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1.
Nanomaterials (Basel) ; 14(13)2024 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-38998684

RESUMO

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.

2.
Environ Res ; 258: 119477, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38909943

RESUMO

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.


Assuntos
Parabenos , Poluentes Químicos da Água , Parabenos/química , Adsorção , Poluentes Químicos da Água/química , Estruturas Metalorgânicas/química , Catálise , Cinética
3.
Chemistry ; 30(13): e202303382, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38150600

RESUMO

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.

4.
Materials (Basel) ; 16(24)2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-38138808

RESUMO

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.

5.
Environ Sci Pollut Res Int ; 30(54): 116078-116090, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37906333

RESUMO

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.


Assuntos
Água , Óxido de Zinco , Óxido de Zinco/química , Luz , Titânio/química , Carbamazepina/química , Preparações Farmacêuticas , Catálise
6.
Environ Sci Pollut Res Int ; 30(49): 107580-107597, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37737945

RESUMO

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.


Assuntos
Vermelho Congo , Staphylococcus aureus , Vermelho Congo/química , Prata/farmacologia , Prata/química , Titânio/química , Antibacterianos/farmacologia , Antibacterianos/química
7.
Int J Mol Sci ; 24(11)2023 May 31.
Artigo em Inglês | MEDLINE | ID: mdl-37298542

RESUMO

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.


Assuntos
Metotrexato , Poluentes Químicos da Água , Fotólise , Peróxido de Hidrogênio/química , Raios Ultravioleta , Titânio/química , Águas Residuárias , Poluentes Químicos da Água/química , Oxirredução , Catálise
8.
ACS Appl Mater Interfaces ; 15(37): 43234-43250, 2023 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-34978785

RESUMO

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.

9.
Polymers (Basel) ; 14(21)2022 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-36365660

RESUMO

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.

10.
Nanomaterials (Basel) ; 12(14)2022 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-35889609

RESUMO

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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