Search Results (254)

The persistence of pharmaceutical pollutants such as ciprofloxacin (CIP) in aquatic environments represents a critical environmental threat due to their potential to induce antimicrobial resistance. Photocatalysis using TiO₂-based materials offers a promising solution for their mineralization; however, the limited visible-light response of TiO₂ and charge carrier recombination restricts its overall efficiency. In this study, Nb-doped TiO₂ nanoparticles were synthesized via the sol–gel method, incorporating Nb⁵⁺, ions into the TiO₂ lattice to modulate the structural and electronic properties of TiO₂ to enhance its photocatalytic performance for CIP degradation under UV and visible irradiation. Comprehensive structural, morphological, and optical analyses revealed that Nb incorporation stabilizes the anatase phase, reduces particle size (from 21.42 nm to 10.29 nm), and induces a slight band gap widening (from 2.85 to 2.87 eV) due to the Burstein–Moss effect. Despite this blue shift, Nb-TiO₂ exhibited significantly improved photocatalytic activity under visible light, achieving 86% CIP degradation with a reaction rate 16 times higher than that of undoped TiO₂. This enhancement was attributed to improved charge separation and higher hydroxyl radical (^•OH) generation, driven by excess conduction band electrons introduced by Nb doping. Density Functional Theory (DFT) calculations further elucidated the electronic structure modifications responsible for this behavior, offering molecular-level insights into Nb dopant-induced property tuning. These findings demonstrate how targeted doping strategies can engineer multifunctional nanomaterials with superior photocatalytic efficiencies, especially under visible light, highlighting the synergy between experimental design and theoretical modeling for environmental applications. Full article

The utility of nanostructured TiO₂ in the degradation of organic compounds and the disinfection of pathogenic microorganisms represents an important endeavor in photocatalysis. However, the low photocatalytic efficiency of TiO₂ remains challenging. Herein, we report a robust photocatalytic route to benzene removal rendered by enhancing its adsorption capacity via rationally designed mesoporous SiO₂-coated TiO₂ colloids. Specifically, amorphous, mesoporous SiO₂-coated TiO₂ nanoparticles (denoted T@S NPs) are produced via a precipitation-gel-hydrothermal approach, possessing an increased specific surface area over pristine TiO₂ NPs for improved adsorption of benzene. Notably, under UV irradiation, the degradation rate of benzene by T@S NPs reaches 89% within 30 min, representing a 3.1-fold increase over that achieved by pristine TiO₂. Moreover, a 99.5% degradation rate within 60 min is achieved and maintains a stable photocatalytic activity over five cycles. Surface coating of TiO₂ with amorphous SiO₂ imparts the T@S composite NPs nearly neutral characteristic due to the formation of Ti-O-Si bonds, while manifesting enhanced light harvesting, excellent stability, adhesion, and photocatalytic bacteriostatic effects. Our study underscores the potential of T@S composites for practical applications in photocatalysis over pristine counterparts. Full article

The search for a simple, scalable, and eco-friendly method for synthesizing micro-sized photocatalysts is an urgent task. Plasma technologies are highly effective and have wide possibilities for targeted synthesis of novel materials. The mass-average temperature of plasma treatment is higher than the stability temperature of anatase and brookite, the most photoactive polymorphs of titanium dioxide. In this work, by optimizing the plasma treatment conditions and selecting source materials, a method for synthesizing micro-sized photocatalyst based on heterocomposite TiO₂/ZnO particles with high anatase content is proposed. The synthesis method involves treating a powder mixture of titanium and zinc by low-temperature argon plasma under atmospheric conditions. The relationship between the structural-phase composition, morphology, and photocatalytic properties of the microparticles was investigated. A model for the synthesis of composite microparticles containing anatase, rutile, and heterostructural contact with zinc oxide is proposed. The photocatalytic degradation of methylene blue and metronidazole was studied to evaluate both sensitized and true photocatalytic processes. The metronidazole degradation confirmed the intrinsic photocatalytic activity of the synthesized composites. Additionally, the features of photocatalysis under UV and solar irradiation were studied, and a photocatalysis mechanism is proposed. The synthesized micro-sized heterocomposite photocatalyst based on TiO₂/ZnO contained anatase (36%), rutile (60), and brookite (4%) and showed a photocatalytic activity during the methylene blue degradation process under UV irradiation (high-pressure mercury lamp, 250 W): 99% in 30 min. Full article

Sorption and advanced oxidative processes (AOPs) are potential strategies for the removal of organic compounds, such as caffeine, from aqueous media. Such strategies tend to be more promising when combined with biopolymeric membranes as sorbents and photocatalyst supports. Therefore, the aim of the present study was to investigate sorption and AOP parameters in the performance of chitosan membranes and chitosan/TiO₂ composite membranes in individual and hybrid systems involving the photolysis, photocatalysis, and sorption of caffeine. Caffeine degradation by photolysis was 19.51 ± 1.14, 28.61 ± 0.05, and 30.64 ± 6.32%, whereas caffeine degradation by photocatalysis with catalytic membrane was 18.33 ± 2.20, 20.83 ± 1.49, and 31.41 ± 3.08% at pH 6, 7, and 8, respectively. In contrast, photocatalysis with the dispersed catalyst achieved degradation of 93.56 ± 2.12, 36.42 ± 2.59, and 31.41 ± 1.07% at pH 6, 7, and 8, respectively. These results indicate that ions present in the buffer solutions affect the net electrical charge on the surface of the composite biomaterial with the change in pH variation, occupying active sorption sites in the structure of the biomaterial, which was characterized by Fourier transform infrared spectrometry, thermogravimetric analysis, differential scanning thermogravimetry, and X-ray diffraction. Thus, it is verified that in a combined process of caffeine removal under UV irradiation and use of chitosan/TiO₂ composite membranes in phosphate-buffered medium, the photolysis mechanism is predominant, with little or no contribution from sorption, and that the TiO₂ catalyst promotes a significant reduction in the percentage of pollutant in the medium only when used dispersed and at low pH. Full article

Titanium dioxide (TiO₂), a widely used semiconductor in photocatalysis owing to its adequate potential for water hydrolysis, chemical stability, low toxicity, and low cost. However, its efficiency is limited by fast charge-carrier recombination and poor visible light absorption. Coupling TiO₂ with a p-type semiconductor, such as nickel oxide (NiO), forming a p-n heterojunction, decreases the recombination of charge carriers and increases photocatalytic activity. In this work, the surface of TiO₂ modified with NiO nanoparticles (NPs) induced by radiolysis for photocatalytic hydrogen production was studied. The photocatalytic activity of NiO/TiO₂ was evaluated using methanol as a hole scavenger under UV–visible light. All modified samples presented superior photocatalytic activity compared to bare TiO₂. The dynamics of the charge carriers, a key electronic phenomenon in photocatalysis, was investigated by time-resolved microwave conductivity (TRMC). The results highlight the crucial role of Ni-based NPs modification in enhancing the separation of the charge carrier and activity under UV–visible irradiation. Furthermore, the results revealed that under visible irradiation, NiO-NPs inject electrons into the conduction band of titanium dioxide. Full article

Due to its persistence and potential negative effects on ecosystems and human health, microplastic pollution in aquatic environments has become a major worldwide concern. Photocatalytic degradation is a sustainable manner to degrade microplastics to non-toxic by-products. In this review, comprehensive discussion focuses on the synergistic effects of various photocatalytic materials including TiO₂, ZnO, WO₃, graphene oxide, and metal–organic frameworks for producing heterojunctions and involving multidimensional nanostructures. Such mechanisms can include the generation of reactive oxygen species and polymer chain scission, which can lead to microplastic breakdown and mineralization. The advancements of material modifications in the (nano)structure of photocatalysts, doping, and heterojunction formation methods to promote UV and visible light-driven photocatalytic activity is discussed in this paper. Reactor designs, operational parameters, and scalability for practical applications are also reviewed. Photocatalytic systems have shown a lot of development but are hampered by shortcomings which include a lack of complete mineralization and production of intermediary secondary products; variability in performance due to the fluctuation in the intensity of solar light, limited UV light, and environmental conditions such as weather and the diurnal cycle. Future research involving multifunctional, environmentally benign photocatalytic techniques—e.g., doped composites or composite-based catalysts that involve adsorption, photocatalysis, and magnetic retrieval—are proposed to focus on the mechanism of utilizing light effectively and the environmental safety, which are necessary for successful operational and industrial-scale remediation. Full article

Peroxymonosulfate (PMS)-based advanced oxidation technology has emerged as an effective means for removing organic pollutants from water due to its strong oxidizing ability. However, enhancing the activation efficiency of PMS represents a key challenge at present. SrTiO₃, a typical perovskite metal oxide, holds potential in the field of the photocatalytic degradation of pollutants, yet its application is limited by the wide bandgap and fast carrier recombination rates. This study optimized the photocatalytic performance of SrTiO₃ by regulating its electronic structure and optical properties through cobalt (Co) doping. Experimental results (TRPL, TPV, UV–Vis DRS, ESR, etc.) and DFT calculations (GGA-PBE) demonstrated that Co doping shifted the d-band center of SrTiO₃ upwards, optimized the adsorption energy of SO₄⁻, enhanced the sunlight response range, and significantly improved carrier extraction efficiency. Under visible light irradiation, 2,4-dichlorophenol (2,4-DCP) could be effectively degraded within 60 min in a wide pH range. Through Fukui function calculation (B3LYP/6-31G*) and experimental characterization analysis (HPLC-MS and IC), the possible degradation pathways of 2,4-DCP and the mechanism for photocatalysis were investigated. The toxicity analysis (T.E.S.T) confirmed the reduced toxicity of the degradation products of 2,4-DCPs. This study provides a reference for the catalyst design and optimization strategy of PMS-based advanced oxidation technology. Full article

Produced water is the waste aqueous phase from petroleum extraction. As it contains salts, a high organic load, and toxic organic compounds, it should be treated before disposal or reuse. In this research, the combination of membrane processes (microfiltration or membrane distillation) with TiO₂-based heterogeneous photocatalysis was assessed to treat synthetic produced water. Pre-treatment with both microfiltration and membrane distillation removed the majority (90–98%) of large organic compounds (humic acids) from produced water. Moreover, membrane distillation also eliminated salt (sodium chloride). However, membrane processes only removed 10–50% of phenol, used here as proxy for low-molecular-weight toxic organic compounds. For this reason, membrane permeates, from microfiltration and membrane distillation, underwent a further photocatalytic treatment aimed at phenol degradation. The application of TiO₂ photocatalysis to membrane distillation permeates was successful (100% phenol removal in 5 min), while the high chloride concentration of microfiltration permeates acted as inhibitor of the photocatalytic process. Overall, good-quality water may be obtained from the combination of membrane distillation and heterogeneous photocatalysis, which performed much better than the two techniques used separately. Indeed, while membrane distillation was not able to remove phenol, produced water was too complex a matrix to be effectively treated with TiO₂/UV photocatalysis alone. Full article

This study investigates a sustainable approach to the photocatalytic degradation of Congo red (CR) dye using titanium dioxide (TiO₂) under simulated solar radiation, with a specific focus on the UV-A component of the radiation. The aim was to optimize reaction conditions to maximize dye removal efficiency while promoting environmentally friendly wastewater treatment practices. A central composite design (CCD) was implemented, and results were analyzed using analysis of variance (ANOVA). The key factors examined included TiO₂ concentration, UV-A radiation intensity, CR dye concentration, and suspension depth. The optimal conditions determined were 222.37 mg/L TiO₂, 20 W/m² UV-A irradiation, 25 µmol/L CR dye concentration, and a suspension depth of 29 mm. Under these conditions, decolorization was achieved with the lowest absorbance (0.367 at 498 nm) and total organic carbon (0.805 mg/L) values, indicating effective dye degradation. The findings confirm that TiO₂-assisted photocatalysis is a green and promising method for wastewater treatment. The potential use of natural solar radiation could reduce operational costs, making the process more sustainable. However, challenges such as photocatalyst recovery, aggregation, and the impact of the real wastewater matrices need further investigation. Full article

Industrial growth led to the expansion of existing environmental problems, where different kinds of pollutants can enter the environment by many known routes, particularly through wastewater. Among other contaminants, pharmaceuticals, such as diazepam, once released, pose a significant challenge related to their removal from complex environmental matrices due to their persistence and potential toxicity. For this reason, it is a great challenge to find suitable methods for the treatment of wastewater. The aim of this paper was to investigate the stability of diazepam, subjecting it to various degradation processes (hydrolysis and photolysis), focusing on photocatalysis, an advanced oxidation process commonly used for the purification of industrial wastewater. The photocatalytic system consisted of UV-A and simulated solar irradiation with titanium dioxide (TiO₂) immobilized on a glass mesh as a photocatalyst, with an additional reaction performed in the presence of an oxidizing agent, i.e., hydrogen peroxide, to improve diazepam removal from water matrices. The kinetic rate of diazepam degradation was monitored with a high-performance liquid chromatograph coupled with a photodiode array detector (HPLC-PDA). The target compound was characterized as a hydrolytically and photolytically stable compound with t_1/2 = 25 h. The presence of an immobilized TiO₂ catalyst contributed significantly to the degradation of diazepam under the influence of UV-A and simulated solar radiation, with t_1/2 in the range of 1.61–2.56 h. Five degradation products of diazepam were identified at the laboratory scale by MS analysis (m/z = 267, m/z = 273, m/z = 301, m/z = 271, and m/z = 303), while the toxicity assessment revealed that diazepam exhibited developmental toxicity and a low bioaccumulation factor. The pilot-scale process resulted in significant improvements in diazepam degradation with the fastest degradation kinetics (0.6888 h⁻¹). These results obtained at the pilot scale highlight the potential for industrial-scale implementation, offering a promising and innovative solution for pharmaceutical removal from wastewater. Full article

In this research, an emerging, non-metallic photocatalyst was prepared by the thermal polymerization method from three different precursors: urea, melamine, and three mixtures of melamine and cyanuric acid. Graphitic carbon nitride (g-C₃N₄) samples from urea and melamine were synthesized in a muffle furnace at three different temperatures: 450°, 500°, and 550 °C for 2 h, while the samples made of a mixture of melamine and cyanuric acid (with mass ratios of 1:1, 1:2, and 2:1) were synthesized at 550 °C for 2 h. All the samples were characterized in order to determine their chemical and physical properties, such as crystallite size and structure, and phase composition by the following techniques: Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS). Nitrogen adsorption/desorption isotherms were used to investigate the Brunauer, Emmett, and Teller (BET) specific surface area and Barrett–Joyner–Halenda (BJH) pore size distribution. Band gap values were determined by diffuse reflectance spectroscopy (DRS). Furthermore, adsorption and photocatalytic degradation of the local anesthetic drug procaine were monitored under UV-A, visible, and simulated solar irradiation in a batch reactor. Kinetic parameters, as well as photocatalytic mechanisms using scavengers, were determined and analyzed. The results of the photocatalysis experiments were compared to the benchmark TiO₂ Evonik Aeroxide P25. The results indicated that the g-C₃N₄ sample synthesized from urea at 500 °C for 2 h exhibited the highest degradation rate of procaine under visible light. Full article

This article presents an integrated strategy that couples high-efficiency photocatalytic degradation with low-cost, rapid detection to overcome the main drawbacks of conventional TiO₂-based photocatalysts, including a weak visible-light response, rapid charge–carrier recombination, and reliance on expensive instrumentation for dye concentration detection. Platinum-decorated TiO₂ (Pt/TiO₂) was prepared by photoreduction deposition, and systematic characterization confirmed the successful loading of zero-valent Pt nanoparticles onto the TiO₂ surface, significantly improving charge separation and extending absorption into the visible region. Methylene blue degradation was quantified under ultraviolet (UV) and simulated sunlight; radical-scavenging tests clarified the reaction pathway. In parallel, smartphone images of the reaction mixture were processed in ImageJto extract red–green–blue (RGB) values, which were related to dye concentration through a partial least-squares (PLS) model validated against reference UV–Vis data. Pt/TiO₂ removed 95.0% of methylene blue within 20 min of UV irradiation and 90.2% within 160 min of simulated sunlight—31.8% and 19.1% faster, respectively, than pristine TiO₂. The RGB-based PLS model achieved a coefficient of determination (R²) of 0.961 for the prediction set. By integrating photocatalysis with smartphone-based colorimetry, the proposed method enables rapid monitoring of organic dyes concentration, providing an intelligent and economical platform for industrial wastewater treatment. Full article

In this work, a newly developed magnetic molecularly imprinted Fe₃O₄/SiO₂/TiO₂/MIP photocatalyst with diclofenac (DIC) as the template was prepared by microwave-assisted synthesis. The molecularly imprinted TiO₂ layer has specific cavities designed for the DIC target molecule (imprint), resulting in a synergistic effect of extraction by adsorption and photocatalysis. For reference, non-imprinted magnetic nanoparticles (Fe₃O₄/SiO₂/TiO₂) were prepared using the same procedure. The obtained particles were characterized by X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), SEM-EDX, vibrating-sample magnetometry (VSM) and diffuse reflectance spectroscopy (DRS). Specific surface area, pore volume and pore size distribution were evaluated using Brunauer–Emmett–Teller (BET) adsorption–desorption isotherms. The synergistic effect of adsorption and photocatalysis as well as the kinetics and mechanism of DIC degradation using Fe₃O₄/SiO₂/TiO₂/MIP and Fe₃O₄/SiO₂/TiO₂ were determined and analysed. The adsorption efficiency of Fe₃O₄/SiO₂/TiO₂/MIP for DIC (10 mg dm⁻³) was around 86% after 60 min. The DIC (10 mg dm⁻³) removal efficiency of Fe₃O₄/SiO₂/TiO₂/MIP was around 80% after 30 min adsorption and 120 min of reaction under both UV-A- and solar-simulated light irradiation. Full article

Methylene blue (MB), a widely used industrial dye, is a persistent pollutant with documented toxicity to aquatic organisms and potential health risks to humans, even at ultra-trace levels. Conventional monitoring techniques such as UV–Vis spectroscopy and fluorescence emission suffer from limited sensitivity, typically failing to detect MB below ~10⁻⁷ M. In this study, we introduce a surface-enhanced Raman spectroscopy (SERS) platform based on silver nanowire (AgNW) substrates that enables MB detection over an unprecedented dynamic range—from 1.5 × 10⁻⁴ M down to 1.5 × 10⁻¹⁶ M. Raman mapping confirmed the presence of individual signal hot spots at the lowest concentration, consistent with the theoretical number of analyte molecules in the probed area, thereby demonstrating near-single-molecule detection capability. The calculated enhancement factors reached up to 1.90 × 10¹², among the highest reported for SERS-based detection platforms. A semi-quantitative calibration curve was established spanning twelve orders of magnitude, and this platform was successfully applied to monitor MB degradation during two advanced oxidation processes (AOPs): TiO₂ nanotube-mediated photocatalysis under UV irradiation and atmospheric-pressure dielectric barrier discharge (DBD) plasma treatment. While UV–Vis and fluorescence techniques rapidly lost sensitivity during the degradation process, the SERS platform continued to detect the characteristic MB Raman peak at ~1626 cm⁻¹ throughout the entire treatment duration. These persistent SERS signals revealed the presence of residual MB or partially degraded aromatic intermediates that remained undetectable by conventional optical methods. The results underscore the ability of AgNW-based SERS to provide ultra-sensitive, molecular-level insights into pollutant transformation pathways, enabling time-resolved tracking of degradation kinetics and validating treatment efficiency. This work highlights the importance of integrating SERS with AOPs as a powerful complementary strategy for advanced environmental monitoring and water purification technologies. By delivering an ultra-sensitive, low-cost sensor (<USD 0.16 per test) and promoting reagent-free treatment methods, this study directly advances SDG 6 (Clean Water and Sanitation) and SDG 12 (Responsible Consumption and Production). Full article

Long-time exposure to volatile organic compounds (VOCs) in the atmosphere can have negative health effects on humans and other living organisms. In order to purify ambient air, these VOCs can be degraded using photocatalysis. In this research, commercially available TiO₂ nanoparticles were immobilized in a porous poly(vinylidene fluoride-co-hexa-fluoropropylene) (PVDF) polymer matrix, synthesized using the phase inversion method. The most used solvent for PVDF is N-methyl-2-pyrrolidone (NMP). However, this solvent is known to be harmful to humans and the environment, and there is a need to replace NMP with a more ecological ‘green’ solvent. Here, triethyl phosphate (TEP), methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv^® PolarClean) and propylene carbonate (PC) were used to dissolve PVDF for the phase inversion synthesis of porous photocatalytically active PVDF/TiO₂ hybrid layers onto aluminium slides. The photocatalytic degradation under UV (365 nm) of gaseous ethanol in an argon/oxygen (Ar/O₂) atmosphere shows that these solvents are suitable replacements for NMP, but optimization is required to improve the performance of the layers. Apart from changing the solvent for PVDF, the UV and photocatalysis stability of PVDF has been determined, as well as the repeatability of the photocatalytic reaction, to prove that PVDF is a suitable polymer for this application. Full article