different synthesis methods, and these are discussed together with the main parameters influencing the process behaviors. The potential environmental risks of engineered photocatalysts are also addressed, considering the toxicity effects presented in the literature.

Polymeric films and in particular polypropylene (PP) films could be selected as excellent substrates for photocatalytic applications based on TiO2. However, hydrophobic surface of PP makes very difficult the adhesion of TiO2 particles on its surface. In this work corona pre-treated PP was used as a support for commercial TiO2 in order to remove organic dye methylene blue (MB) from aqueous solution under UV irradiation. In details, the pre-treated polypropylene PP films were coated with TiO2 particles by dip-coating technique. The corona pre-treatment is a practical and effective method to increase the wettability of organic polymers due to the introduction of negative groups (COO- , –O–O- ) onto the surfaces, which results in a better adhesion of the photocatalyst. The obtained coated films were characterized with different techniques sand the photocatalytic effect under UV light was analyzed in the degradation of MB dye. The photocatalytic tests were carried out in a batch photoreactor irradiated by a UV lamp (nominal power of 8 W and wavelength emission 365 nm). The experimental results showed that the coating of TiO2 onto PP films allowed to achieve a MB discoloration of 47% after about 180 min of UV irradiation. In contrast the unfunctionalized PP film did not shown any photocatalytic activity under the same irradiation conditions.

Acid Orange 7 (AO7) is an azo dye present in the effluents coming from the textile industry. It is a coloring agent consisting of an azo group bonded to aromatic rings. This azo dye can react with other chemical substances producing aromatic amines which cause toxic and carcinogenic effects in the environment. For this reason, it is necessary to eliminate this compound from aqueous discharges. Recently, the scientific research has focused the attention on heterogeneous photocatalysis based on semiconductor oxides because it is a technology able to completely degrade many organic pollutants to carbon dioxide and water at ambient temperature under UV/visible light irradiation. In photocatalysis, the most used semiconductor is titanium dioxide (TiO2). TiO2 presents various crystalline phase and a wide band gap (3.2 eV for anatase), therefore, it can be activated only under UV light irradiation. In order to make TiO2 active under visible light, in this work TiO2 doped with metallic (Fe) and non-metallic element (N) was synthetized through sol-gel method. The photocatalytic tests on discoloration of AO7 aqueous solution were carried in a photoreactor surrounded by visible-LEDs strip. To determine the optimum conditions for the photodegradation, the influence of photocatalyst dosage (1.5 - 6 g L-1), initial AO7 concentration (5 - 20 mg L-1), initial pH of the solution (3-8) and the incident visible light intensity (3.25 to 13 mW cm-2) was investigated. It was observed that the Fe-N-TiO2 photocatalyst reached about 90% of AO7 discoloration and 83% of mineralization efficiency under the optimized working conditions, in a very short time (60 min) using a photocatalyst dosage of 3 g L-1 and AO7 initial concentration of 10 mg L-1.

Nowadays one of the topics of greatest interest to the scientific community is the search for new eco-friendly technologies that allow the production of energy. In particular, one of the main players in this area is hydrogen. Several innovative processes are proposed in the literature for the production of hydrogen. One of these is the heterogeneous photocatalysis. Furthermore, it is also interesting to evaluate the source from which hydrogen is obtained. An interesting solution is glucose, one of the most familiar biomass, which can be used to produce hydrogen from a photocatalytic process. For this reason, in this work we propose the use of Ni as active phase supported on LaFeO3 photocatalyst for the renewable H2 production from glucose aqueous solution. Perovskite photocatalysts are quite encouraging materials for H2 production from aqueous solution owing to their stability in water. Low-cost nickel can be used to improve the performance of perovskites, modifing their surface and thus avoiding the use of expensive noble metal based cocatalysts. Specifically, the LaFeO3 catalyst was prepared by solution combustion synthesis using citric acid as organic fuel. A specific amount of Ni was deposited on LaFeO3 surface by chemical reduction method, using sodium borohydride (NaBH4) as a reducing agent. The prepared samples were characterized by different techniques, such as XRD and UV-Vis. The photocatalytic tests were carried out in a pyrex cylindrical reactor equipped with a N2 distributor device and irradiated by four UV lamps (emitting at 365 nm) positioned at the same distance from the external surface of the reactor (about 30 mm). The tests were realized with a solution volume equal to 80 ml, an initial concentration of glucose equal to 5550 µmol L-1 and a catalyst dosage equal to 1.5 g L-1. The experimental results evidenced that the presence of Ni on LaFeO3 surface enhanced the H2 production and in particular the highest hydrogen production (about 2242 µmol L-1 after 4 h of irradiation time) was obtained with Ni/LaFeO3, whereas the raw LaFeO3 was able to produce a lower H2 amount (about 1394 µmol L-1 after the same irradiation time).

Nowadays one of the most significant environmental problems is related to wastewater treatment because the release of pollutants into the environment has posed a risk to natural ecosystems and human health. Therefore, it is necessary to treat wastewater in appropriately way. Three main steps are applied in wastewater treatments that are commonly called preliminary, secondary and tertiary treatment. The preliminary and secondary treatment steps are based on physical and chemical processes. However, in most cases these types of processes are not enough alone. Among tertiary process treatment, compared to the common processes used for wastewater disinfection, new methods without the formation of disinfection by-products have been recently investigated by researchers. In this sense, among advanced oxidation process (AOPs), heterogeneous photocatalysis is a powerful alternative technique to treat polluted water because it is able to mineralize many organic compounds through the generation of hydroxyl radicals thanks to the presence of a semiconductor activated by a light source. For engineering applications, the immobilization of catalyst powders onto a suitable solid inert support is required. In this work, ZnO immobilized on macroscopic polystyrene pellets has been prepared, characterized and studied in the photocatalytic treatment of four wastewaters samples coming from secondary and tertiary processes of wastewater treatment plant by leather industries. The efficiency of the system has been determined by measuring chemical oxygen demand (COD) and total organic carbon (TOC). Photocatalytic results showed in all cases a significant COD and TOC reduction, after 7 h of UV light irradiation.

In this work, the optimization of Ni amount on LaFeO3 photocatalyst was studied in the photocatalytic molecular hydrogen production from glucose aqueous solution under UV light irradiation. LaFeO3 was synthesized via solution combustion synthesis and different amount of Ni were dispersed on LaFeO3 surface through deposition method in aqueous solution and using NaBH4 as reducing agent. The prepared samples were characterized with different techniques: Raman spectroscopy, UltraViolet-Visible Diffuse Reflectance Spettroscopy (UV–Vis-DRS), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), X-ray Fluorescence (XRF), Transmission Electron microscopy (TEM), and Scanning Electron microscopy (SEM) analyses. For all the investigated photocatalysts, the presence of Ni on perovskite surface resulted in a better activity compared to pure LaFeO3. In particular, it is possible to identify an optimal amount of Ni for which it is possible to obtain the best hydrogen production. Specifically, the results showed that the optimal Ni amount was equal to nominal 0.12 wt% (0.12Ni/LaFeO3), for which the photocatalytic H2 production was equal to 2574 μmol/L after 4 h of UV irradiation. The influence of different of photocatalyst dosage and initial glucose concentration was also evaluated. The results of the optimization of operating parameters indicated that the highest molecular hydrogen production was achieved on 0.12Ni/LaFeO3 sample with 1.5 g/L of catalyst dosage and 1000 ppm initial glucose concentration. To determine the reactive species that play the most significant role in the photocatalytic hydrogen production, photocatalytic tests in the presence of different radical scavengers were performed. The results showed that •OH radical plays a significant role in the photocatalytic conversion of glucose in H2. Moreover, photocatalytic tests carried out with D2O instead of H2O evidenced the role of water molecules in the photocatalytic production of molecular hydrogen in glucose aqueous solution.

Different tri-doped TiO2 photocatalysts (Fe-N-P/TiO2, Fe-N-S/TiO2, Fe-Pr-N/TiO2, Pr-N-S/TiO2, and P-N-S/TiO2) were successfully prepared and tested in the photocatalytic removal of thiacloprid (THI) under UV-A, visible, and direct solar light irradiation. The physical-chemical properties of the prepared catalysts were analyzed by different characterization techniques, revealing that dopants are effectively incorporated into the anatase TiO2 lattice, resulting in a decrease of the energy band gap. The reduction of photoluminescence intensity indicates a lower combination rate and longer lifespan of photogenerated carriers of all doped samples in comparison with the un-doped TiO2. The doped photocatalysts not only significantly promote the photodegradation under UV-A light irradiation but also extend the optical response of TiO2 to visible light region, and consequently improve the visible light degradation of THI. Fe-N-P tri-doped TiO2 sample exhibits the highest THI photodegradation degree (64% under UV-A light, 29% under visible light and 73% under solar light).

Fe-doped titania photocatalysts (with 1, 2.5, and 3.5 wt. % Fe nominal content), showing photocatalytic activity under visible light, were prepared by a soft-template assisted sol–gel approach in the presence of the triblock copolymer Pluronic P123. An undoped TiO2 photocatalyst was also prepared for comparison. The photocatalysts were characterized by means of X-ray powder Diffraction (XRPD), Quantitative Phase Analysis as obtained by Rietveld refinement, Diffuse Reflectance (DR) UV−Vis spectroscopy, N2 adsorption/desorption at −196 °C, electrophoretic mobility in water (ζ-potential), and X-ray photoelectron spectroscopy (XPS). The physico-chemical characterization showed that all the samples were 100% anatase phase and that iron was present both in the bulk and at the surface of the Fe-doped TiO2. Indeed, the band gap energy (Eg) decreases with the Fe content, with Tauc’s plot determined values ranging from 3.35 (undoped TiO2) to 2.70 eV (3.5 wt. % Fe). Notwithstanding the obtained Eg values, the photocatalytic activity results under visible light highlighted that the optimal Fe content was equal to 2.5 wt. % (Tauc’s plot determined Eg = 2.74 eV). With the optimized photocatalyst and in selected operating conditions, under visible light it was possible to achieve 90% AO7 discoloration together with a TOC removal of 40% after 180 min. The kinetic behavior of the photocatalyst was also analyzed. Moreover, the tests in the presence of three different scavengers revealed that the main reactive species are (positive) holes and superoxide species. Finally, the optimized photocatalyst was also able to degrade phenol under visible light.

Ceria-supported vanadium catalysts were studied for H2S removal via partial and selective oxidation reactions at low temperature. The catalysts were characterized by N2 adsorption at 77 K, Raman spectroscopy, X-ray diffraction techniques, and X-ray fluorescence analysis. X-ray diffraction and Raman analysis showed a good dispersion of the V-species on the support. A preliminary screening of these samples was performed at fixed temperature (T = 327 °C) and H2S inlet concentration (10 vol%) in order to study the catalytic performance in terms of H2S conversion and SO2 selectivity. For the catalyst that exhibited the higher removal efficiency of H2S (92%) together with a lower SO2 selectivity (4%), the influence of temperature (307–370 °C), contact time (0.6–1 s), and H2S inlet concentration (6–15 vol%) was investigated.

“Non-thermal plasma technology” (NTP) has notably increased [...]

Conventional methods generally used to synthesize heterogeneous photocatalysts have some drawbacks, mainly the difficult control/preservation of catalysts’ morphology, size or structure, which strongly affect the photocatalytic activity. Supercritical carbon dioxide (scCO2)-assisted techniques have recently been shown to be a promising approach to overcome these limitations, which are still a challenge. In addition, compared to traditional methods, these innovative techniques permit the synthesis of high-performance photocatalysts by reducing the use of toxic and polluting solvents and, consequently, the environmental impact of long-term catalyst preparation. Specifically, the versatility of scCO2 allows to prepare catalysts with different structures (e.g., nanoparticles or metal-loaded supports) by several supercritical processes for the photocatalytic degradation of various compounds. This is the first updated review on the use of scCO2-assisted techniques for photocatalytic applications. We hope this review provides useful information on different approaches and future perspectives.

P-nitrophenol (PNP) is a toxic organic pollutant and it is difficult to remove from wastewater by means of conventional treatment processes. Therefore, effective and low cost alternative water treatment technologies are required. In the last years there has been a growing interest in advanced oxidation processes involving semiconductor mediated photocatalysis because the process mineralizes many toxic organic pollutants to carbon dioxide and water at ambient temperature under UV light. The aim of this work is to synthetize ZnS photocatalyst starting from formerly ZnO prepared with different precursors such as zinc sulphate and zinc nitrate by means of precipitation method. ZnS was then obtained by sulfuration of ZnO particles. The sulfuration step was carried out at 450°C in presence of N2 gaseous stream containing H2S at 5 vol%. The prepared photocatalysts were characterized from chemical-physical point of view using different techniques (XRD, BET, UV-vis DRS, Raman). The photocatalytic tests were carried out in a recirculating batch cylindrical photoreactor irradiated by a UV-LEDs strip (nominal power of 12W/m and wavelength emission peak at about 365 nm) surrounding the external surface of the reactor. The experimental results evidenced that the optimal sample is ZnS obtained from the sulphuration of ZnO synthetized by zinc sulphate. In particular, this sample was able to achieve about 51% PNP degradation after 240 min of UV light irradiation.

In this work the photocatalytic hydrogen production from aqueous solution containing organic compounds, using perovskite based photocatalyst supported on magnetic particles, was studied. In particular a photocatalyst based on Ru doped LaFeO3 was used. The photocatalyst was prepared by solution combustion synthesis using citric acid as organic fuel, and it was characterized by different techniques, such as XRD, UV-Vis DRS and Raman spectroscopy. This semiconductor has shown photocatalytic activity in presence of visible light and it was supported on Fe2O3 magnetic particles in order to remove it easily at the end of the process. The Fe2O3 particles were prepared by combustion flame synthesis, using citric acid as organic fuel and metal nitrate as iron oxide precursor. The Ru-LaFeO3 photocatalyst was coupled with magnetic Fe2O3 particles by a physical mixture in order to ensure a tight contact between the two solid phases (Ru-LaFeO3/Fe2O3). Photocatalytic tests were carried out in a pyrex cylindrical reactor equipped with a N2 distributor device and irradiated by visible-LEDs. Different aqueous solution containing organic compounds such as ethanol, glycerol or methanol were tested. The experimental results evidenced that the higher hydrogen production (about 10000 µmol L-1 after 4 h of irradiation time) was obtained in presence of methanol. The magnetic composite showed a very high stability also after several reuse cycles.

The hydrolysis of carbonyl sulfide (COS) was studied in a gas-liquid reactor at room temperature and ambient pressure in presence of alkanolamines, such as monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA) and diisopropylamine (DIPA). The activity and stability of the different amines was investigated at fixed COS inlet concentration and reaction volume. The highest removal efficiency of COS was obtained in presence of DEA aqueous solution (25 %), while the lowest COS conversion was observed with the tertiary amine MDEA (< 10 %). A greater COS removal was obtained in presence of the higher reaction volume (400 cm3) that was equal to 25 % for DEA and 26 % for DIPA, respectively. Finally, the evaluation of the kinetic constant for the COS hydrolysis reaction with DEA was performed.

The aim of this work was to evaluate the effectiveness of TiO2 pellets for the photocatalytic oxidation of As(III) to As(V) under UV light with simultaneous adsorption of As(V) in a continuous packed bed photoreactor. In particular commercial cylindrical pellets of TiO2 were used as photocatalyst. Experimental photocatalytic tests were carried out in a cylindrical pyrex photoreactor (irradiated by UV-LEDs) which operates in continuous mode in order to treat aqueous solution contaminated with arsenic at different initial As(III) concentration. Preliminary tests conducted in a batch configuration showed that TiO2 pellets adsorb As(V) produced from the photoreaction, without leading to a deactivation of the active sites and evidencing that the As(V) produced is completely released into the solution. Moreover, TiO2 pellets maintained an excellent photoactivity and durability after several cycles making it a very promising catalyst to be employed in continuous reactors for the photocatalytic treatment of water polluted by arsenic, obtaining 98% As(III) oxidation yield after only 15 min of UV-LEDs irradiation. Moreover, the use of a continuous packed bed reactor filled with the stable TiO2 catalyst pellets irradiated by UV light allows to reach a steady state As(III) concentration without any deactivation phenomena. Finally, with 1 mg L-1 As(III) initial concentration, no As(V) release was observed from TiO2 surface during the irradiation time evidencing that the total arsenic removal could be achieved thanks to the photocatalytic properties and adsorption ability of the TiO2 pellets.

In this work it was investigated the photocatalytic activity of ZnO coupled with inorganic “up-conversion” phosphors for the treatment of aqueous solutions polluted with methylene blue (MB), in the presence of visible light irradiation. Specifically, the successfully prepared “up-conversion” phosphors nanoparticles emit, when excited with visible light, UV light with main emission at 365 nm. The photocatalytic tests were carried out in a cylindrical pyrex photoreactor equipped with a magnetic stirrer to ensure the continuous mixing of the physical mixtures of “up-conversion” phosphors and commercial ZnO nanoparticles in the solution and irradiated by visible light instead of UV light normally required to excite ZNO. Experimental results were analysed by evaluating the MB decolourization through spectrophotometric method and the total organic carbon (TOC) through high temperature combustion method. In particular, it was found that the photocatalytic performances obtained using ZnO nanoparticles coupled with “up-conversion” phosphors are strongly increased compared to the use of ZnO alone. These results confirmed the enhancement of photocatalytic performances induced by UV photons emitted by “up-conversion” phosphors nanoparticles, able to activate ZnO, demonstrating how their use in photocatalytic systems can be an alternative to the traditional UV lamps, thus preserving human health, environmental and, at the same time, allows to save the energy in process management.

In this work, two different commercial macroscopic adsorbent materials (Na-ZSM5 zeolite in spherical pellets and TiO2 cylindrical pellets) has been tested in the removal of model organic food dyes (Patent blue V, E131) and they were regenerated using an innovative techniques based on non-thermal plasma process. The adsorption experiments were carried out using a pyrex cylindrical reactor and liquid samples were analyzed in continuous mode by spectrophotometric measurement at ? = 636 nm. The results demonstrated that these materials were able to remove Patent blue V dye, with removal efficiency equal to 80% for the zeolite and 95% for TiO2 pellets after 400 min of treatment time. The adsorbent materials have been used for several cycles until their saturation. In particular, after seven adsorption cycles, the adsorbing capacity was reduced of about 60 and 20% for zeolite and TiO2 pellets, respectively. Subsequently, the materials were regenerated by non-thermal plasma and reused in the adsorption system. The results evidenced that the regeneration by non-thermal plasma was able to induce the complete degradation of the absorbed organic substance and consequently restoring the initial adsorption capacity of both macroscopic adsorbent materials

In this paper, the photocatalytic degradation of glyphosate by zinc oxide (ZnO) photocatalysts doped with tungsten (W) was investigated under solar simulated light. The photocatalysts were successfully synthesized through a simple precipitation method and subsequently characterized by different techniques: Raman spectroscopy, UV–Vis, N2 adsorption at −196 °C, X-ray diffraction, and SEM analysis. In particular, all the prepared catalysts were characterized by a crystallite size of about 28 nm and a hexagonal wurtzite structure. After the W doping, the bandgap energy decreased from 3.22 of pure ZnO to 3.19 for doped ZnO. This allowed us to obtain good results in terms of glyphosate degradation and simultaneous mineralization under solar simulated lamps, making the process environmentally friendly and with almost zero energy costs. In particular, the best photocatalytic performance was obtained with 100 W-ZnO (prepared with 1.5 mol% of W). With this catalyst, after 180 min of exposure to solar simulated light, the glyphosate degradation and mineralization was equal to 74% and 30%, respectively. Furthermore, it has been shown that the best catalyst dosage was equal to 1.5 g/L. The study on the influence of pH evidenced that the best photocatalytic performances are obtained at spontaneous (neutral) pH conditions. Finally, to determine the main reactive species in the glyphosate oxidation, the effects of different radical scavengers were tested. The results evidenced that the glyphosate oxidation mechanism seems to be related mainly to the O2•− generated under simulated solar light irradiation, but also in minor part to h+.

Phenol is an important chemical compound since it is a precursor of the industrial production of many materials and useful compounds. Nowadays, phenol is industrially produced from benzene by the multi-step “cumene process”, which is energy consuming due to high temperature and high pressure. Moreover, in the “cumene process”, the highly explosive cumene hydroperoxide is produced as an intermediate. To overcome these disadvantages, it would be useful to develop green alternatives for the synthesis of phenol that are more efficient and environmentally benign. In this regard, great interest is devoted to processes in which the one-step oxidation of benzene to phenol is achieved, thanks to the use of suitable catalysts and oxidant species. This review article discusses the direct oxidation of benzene to phenol in the liquid phase using different catalyst formulations, including homogeneous and heterogeneous catalysts and photocatalysts, and focuses on the reaction mechanisms involved in the selective conversion of benzene to phenol in the liquid phase.

Non-thermal plasma is one of the most promising technologies used for the degradation of hazardous pollutants in wastewater. Recent studies evidenced that various operating parameters influence the yield of the Non-Thermal Plasma (NTP)-based processes. In particular, the presence of a catalyst, suitably placed in the NTP reactor, induces a significant increase in process performance with respect to NTP alone. For this purpose, several researchers have studied the ability of NTP coupled to catalysts for the removal of different kind of pollutants in aqueous solution. It is clear that it is still complicated to define an optimal condition that can be suitable for all types of contaminants as well as for the various types of catalysts used in this context. However, it was highlighted that the operational parameters play a fundamental role. However, it is often difficult to understand the effect that plasma can induce on the catalyst and on the production of the oxidizing species most responsible for the degradation of contaminants. For this reason, the aim of this review is to summarize catalytic formulations coupled with non-thermal plasma technology for water pollutants removal. In particular, the reactor configuration to be adopted when NTP was coupled with a catalyst was presented, as well as the position of the catalyst in the reactor and the role of the main oxidizing species. Furthermore, in this review, a comparison in terms of degradation and mineralization efficiency was made for the different cases studied.

The aim of this work was the optimization of the performance of the cold plasma technology coupled with a structured catalyst for the discoloration and mineralization of “acid orange 7” (AO7) azo dye. The structured catalyst consists of Fe2O3 immobilized on glass spheres, and it was prepared by the “dip coating” method and characterized by different chemico-physical techniques. The experiments were carried out in a dielectric barrier discharge (DBD) reactor. Thanks to the presence of the catalytic packed material, the complete discoloration and mineralization of the dye was achieved with voltage equal to 12 kV, lower than those generally used with this technology (approximately 20–40 kV). The best result in terms of discoloration and mineralization (80% after only 5 min both for discoloration and mineralization) was obtained with 0.25 wt% of Fe2O3 immobilized on the glass spheres, without formation of reaction by-products, as shown by the HPLC analysis. The optimized catalyst was reused for several reuse cycles without any substantial decrease of performances. Moreover, tests with radical scavengers evidenced that the most responsible oxidizing species for the degradation of AO7 dye was O2•−.

The aim of this work was to study photocatalysts based on Titania doped with Fe, active in the presence of visible light and effective in the oxidation of As(III) to As(V). Fe-doped TiO2 photocatatysts were prepared using sol-gel method and characterized by different techniques, such as XRD, UV-Vis DRS and Raman spectroscopy. Photocatalytic experiments were carried out using a cylindrical photoreactor irradiated with a strip of visible-LEDs (nominal power: 10W) with emission in the range 400 - 600 nm. Aqueous samples containing 6 mg L-1 of As(III) were used in photocatalytic experiments. Chemical-physical characterization results evidenced that the doping of TiO2 with Fe induced a decrease of band gap value from 3.2 eV to 2.9 eV, thus making the photocatalyst active under visible light. Consistently with the characterization results, the semiconductor Fe-doped TiO2 exhibited good photoactivity in the visible light driven tests: the complete oxidation of As(III) to As(V) took place after only 30 min of irradiation in distilled water and after 60 min in drinking water.

In recent years, in order to solve the environmental problems associated with electricity production, alternative systems to traditional methods have been developed. In this contest, fuel cells are widely considered to be an efficient and non-polluting power source and therefore, they are considered to be promising energy devices for the transport, mobile, and stationary sectors. At the current stage of technology, among different types of developed fuel cells, proton exchange membrane fuel cells (PEM) deserve major attention. Pt/C deposited on Nafion membrane is the most used electrocatalyst for PEM due to the highest oxygen reduction catalytic activity. The most used conventional deposition methods on Nafion polymeric membranes for commercial PEM are screen printing and transfer printing. In order to improve the specific activity of Pt, alternative and cheap techniques are under investigation. Therefore, in this work the performances of Pt/C samples deposited by dipping method and spray coating method have been compared, using a commercial system, as reference. Experimental tests were performed using a commercial Pt/C catalyst (20 wt. % Pt on Carbon Vulcan XC-72) deposited on Nafion membrane and tested in the 100 cm2 single-cell testing kits. At the same cell voltage (0.3 V) and Pt loading (0.12 mgPt cm-2), the results showed that the spray coating provided both a higher current density and a higher maximum power density (90 mW·cm-2) compared to the dipping method (38 mW·cm-2). Subsequently, the influence of Pt/C electrocatalyst load on PEM by spray coating method has been investigated and a Pt loading equal to 0.12 mgPt·cm-2 has guaranteed the best performances. Moreover, the performances of a commercial PEM containing a Nafion membrane functionalized by screen printing method with 0.5 mgPt·cm-2 has been compared to the PEM with the membrane prepared by spray coating method loaded with 0.12 mgPt·cm-2. Experimental results showed that, at the same cell voltage, the PEM prepared with spray coating method allowed to obtain an electrical power higher than that obtained using commercial PEM. Finally, the use of PEM at 0.12 mgPt·cm-2 obtained by spray coating method showed a remarkable stability because there was no decrease in the generated current also for long test time (higher than 30 h).

A supported metal sulphide - based catalyst was prepared and studied for the reaction of H2S oxidative decomposition to produce simultaneously H2 and sulphur. The study was carried out by investigating different operating conditions such as H2S inlet concentration (10 - 40 vol%), O2/H2S feeding molar ratio (0.2 - 0.35) and reaction temperature (700 – 1,100 °C) with the aim to minimize SO2 selectivity and maximize the H2 yield together with a good H2S conversion. From the preliminary experimental tests, it was possible to identify the optimal operating conditions (T = 1,100 °C, H2S = 10 vol%, O2/H2S = 0.2), suitable to obtain a high H2S conversion (59 %), a good H2 yield (20 %) and depressing the SO2 selectivity (< 0.05 %). The catalyst showed a good activity and stability during 10 h of time on stream without any deactivation phenomena. The presence of the catalyst resulted in an improvement of both H2S decomposition reaction to produce H2 and partial oxidation reaction to sulphur, realizing simultaneously the abatement of SO2 by the Claus reaction.

The aim of this work is to demonstrate the effectiveness of the photocatalytic process in the Methyl Orange azo dye degradation and simultaneous H2 production by using ZnO doped with ruthenium. Ru-modified ZnO photocatalysts were prepared by precipitation method and were characterized by different techniques (XRF, Raman, XRD, N2 adsorption at −196 °C, and UV−vis DRS). The experiments were carried out in a pyrex cylindrical reactor equipped with a nitrogen distributor device and irradiated by four UV lamps with the main wavelength emission at 365 nm. Different Ru amounts (from 0.10 to 0.50 mol%) were tested in order to establish the optimal amount of the metal to be used for the ZnO doping. The photocatalytic activity was evaluated both in terms of Methyl Orange removal and hydrogen production. The experimental results showed that the best activity, both in terms of H2 production and Methyl Orange degradation, was obtained with the Ru-modified ZnO photocatalyst at 0.25 mol% Ru loading. In particular, after four hours of UV irradiation time, the discoloration and mineralization degree were equal to 83% and 78%, with a simultaneous hydrogen production of 1216 µmol L−1. This result demonstrates the ability of the photocatalytic process to valorize a dye present in wastewater, managing to obtain a hydrogen production comparable with the data present in the literature today in the presence of other sacrificial substances.

Highly porous monolithic aerogels based on ZnO photocatalyst and syndiotactic polystyrene (s-PS) were obtained by supercritical CO2 treatment of ZnO/s-PS gels. The prepared aerogels were characterized and their photocatalytic activity was evaluated using phenol and toluene as water pollutant models. The s-PS nanoporous crystalline phase, able to absorb pollutant molecules, was proven to be necessary to ensure high photocatalytic efficiency as the aerogel acts not only as a support, but also as pollutant pre-concentrator. The reusability of ZnO/s-PS aerogels is also strong showing no decrease in photocatalytic activity after six consecutive degradation trials. Finally, the aerogel matrix prevents ZnO dissolution occurring under acidic conditions and promotes a selective removal of the pollutants. The synergy between the photocatalyst and the innovative polymeric support provides the composite system with robustness, chemical stability, easy recovery after treatment, high efficiency of pollutant removal with a marked selectivity which make these materials promising for large scale applications.

The aim of this work was to analyze the effect of visible LED dimming duty-cycle modulation techniques in a photocatalytic system for urea degradation using a visible light photocatalyst immobilized on macroscopic supports. For this reason, the effect of different LED dimming techniques was investigated and compared in terms of urea degradation together with ammonia and nitrate production during the irradiation time. The experimental results evidenced that using a visible LED dimming modulation with variable-peak variable-duty pulse-width modulation (PWM) allows to improve the photocatalytic degradation process, with respect to classical LED dimming with fixed-peak fixed-duty PWM, and influences the product’s distribution of ammonia and nitrate in water. Therefore, the proof of concept herein proposed could be considered as preliminary potential results to be used in water recycling applications with a particular emphasis in recovery of urea photodegradation byproducts, such as ammonia, from wastewater that could be used as potential resources and an energy resource.

Cu-doped ZnO photocatalysts at different Cu loadings were prepared by a precipitation method. The presence of Cu in the ZnO crystal lattice led to significant enhancement in photocatalytic activity for H2 production from an aqueous glycerol solution under visible light irradiation. The best Cu loading was found to be 1.08 mol %, which allowed achieving hydrogen production equal to 2600 μmol/L with an aqueous glycerol solution at 5 wt % initial concentration, the photocatalyst dosage equal to 1.5 g/L, and at the spontaneous pH of the solution (pH = 6). The hydrogen production rate was increased to about 4770 μmol/L by increasing the initial glycerol concentration up to 10 wt %. The obtained results evidenced that the optimized Cu-doped ZnO could be considered a suitable visible-light-active photocatalyst to be used in photocatalytic hydrogen production without the presence of noble metals in sample formulation.

The presence of azo dyes in textile effluents is an issue of major concern due to their potential impact on the environment and human health. In this study we investigate the photocatalytic degradation under visible light of Reactive Violet 5 (RV5), an azo dye widely used in the textile industry. A preliminary screening of different titania-based catalysts was carried out to identify the best candidate for RV5 removal. The selected catalyst was then tested in a stirred and aerated lab-scale reactor illuminated with a blue light-emitting diode (LED) source emitting in the wavelength range of 460−470 nm. The effects of pH, catalyst load, and hydrogen peroxide additions on the efficiency of dye removal were evaluated. Under the best conditions (pH 10, 3 g/L of catalyst, and 60 mM hydrogen peroxide), the dye solution was completely decolorized in about 2 h. Overall, the results obtained suggest that the proposed process may represent a suitable method for the removal of RV5 from textile effluents.

In this work, the synthesis of zinc oxide (ZnO) photocatalyst from thermal decomposition of zinc acetate (ZnAc) nanoparticles obtained by supercritical antisolvent (SAS) precipitation was investigated. The optimization of calcination conditions of the SAS ZnAc was carried out, studying the effect of temperature (in the range 300–600 °C) on the production of ZnO nanoparticles. In particular, it was demonstrated that the organic residues in ZnO and its particle size, thus the specific surface area, strongly affect the photocatalytic performances. SAS micronization of ZnAc produces regular nanoparticles with a mean diameter of about 54.5 ± 11.5 nm, whereas unprocessed ZnAc is characterized by very large crystals. The experimental results evidenced that ZnAc prepared by SAS process calcined at 500 °C showed a regular nanometric structure (mean diameter: 65.0 ± 14.5 nm) and was revealed to be the best choice for the photocatalytic removal of crystal violet dye (CV). In fact, the photocatalytic activity performances of ZnO nanoparticles prepared by this route were higher with respect to that of ZnO from unprocessed ZnAc calcined at 500 °C (which is characterized by irregular tetrapods with mean size 181.1 ± 65.5 nm). The optimized photocatalyst was able to assure the complete CV decolorization in 60 min of UV irradiation time and a mineralization degree higher than 90% after 120 min of treatment time.

The threat of antibiotic resistance to the wellbeing of societies is well established. Urban wastewater treatment plants (UWTPs) are recognised sources for antibiotic resistance dissemination in the environment. Herein a novel cerium-doped zinc oxide (Ce-ZnO) photocatalyst is compared to ZnO and the benchmark TiO2-P25 in the immobilised form on a metallic support, to evaluate a photocatalytic process as a possible tertiary treatment in UWTPs. The catalysts were compared for the removal of two antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), and for the inactivation of Escherichia coli (E. coli) strain DH5-Alpha in isotonic sodium chloride solution and of autochthonous bacteria in real secondary wastewater. In real wastewater, E. coli and other coliforms were monitored, as well as the respective fractions resistant to ofloxacin and azithromycin. In parallel, Pseudomonas aeruginosa and the respective sub-population resistant to ofloxacin or ciprofloxacin were also monitored. Photocatalysis with both ZnO and Ce-ZnO was faster than using TiO2-P25 at degrading the antibiotics, with Ce-ZnO the fastest against SMX but slower than undoped ZnO in the removal of TMP. Ce-ZnO catalyst reuse in the immobilised form produced somewhat slower kinetics maintained >50% of the initial activity, even after five cycles of use. Approximately 3 log10 inactivation of E. coli in isotonic sodium chloride water was recorded with reproducible results. In the removal of autochthonous bacteria in real wastewater, Ce-ZnO performed better (more than 2 log values higher) than TiO2-P25. In all cases, E. coli and other coliforms, including their resistant subpopulations, were inactivated at a higher rate than P. aeruginosa. With short reaction times no evidence for enrichment of resistance was observed, yet with extended reaction times low levels of bacterial loads were not further inactivated. Overall, Ce-ZnO is an easy and cheap photocatalyst to produce and immobilise and the one that showed higher activity than the industry standard TiO2-P25 against the tested antibiotics and bacteria, including antibiotic-resistant bacteria.

In this work, the influence of simple acids in the room temperature sol-gel synthesis of TiO2 was investigated and the efficiency of prepared photocatalysts was evaluated in the removal of caffeine. To improve the photoactivity of TiO2, vanadium-doped TiO2 (VTiO2) samples were obtained starting from different amount of vanadyl sulphate as a dopant source. The samples were centrifuged, washed and finally dried at room temperature, and no calcination step was carried out. The prepared photocatalysts were characterized by different techniques (X-ray powder diffraction (XRD), specific surface area (SSA), ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) and Raman). VTiO2 photocatalysts were tested in the photocatalytic removal of aqueous solutions containing caffeine. The photocatalytic tests were carried out in a recirculating batch cylindrical photoreactor irradiated by a UV LEDs strip (nominal power of 12 W and wavelength emission peak at about 365 nm) surrounding the external surface of the reactor. The optimized VTiO2 photocatalyst was able to reach a caffeine degradation of about 96% after 360 min of UV light irradiation with a total organic carbon (TOC) removal of 72%.