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Cu2ZnSnSe4 (CZTSe) nanoparticles (NPs) were successfully synthesized via a solvothermal method. Their structural, compositional, morphological, optoelectronic, and electrochemical properties have been characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Field-emission scanning electron microscopy (FE-SEM), transmission electron microscope (TEM), UV-vis absorption spectroscopy, and electrochemical impedance spectroscopy (EIS) techniques. Porosimetry and specific surface area in terms of the Brunauer-Emmett-Teller (BET) technique have also been studied. XRD indicates the formation of a polycrystalline kesterite CZTSe phase. Raman peaks at 173 and 190 cm-1 confirm the formation of a pure phase. TEM micrographs revealed the presence of nanoparticles with average sizes of ~90 nm. A BET surface area of 7 m2/g was determined. The CZTSe NPs showed a bandgap of 1.0 eV and a p-type semiconducting behavior. As a proof of concept, for the first time, the CZTSe NPs have been used as a visible-light-driven photocatalyst to Congo red (CR) azo dye degradation. The nanophotocatalyst material under simulated sunlight results in almost complete degradation (96%) of CR dye after 70 min, following a pseudo-second-order kinetic model (rate constant of 0.334 min-1). The prepared CZTSe was reusable and can be repeatedly used to remove CR dye from aqueous solutions.

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In this study, UiO-67 (Zr)/g-C3N4 composites (U67N) were synthesized at wt.% ratios of 05:95, 15:85, and 30:70 using the solvothermal method at 80 °C for 24 h followed by calcination at 350 °C. The composites were characterized using UV-Vis diffuse reflectance spectroscopy, Fourier-transform infrared spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy-energy-dispersive X-ray spectroscopy, transmission electron microscopy, and nitrogen physisorption analysis. In addition, thermal stability analysis of UiO-67 was conducted using thermogravimetric analysis. The photocatalytic performance of the composites was assessed during the degradation and mineralization of a mixture of methylparaben (MeP) and propylparaben (PrP) under simulated sunlight. The adsorption process of U67N 15:85 was characterized through kinetic studies and adsorption capacity experiments, which were modeled using pseudo-first-order and pseudo-second-order kinetics and Langmuir and Freundlich isotherms, respectively. The influence of pH levels 3, 5, and 7 on the photocatalytic degradation of the mixture was investigated, revealing enhanced degradation and mineralization at pH 3. The U67N composite exhibited dual capability in removing contaminants through adsorption and photocatalytic processes. Among the prepared composites, U67N 15:85 demonstrated the highest photocatalytic activity, achieving removal efficiencies of 96.8% for MeP, 92.5% for PrP, and 45.7% for total organic carbon in 300 kJ/m2 accumulated energy (3 h of reaction time). The detoxification of the effluent was confirmed through acute toxicity evaluation using the Vibrio fischeri method. The oxidation mechanism of the heterojunction formed between UiO-67 (Zr) and g-C3N4 was proposed based on PL analysis, photoelectrochemistry studies (including photocurrent response, Nyquist, and Mott-Schottky analyses), and scavenger assays.

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In this work, the synthesis and characterization of a heterogeneous photocatalyst based on spherical silica nanoparticles superficially modified with anthraquinone 2-carboxylic acid (AQ-COOH) are presented. The nanomaterial was characterized by TEM, SEM, FT-IR, diffuse reflectance, fluorescence, NMR, DLS, XRD and XPS. These analyses confirm the covalent linking of AQ-COOH with the NH2 functionality in the nanomaterial and, more importantly, the photocatalyst retains its photophysical properties once bound. The heterogeneous photocatalyst was successfully employed in the aerobic hydroxylation of arylboronic acids to phenols under sustainable reaction conditions. Phenols were obtained in high yields (up to 100 %) with low catalyst loading (3.5 mol %), reaching TOF values of 3.7 h-1 . Using 2-propanol as solvent at room temperature, the visible light photocatalysis produced H2 O2 as a key intermediate to promote the aerobic hydroxylation of arylboronic acids. The heterogeneous photocatalyst was reused at least 5 times, without modification of the nanomaterial structure and morphology. This simple heterogeneous system showed great catalytic activity under sustainable reaction conditions.

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DyMnO3 is a p-type semiconductor oxide with two crystal systems, orthorhombic and hexagonal. This material highlights its ferroelectric and ferromagnetic properties, which have been the subject of numerous studies. Nevertheless, its photocatalytic activity has been less explored. In this work, the photocatalytic activity of DyMnO3 is evaluated through the photodegradation of MG dye. For the synthesis of this oxide, a novel and effective method was used: polymer-decomposition. The synthesized powders contain an orthorhombic phase, with a range of absorbances from 300 to 500 nm and a band gap energy of 2.4 eV. It is also highlighted that, when using this synthesis method, some of the main diffraction lines related to the orthorhombic phase appear at 100 °C. Regarding its photocatalytic activity, it was evaluated under visible light (λ = 405 nm), reaching a photodegradation of approximately 88% in a period of 30 min. Photocurrent tests reveal a charge carrier separation (e-,h+) at a 405 nm wavelength. The main reactive oxygen species (ROS) involved in the photodegradation process were radicals, OH•, and photo-holes (h+). These results stand out because it is the first time that the photodegradation capability of this oxide in the visible spectrum has been evaluated.

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Carbamazepine is a widely used antiepileptic drug to control and treat a variety of disorders that is frequently detected in surface water, and in municipal and urban wastewater. This recalcitrant pollutant could be removed by alternative advanced oxidation technology such as heterogeneous photocatalysis. Ce-modified ZnO and Pd-modified TiO2 were synthesized by a microwave-assisted sol-gel method. According to the characterizations (Raman spectroscopy, UV-Vis diffuse reflectance spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy), a mixture of oxides was determined in both materials: CeO2/ZnO and PdO/TiO2. Photocatalytic degradation of carbamazepine in pure water under visible light (3 h) was assayed. The degradation percentage obtained with each catalyst was 80%, 53%, 20%, and 9% for ZnO, Ce-modified ZnO, TiO2, and Pd-modified TiO2, respectively. The leaching of Zn as a possible source of water contamination was tested, finding the lowest value for Ce-modified ZnO by adjusting the initial pH up to neutrality. Later, an environmentally relevant concentration of carbamazepine (228 µg L-1) was assayed, using local surface water (pH = 8.3). Despite the presence of other compounds in the real water matrix, after 5 h of photocatalysis, a 56% of degradation of the pharmaceutical and low leaching of Zn were achieved. The use of Ce-modified ZnO activated by visible light is a promising strategy for the abatement of pharmaceutical active compounds.

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In this article, we propose a simple photochemical method to synthesize pure La2Ti2O7 films and La2Ti2O7 films doped with silver at 1.0, 3.0, and 5.0 mol%. After annealing the photo-deposited films at 900 °C, XRD, SEM, and XPS analyses showed the formation of a monoclinic La2Ti2O7 phase and the presence of Ag and AgO in doped samples. Photocatalytic tests for Congo red degradation demonstrated that pure La2Ti2O7 achieved 25.4% degradation, while doped samples reached a maximum of 92.7% degradation. Moreover, increasing silver doping on La2Ti2O7 films significantly reduced the growth of Staphylococcus aureus, indicating potential antibacterial properties. The enhanced photoactivity was attributed to the formation of a type I heterojunction between La2Ti2O7 and AgO, and a degradation mechanism was proposed based on Congo red degradation.

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Methotrexate (MTX) is a folic acid analog and has been used to treat a wide variety of malignant and non-malignant diseases. The wide use of these substances has led to the continuous discharge of the parent compound and its metabolites in wastewater. In conventional wastewater treatment plants, the removal or degradation of drugs is not complete. In order to study the MTX degradation by photolysis and photocatalysis processes, two reactors were used with TiO2 as a catalyst and UV-C lamps as a radiation source. H2O2 addition was also studied (absence and 3 mM/L), and different initial pHs (3.5, 7, and 9.5) were tested to define the best degradation parameters. Results were analyzed by means of ANOVA and the Tukey test. Results show that photolysis in acidic conditions with 3 mM of H2O2 added is the best condition for MTX degradation in these reactors, with a kinetic constant of 0.028 min-1. According to the ANOVA test, all considered factors (process, pH, H2O2 addition, and experimentation time) caused statistically significant differences in the MTX degradation results.

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The attractive properties of magadiite, a lamellar and crystalline material, could give rise to new industrial processes due to its unique and modulating intrinsic properties. In this context, the high degree of expansion of its lamellae, a key factor for its potential use in several areas of scientific research, has attracted the attention of several researchers. The aim of this review is to provide a historical overview of the hypothetical models developed to explain the magadiite crystalline structure. Furthermore, different synthesis strategies for the preparation of magadiites as sodic, protonic, and hybrid (inorganic-inorganic and inorganic-organic) materials are discussed along with several routes for obtaining modified magadiites. Also, the use of magadiite in catalytic reactions, notably in ethanol dehydration and fructose conversion reactions, is a growing area of research. Other potential applications include the adsorption and absorption of environmental pollutants (e.g., phenol and methylene blue in wastewater), use as a photocatalyst in the oxidation of toluene, and use in medicine (e.g., as a drug delivery or antibacterial/antifungal agent). This highlights the many opportunities for the development of new synthesis methods to obtain multifunctional materials in the search for new applications.

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In this study, composite material films of pyridine-based polymer and metal oxides (ZnO and TiO2) were successfully deposited by spin coating method for environmental remediation. Firstly, the polymers poly(2-vinylpyridine) P(2-VP), and poly(4-vinylpyridine) P(4-VP) were synthesized via solution polymerization. The analysis by grazing incidence X-ray diffraction (GIXRD) reveals semicrystalline nature and scanning electron microscopy (SEM) indicates that the poly(vinylpyridines) clusters of particles were observed on the surface of the films. It was also shown that the morphology of composite materials is completely dependent on the chemical nature of the oxide. In the case of P(2-VP)-TiO2 and P(4-VP)-TiO2, some channels or pathways of TiO2 on the surface of films were observed. However, the surface morphology of the polymer composites formulated with ZnO shows a homogeneous distribution in P(2-VP) and P(4-VP) matrix. The effectiveness of the composite materials in the photodegradation of methyl orange (MO) was evaluated by photocatalysis. According to the results, the P(4-VP)-ZnO composite exhibited the highest photodegradation of MO, allowing the separation of photogenerated species required for the photocatalytic reaction. The P(4-VP)-ZnO composite was also tested in benzoic acid (BA) photodegradation in water. The presence of some scavengers in the reaction system reveals that hydroxyl radicals (OH•), superoxide radicals (O2-•) and holes (h+) are responsible for the BA reduction by photocatalysis.

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TiO2/Karaya composite was synthesized by the sol-gel method for the photoinactivation of pathogens. This is the first time that we have reported this composite for an antimicrobial approach. The structure, morphology, and optical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-rays (EDS), Fourier transform infrared spectroscopy (FTIR), and diffuse reflectance, and the surface area was characterized by the BET method. The XRD and EDS results showed that the TiO2/Karaya composite was successfully stabilized by the crystal structure and pore diameter distribution, indicating a composite of mesoporous nature. Furthermore, antibacterial experiments showed that the TiO2/Karaya composite under light was able to photoinactivate bacteria. Therefore, the composite is a promising candidate for inhibiting the growth of bacteria.

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Photoelectrocatalysis has been highlighted as a tertiary wastewater treatment in the textile industry due to its high dye mineralisation capacity. However, design improvements are necessary to overcome photo-reactors limitations. The present work proposes a preliminary configuration of a photoelectrocatalytic reactor to degrade Reactive Red 239 (RR239) textile dye, using computational fluid dynamics (CFD) to analyse the mass transfer rate, radiation intensity loss (RIL), and its effect on kinetics degradation, over a photoelectrode based on a TiO2 nanotube. A study to increase the space-time yield (STY) was carried out through mass transfer rate and kinetic analysis, varying the optical thickness (δ) between the radiation entrance and the photocatalytic surface, photoelectrode geometry, inlet flow rate, and the surface radiation intensity. The RIL was determined using a 1D Beer-Lambert-based model, and an extinction coefficient experimentally determined by UV-Vis spectroscopy. The results show that in RR239 solutions below concentrations of 6 mg/L, a woven mesh photoelectrode and an optimal optical thickness δ of 1 cm is enough to keep the RIL below 15% and maximise the mass transfer and the STY in around 110 g/m3-day.

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The present study reports on the synthesis of Cu-bismuth oxide (CuBi2O4)-based nanorods by using a simple co-precipitation method for the photocatalytic degradation of caffeic acid (CA). The incorporation of Cu metal ions during the synthesis of CuBi2O4 nanorods might be advantageous to avoid the aggregation and control the leach out of metal ions. The calculated bandgap values of ~ 1.04, 1.02, and 0.94 eV were observed for CuBi2O4 with different amounts of Cu 1.0, 0.50, and 0.25 g, respectively. Varying the quantity of Cu metal ions easily tuned the bandgap value within the CuBi2O4-based nanorods. However, a further decrease in the bandgap value increased the recombination rate, and the less photocatalyst performance was observed. The CA degradation could be explained based on the species distribution. The CA pKa was mainly located between pKa1 and pKa2 of 4.43 and 8.6, respectively. The Cu within the CuBi2O4-based nanorods changed the electronic properties and the antibacterial ability. Therefore, the synthesized CuBi2O4-based nanorod cluster might be a promising material for the photocatalytic degradation of CA.

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Nanomaterials have attracted much attention over the last decades due to their very different properties compared to those of bulk equivalents, such as a large surface-to-volume ratio, the size-dependent optical, physical, and magnetic properties. A number of solution fabrication methods have been developed for the synthesis of metal and metal oxides nanoparticles, but few solid-state methods have been reported. The application of nanostructured materials to electronic solid-state devices or to high-temperature technology requires, however, adequate solid-state methods for obtaining nanostructured materials. In this review, we discuss some of the main current methods of obtaining nanomaterials in solid state, and also we summarize the obtaining of nanomaterials using a new general method in solid state. This new solid-state method to prepare metals and metallic oxides nanostructures start with the preparation of the macromolecular complexes chitosan·Xn and PS-co-4-PVP·MXn as precursors (X = anion accompanying the cationic metal, n = is the subscript, which indicates the number of anions in the formula of the metal salt and PS-co-4-PVP = poly(styrene-co-4-vinylpyridine)). Then, the solid-state pyrolysis under air and at 800 °C affords nanoparticles of M°, MxOy depending on the nature of the metal. Metallic nanoparticles are obtained for noble metals such as Au, while the respective metal oxide is obtained for transition, representative, and lanthanide metals. Size and morphology depend on the nature of the polymer as well as on the spacing of the metals within the polymeric chain. Noticeably in the case of TiO2, anatase or rutile phases can be tuned by the nature of the Ti salts coordinated in the macromolecular polymer. A mechanism for the formation of nanoparticles is outlined on the basis of TG/DSC data. Some applications such as photocatalytic degradation of methylene by different metal oxides obtained by the presented solid-state method are also described. A brief review of the main solid-state methods to prepare nanoparticles is also outlined in the introduction. Some challenges to further development of these materials and methods are finally discussed.

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Photocatalysts supported in magnetic nanocomposites for application in environmental remediation processes have been evaluated for removing contaminants due to easy recovery and low toxicity to the ecosystem. In this work, copper oxide (CuO) nanoparticles with photocatalytic properties were decorated on magnetic support constituted by hydroxyapatite (HAP) and ferrite to achieve efficiency in contaminated water remediation under visible light irradiation. First, nanomaterials were obtained by precipitation route, allowing fast and straightforward synthesis. Then, CuO nanoparticles with 6 nm diameter were efficiently decorated on magnetic support (25 nm), showing a high ability to absorb visible light irradiation (bandgap) to promote electronic transition and charge separation. Under visible irradiation, CuO promotes the H2O2 reduction in the conduction band (BC) to form hydroxyl radicals (•OH), which are responsible for rhodamine B (RhB) dye degradation (> 90% in 60 min). Magnetic hysteresis assays confirmed the magnetic properties of HAP/ferrite support, which enabled the recovery and reuse of the magnetic photocatalyst efficiently up to 3 cycles. Due to low Cu2+ leaching after the photocatalytic application stage, cytotoxicity assay for the Allium cepa seeds did not exhibit abnormal cells other than those commonly found. Furthermore, the CuO-decorated nanoparticles showed bactericidal activity against S. aureus (Gram-positive) and E. coli (Gram-negative) microorganisms, being more significant for the first one. Thus, the developed nanocomposite of CuO nanoparticles decorated on the magnetic support surface showed to be a complete system for water remediation, acting in contaminant degradation under visible light irradiation and bactericidal control with environmentally friendly characteristics.Graphical abstract CuO nanoparticles decorated on hydroxyapatite/ferrite magnetic support acting as a photocatalytic and bactericidal system.

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Polymeric composite films have been explored for many photocatalytic applications, from water treatment to self-cleaning devices. Their properties, namely, thickness and porosity, are controlled mainly by the preparation conditions. However, little has been discussed on the effect of thickness and porosity of polymeric composite films for photocatalytic processes, especially in gas phase. In the present study, different preparation treatments of ZnO-based polymeric composite films and their effects on its performance and stability were investigated. The polymeric composites were prepared by solution mixing followed by non-solvent induced phase separation (NIPS), using poly(vinylidene fluoride) (PVDF) as the matrix and ZnO-based photocatalysts. Different wet thickness, photocatalyst mass, and treatments (e.g., using or not pore-forming agent and compatibilizer) were assessed. A low ZnO/PVDF ratio and higher wet thickness, together with the use of pore-forming agent and compatibilizer, proved to be a good strategy for increasing photocatalytic efficiency given the low agglomerate formation and high polymer transmittance. Nonetheless, the composites exhibited deactivation after several minutes of exposure. Characterization by XRD, FTIR-ATR, and SEM were carried out to further investigate the polymeric film treatments and stability. ZnO film was most likely deactivated due to zinc carbonate formation intensified by the polymer presence.

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The treatment of industrial waste and harmful bacteria is an important topic due to the release of toxins from the industrial pollutants that damage the water resources. These harmful sources frighten the life of every organism which was later developed as the carcinogenic and mutagenic agents. Therefore, the current study focuses on the breakdown or degradation of 4-chlorophenol and the antibacterial activity against Escherichia coli (E. coli). As a well-known catalyst, pure titanium-di-oxide (TiO2) had not shown the photocatalytic activity in the visible light region. Hence, band position of TiO2 need to be shifted to bring out the absorption in the visible light region. For this purpose, the n-type TiO2 nanocrystalline material's band gap got varied by adding different ratios of p-type CuO. The result had appeared in the formation of p (CuO) - n (TiO2) junction synthesized from sol-gel followed by chemical precipitation methods. The optical band gap value was determined by Kubelka-Munk (K-M) plot through UV-Vis diffusive reflectance spectroscopy (DRS). Further, the comprehensive mechanism and the results of photocatalytic and antibacterial activities were discussed in detail. These investigations are made for tuning the TiO2 catalyst towards improving or eliminating the existing various environmental damages.

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Enormous research studies on the abatement of anthropogenic aquatic pollutants including organic dyes, pesticides, cosmetics, antibiotics and inorganic species by using varieties of semiconductor photocatalysts have been reported in recent decades. Besides, many of these photocatalysts suffer in real applications owing to their high production cost and low stability. In many cases, the photocatalysts themselves are being considered as secondary pollutants. To eliminate these drawbacks, the green synthesized photocatalysts and the use of biopolymers as photocatalyst supports are considered in recent years. In this context, recent developments in green synthesized metals, metal oxides, other metal compounds, and carbon based photocatalysts in water purification are critically reviewed. Furthermore, the pivotal role of biopolymers including chitin, chitosan, cellulose, natural gum, hydroxyapatite, alginate in photocatalytic removal of aquatic pollutants is comprehensively reviewed. The presence of functional groups, electron trapping ability, biocompatibility, natural occurrence, and low production cost are the major reasons for using biopolymers in photocatalysis. Finally, the summary and conclusion are presented along with existing challenges in this research area.

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Organoselenium compounds constitute an important class of substances with applications in the biological, medicinal and material sciences as well as in modern organic synthesis, attracting considerable attention from the scientific community. Therefore, the construction of the C-Se bond via facile, efficient and sustainable strategies to access complex scaffolds from simple substrates are an appealing and hot topic. Visible light can be regarded as an alternative source of energy and is associated with environmentally-friendly processes. Recently, the use of visible-light mediated seleno-functionalization has emerged as an ideal and powerful route to obtain high-value selenylated products, with diminished cost and waste. This approach, involving photo-excited substrates/catalyst and single-electron transfer (SET) between substrates in the presence of visible light has been successfully used in the versatile and direct insertion of organoselenium moieties in activated and unactivated C(sp3 )-H, C(sp2 )-H, C(sp)-H bonds as well as C-heteroatom bonds. In most cases, ease of operation and accessibility of the light source (LEDs or commercial CFL bulbs) makes this approach more attractive and sustainable than the traditional strategies.

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In recent times, cost effective synthesis of semiconductor materials has been a subject of concern for the day to today applications. In this work, novelty has been made on the facile synthesis of metal oxides (TiO2 and CeO2) and nanocomposites (TiO2-CeO2) through sol-gel and precipitation methods of imparting lemon extract. The synthesized materials behave as the functional catalysts which has been further carried out for the photocatalytic degradation against 2,4-Dichlorophenol (2,4-DCP). The materials are then valued for the structural and optical properties. The lemon extract used in synthesis has played a premier role in upgrading the charge carrier separation, bandgap, and size reduction of the composite system. Further, the CeO2 supported TiO2 sample acts as the better visible light catalyst, due to the prevention of aggregation and existence of line dislocation that supported to access the additional electron trap sites.

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In this study, plastic optical fibre (POF) was considered as a light-transmitting medium and substrate for use in a photocatalytic environmental purification system, using Ag2MoO4 and ß-Ag2MoO4/Ag3PO4 as photocatalysts. Pure Ag2MoO4 and a ß-Ag2MoO4/Ag3PO4 composite were synthesized using a facile precipitation method. The composition, structures and optical properties of as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), field-emission scanning electron microscopy (FESEM), UV/Vis diffuse reflectance spectroscopy (UV/Vis DRS), BET surface area and TGA/DTG. The catalysts were immobilized on POF and on the glass reactor surface and their efficiency in the phenol degradation was evaluated in a batch reactor under visible light. The use of POF offers advantages such as ease of handling and good adherence characteristics to support Ag2MoO4. The photoactivity follows the order ß-Ag2MoO4/Ag3PO4 ≅ Ag2MoO4 > TiO2 P25, for photocatalysts immobilized on the glass reactor surface or in aqueous suspension. The immobilization of Ag2MoO4 on POF revealed that thinner Ag2MoO4 coatings achieved faster pollutant removal rates from solution, and the optimal catalyst deposition is 0.64 mg/cm2, causing maximum the light penetration and electron-hole generation close to the solid-liquid interface.

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