RESUMEN
A rapid photoelectrochemical (PEC) sensor was constructed for nitrite detection in food based on the one-step chemical etching strategy of BiOCl/Zn0.5Cd0.5S (BOC/ZCS) nanocomposites by nitrite. BOC/ZCS heterojunction was prepared by a simple coprecipitation method, and it was found that BOC/ZCS showed significant photoelectrochemical (PEC) activity. The results of this study confirmed that the decrease in the photocurrent of the sensor was linked to the etching of ZCS by nitrite under acidic conditions. Under optimized conditions, the BOC/ZCS-based PEC sensor showed good analytical properties for detecting nitrite, with linear ranges of 1-100 µM and 100-600 µM. The detection limit of the sensor was 0.41 µM (S/N = 3). Excellent repeatability, reproducibility, low background noise, and immunity to interference were demonstrated using the proposed system, and satisfactory results were achieved for the nitrite assay using real samples. These results demonstrate a new method for nitrite detection developed using the proposed PEC sensor.
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Técnicas Electroquímicas , Límite de Detección , Nitritos , Nitritos/análisis , Técnicas Electroquímicas/instrumentación , Bismuto/química , Zinc/química , Zinc/análisis , Nanocompuestos/química , Procesos Fotoquímicos , Contaminación de Alimentos/análisisRESUMEN
Developing heterojunction photocatalyst with well-matched interfaces and multiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal, but still remains a great challenge. In present work, a new strategy of chloride anion intercalation in Bi2O3 via one-pot hydrothermal process is proposed. The as-prepared Ta-BiOCl/Bi24O31Cl10 (TBB) heterojunctions are featured with Ta-Bi24O31Cl10 and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces. In this TBB heterojunctions, the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer and multiple transfer paths, respectively, leading to enhanced visible light response and improved photogenerated charge separation. Meanwhile, a type-II heterojunction for photocharge separation has been obtained, in which photogenerated electrons are drove from the CB (conduction band) of Ta-Bi24O31Cl10 to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl, while the photogenerated holes are left on the VB (valence band) of Ta-Bi24O31Cl10, effectively hindering the recombination of photogenerated electron-hole pairs. Furthermore, the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species (·O2-). Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride (TCH) solution to Bi2O3, Ta-BiOCl and Ta-Bi24O31Cl10. This work not only proposes a Ta-BiOCl/Bi24O31Cl10 shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-II heterojunction for highly efficient photocatalytic activity, but offers a new insight into the design of highly efficient heterojunction through phase-structure synergistic transformation strategy.
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Antibacterianos , Bismuto , Contaminantes Químicos del Agua , Bismuto/química , Antibacterianos/química , Contaminantes Químicos del Agua/química , Catálisis , Procesos FotoquímicosRESUMEN
Cerium and cobalt loaded Co-Ce/TiO2 catalyst prepared by impregnation method was investigated for photothermal catalytic toluene oxidation. Based on catalyst characterizations (XPS, EPR and H2-TPR), redox cycle between Co and TiO2 (Co2+ + Ti4+ â Co3+ + Ti3+) results in the formation of Co3+, Ti3+ and oxygen vacancies, which play important roles in toluene catalytic oxidation reaction. The introduction of Ce brings in the dual redox cycles (Co2+ + Ti4+ â Co3+ + Ti3+, Co2+ + Ce4+ â Co3+ + Ce3+), further promoting the elevation of reaction sites amount. Under full spectrum irradiation with light intensity of 580 mW/cm2, Co-Ce/TiO2 catalyst achieved 96% of toluene conversion and 73% of CO2 yield, obviously higher than Co/P25 and Co/TiO2. Co-Ce/TiO2 efficiently maintains 10-hour stability test under water vapor conditions and exhibits better photothermal catalytic performance than counterparts under different wavelengths illumination. Photothermal catalytic reaction displays improved activities compared with thermal catalysis, which is attributed to the promotional effect of light including photocatalysis and light activation of reactive oxygen species.
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Cerio , Cobalto , Oxidación-Reducción , Titanio , Tolueno , Titanio/química , Cobalto/química , Catálisis , Tolueno/química , Cerio/química , Modelos Químicos , Procesos FotoquímicosRESUMEN
Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry. In iodine-adduct chemical ionization mass spectrometry (CIMS), the low utilization efficiency of methyl iodide and humidity interference are two major issues of the vacuum ultraviolet (VUV) lamp initiated CIMS for on-line gaseous formic and acetic acids analysis. In this work, we present a new CIMS based on VUV lamp, and the ion-molecular reactor is separated into photoionization and chemical ionization zones by a reducer electrode. Acetone was added to the photoionization zone, and the VUV photoionization acetone provided low-energy electrons for methyl iodide to generate I-, and the addition of acetone reduced the amount of methyl iodide by 2/3. In the chemical ionization zone, a headspace vial containing ultrapure water was added for humidity calibration, and the vial changes the sensitivity as a function of humidity from ambiguity to well linear correlation (R2 > 0.95). With humidity calibration, the CIMS can quantitatively measure formic and acetic acids in the humidity range of 0%-88% RH. In this mode, limits of detection of 10 and 50 pptv are obtained for formic and acetic acids, respectively. And the relative standard deviation (RSD) of quantitation stability for 6 days were less than 10.5%. This CIMS was successfully used to determine the formic and acetic acids in the underground parking and ambient environment of the Shandong University campus (Qingdao, China). In addition, we developed a simple model based formic acid concentration to assess vehicular emissions.
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Espectrometría de Masas , Espectrometría de Masas/métodos , Contaminantes Atmosféricos/análisis , Yoduros/análisis , Yoduros/química , Rayos Ultravioleta , Formiatos/análisis , Formiatos/química , Atmósfera/química , Monitoreo del Ambiente/métodos , Procesos Fotoquímicos , Ácido Acético/análisis , Ácido Acético/química , Hidrocarburos Yodados/análisis , Hidrocarburos Yodados/químicaRESUMEN
In the quest for effective solutions to address Environ. Pollut. and meet the escalating energy demands, heterojunction photocatalysts have emerged as a captivating and versatile technology. These photocatalysts have garnered significant interest due to their wide-ranging applications, including wastewater treatment, air purification, CO2 capture, and hydrogen generation via water splitting. This technique harnesses the power of semiconductors, which are activated under light illumination, providing the necessary energy for catalytic reactions. With visible light constituting a substantial portion (46%) of the solar spectrum, the development of visible-light-driven semiconductors has become imperative. Heterojunction photocatalysts offer a promising strategy to overcome the limitations associated with activating semiconductors under visible light. In this comprehensive review, we present the recent advancements in the field of photocatalytic degradation of contaminants across diverse media, as well as the remarkable progress made in renewable energy production. Moreover, we delve into the crucial role played by various operating parameters in influencing the photocatalytic performance of heterojunction systems. Finally, we address emerging challenges and propose novel perspectives to provide valuable insights for future advancements in this dynamic research domain. By unraveling the potential of heterojunction photocatalysts, this review contributes to the broader understanding of their applications and paves the way for exciting avenues of exploration and innovation.
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Restauración y Remediación Ambiental , Restauración y Remediación Ambiental/métodos , Catálisis , Energía Solar , Luz Solar , Semiconductores , Energía Renovable , Procesos FotoquímicosRESUMEN
In the present study, we investigated the influence of surface fluorine (F) on TiO2 for the photocatalytic oxidation (PCO) of toluene. TiO2 modified with different F content was prepared and tested. It was found that with the increasing of F content, the toluene conversion rate first increased and then decreased. However, CO2 mineralization efficiency showed the opposite trend. Based on the characterizations, we revealed that F substitutes the surface hydroxyl of TiO2 to form the structure of Ti-F. The presence of the appropriate amount of surface Ti-F on TiO2 greatly enhanced the separation of photogenerated carriers, which facilitated the generation of ·OH and promoted the activity for the PCO of toluene. It was further revealed that the increase of only ·OH promoted the conversion of toluene to ring-containing intermediates, causing the accumulation of intermediates and then conversely inhibited the ·OH generation, which led to the decrease of the CO2 mineralization efficiency. The above results could provide guidance for the rational design of photocatalysts for toluene oxidation.
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Fluoruros , Oxidación-Reducción , Titanio , Tolueno , Tolueno/química , Titanio/química , Catálisis , Fluoruros/química , Procesos Fotoquímicos , Modelos QuímicosRESUMEN
BACKGROUND: Temperature sensing is commonly used in point-of-care (POC) detection technologies, yet the portability and convenience of use are frequently compromised by the complexity of thermosensitive processes and signal transduction. Especially, multi-step target recognition reactions and temperature measurement in the reaction vessel present challenges in terms of stability and integration of detection devices. To further combine photothermal reaction and signal readout in one assay, these two processes enable to be integrated into miniaturized microfluidic chips, thereby facilitating photothermal sensing and achieving a simple visual temperature sensing as POC detection. RESULTS: A copper ion (Cu2+)-catalyzed photothermal sensing system integrated onto a microfluidic distance-based analytical device (µDAD), enabling the visual, portable, and sensitive quantitative detection of multiple targets, including ascorbic acid, glutathione, and alkaline phosphatase (ALP). The polydopamine nanoparticles (PDA NPs) were synthesized by the regulation of free Cu2+ through redox or coordination reactions, facilitating the transduction of distinct photothermal response signals and providing the versatile Cu2+-responsive sensing systems. Promoted by integration with a photothermal µDAD, the system combines PDA's photothermal responsiveness and thermosensitive gas production of ammonium bicarbonate for improved sensitivity of ALP detection, reaching the detection limit of 9.1 mU/L. The system has successfully achieved on-chip detection of ALP with superior anti-interference capability and recoveries ranging from 96.8 % to 104.7 %, alongside relative standard deviations below 8.0 %. SIGNIFICANCE AND NOVELTY: The µDAD design accommodated both the photothermal reaction of PDA NPs and thermosensitive gas production reaction, achieving the rapid sensing of visual distance signals. The µDAD-based Cu2+-catalyzed photothermal sensing system holds substantial potential for applications in biochemical analysis and clinical diagnostics, underscored by the versatile Cu2+ regulation mechanism for a broad spectrum of biomarkers.
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Ácido Ascórbico , Cobre , Indoles , Pruebas en el Punto de Atención , Polímeros , Cobre/química , Indoles/química , Polímeros/química , Catálisis , Ácido Ascórbico/análisis , Ácido Ascórbico/química , Límite de Detección , Fosfatasa Alcalina/metabolismo , Fosfatasa Alcalina/análisis , Fosfatasa Alcalina/química , Temperatura , Humanos , Glutatión/análisis , Glutatión/química , Nanopartículas/química , Procesos Fotoquímicos , Dispositivos Laboratorio en un Chip , Técnicas BiosensiblesRESUMEN
A highly water-soluble and fluorescent N,S-doped carbon dots/europium (N,S-CDs/Eu) was successfully synthesized via a secondary hydrothermal method. This involved surface modification of N,S-CDs derived from sunflower stem pith (SSP) with europium ions (Eu3+) doping. When excited within the range of 400-470 nm, N,S-CDs/Eu exhibited a stable and broad optimal emission wavelength ranging from 505 to 540 nm. Notably, the photoluminescence quantum yield (PLQY) of N,S-CDs/Eu is 31.4%, significantly higher than the 19.5% observed for N,S-CDs. Additionally, by dissolving N,S-CDs/Eu into polyvinyl alcohol (PVA), a uniform fluorescent anti-counterfeiting ink can be prepared. The N,S-CDs/Eu/TiO2 composite demonstrates excellent photocatalytic degradation ability towards the organic dye methylene blue (MB). N,S-CDs/Eu has potential in the field of fluorescent inks and photocatalysis due to its simple and efficient preparation and excellent properties.
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Carbono , Europio , Helianthus , Tinta , Puntos Cuánticos , Europio/química , Carbono/química , Catálisis , Puntos Cuánticos/química , Helianthus/química , Procesos Fotoquímicos , Colorantes Fluorescentes/química , Colorantes Fluorescentes/síntesis química , Azul de Metileno/química , FluorescenciaRESUMEN
Regulating photocurrent polarity is highly attractive for fabricating photoelectrochemical (PEC) biosensors with improved sensitivity and accuracy in practical samples. Here, a new approach that adopts the in situ generated AgI precipitate and AgNCs to reversal Bi2WO6 polarity with formation of Z-type heterojunction was proposed for the first time, which coupled with a high-efficient target conversion strategy of exonuclease III (Exo III)-assisted triple recycling amplification for sensing miRNA-21. The target-related DNA nanospheres in situ generated on electrode with loading of plentiful AgI and AgNCs not only endowed the photocurrent of Bi2WO6 switching from the anodic to cathodic one due to the changes in the electron transfer pathway but also formed AgI/AgNCs/Au/Bi2WO6 Z-type heterojunction to improve the photoelectric conversion efficiency for acquiring extremely enhanced PEC signal, thereby significantly avoiding the problem of high background signal derived from traditional unidirectional increasing/decreasing response and false-positive/false-negative. Experimental data showed that the PEC biosensor had a low detection limit down to 0.085 fM, providing a new polarity-reversal mechanism and expected application in diverse fields, including biomedical research and clinical diagnosis.
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Técnicas Biosensibles , Técnicas Electroquímicas , MicroARNs , Compuestos de Plata , MicroARNs/análisis , Compuestos de Plata/química , Procesos Fotoquímicos , Exodesoxirribonucleasas/química , Exodesoxirribonucleasas/metabolismo , Límite de Detección , Humanos , Electrodos , YodurosRESUMEN
Antibiotic residues have been found in several aquatic ecosystems as a result of the widespread use of antibiotics in recent years, which poses a major risk to both human health and the environment. At present, photocatalytic degradation is the most effective and environmentally friendly method. Titanium silicon molecular sieve (TS-1) has been widely used as an industrial catalyst, but its photocatalytic application in wastewater treatment is limited due to its small pores and few active sites. In this paper, we report a method for preparing multistage porous TS-1 with a high specific surface area by alkali treatment. In the photocatalytic removal of CIP (ciprofloxacin) antibiotic wastewater experiments, the alkali-treated catalyst showed better performance in terms of interfacial charge transfer efficiency, which was 2.3 times higher than that of TS-1 synthesized by the conventional method, and it was found to maintain better catalytic performance in the actual water source. In addition, this research studied the effects of solution pH, contaminant concentration, and catalyst dosage on CIP degradation, while liquid chromatography-mass spectrometry (LC-MS) was used to identify intermediates in the degradation process and infer possible degradation pathways and the toxicity of CIP, and its degradation product was also analyzed using ECOSAR 2.2 software, and most of the intermediates were found to be nontoxic and nonharmful. Finally, a 3:5:1 artificial neural network model was established based on the experiments, and the relative importance of the influence of experimental conditions on the degradation rate was determined. The above results confirmed the feasibility and applicability of photocatalytic treatment of wastewater containing antibiotics using visible light excitation alkali post-treatment TS-1, which provided technical support and a theoretical basis for the photocatalytic treatment of wastewater containing antibiotics.
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Redes Neurales de la Computación , Titanio , Catálisis/efectos de la radiación , Titanio/química , Titanio/efectos de la radiación , Porosidad , Antibacterianos/química , Silicio/química , Contaminantes Químicos del Agua/química , Procesos Fotoquímicos , Ciprofloxacina/química , Aguas Residuales/química , Fotólisis/efectos de la radiaciónRESUMEN
Smart photochromic and fluorescent textile refers to garments that alter their colorimetric properties in response to external light stimulus. Cotton fibers have been reported as a main resource for many textile and non-textile industries, such as automobiles, medical devices, and furniture applications. Cotton is a natural fiber that is distinguished with breathability, softness, cheapness, and highly absorbent. However, there have been growing demands to find other resources for cotton textiles at high quality and low cost for various applications, such as sensor for harmful ultraviolet radiation. Herein, we present a novel method toward luminescent and photochromic nonwoven textiles from recycled cotton waste. Using the screen-printing technology, a cotton fabric that is both photochromic and fluorescent was developed using aqueous inorganic phosphor nanoparticles (10-18 nm)-containing printing paste. Both CIE Lab color coordinates and photoluminescence spectra showed that the transparent film printed on the nonwoven fabric develops a reversible green emission (519 nm) under ultraviolet light (365 nm), even at low pigment concentration (2%) in the printing paste. Colorfastness of printed fabrics showed high durability and photostability.
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Celulosa , Fibra de Algodón , Estroncio , Fibra de Algodón/análisis , Celulosa/química , Estroncio/química , Textiles , Rayos Ultravioleta , Dispositivos Electrónicos Vestibles , Luminiscencia , Óxido de Aluminio/química , Impresión , Procesos Fotoquímicos , ReciclajeRESUMEN
Pharmaceuticals and personal care products (PPCPs) which include antibiotics such as tetracycline (TC) and ciprofloxacin (CIP), etc., have attracted increasing attention worldwide due to their potential threat to the aquatic environment and human health. In this work, a facile sol-gel method was developed to prepare tungsten-doped TiO2 with tunable W5+/W6+ ratio for the removal of PPCPs. The influence of solvents in the synthesis of the three different tungsten precursors doped TiO2 is also taken into account. WCl6, ammonium metatungstate (AMT), and Na2WO4â2H2O not only acted as the tungsten precursors but also controlled the tungsten ratio. The photocatalyst prepared by WCl6 as the tungsten precursor and ethanol as the solvent showed the highest photodegradation performance for ciprofloxacin (CIP) and tetracycline (TC), and the photodegradation performance for tetracycline (TC) was 2.3, 2.8, and 7.8 times that of AMT, Na2WO4â2H2O as the tungsten precursors and pristine TiO2, respectively. These results were attributed to the influence of the tungsten precursors and solvents on the W5+/W6+ ratio, sample crystallinity and surface properties. This study provides an effective method for the design of tungsten-doped TiO2 with tunable W5+/W6+ ratio, which has a profound impact on future studies in the field of photocatalytic degradation of PPCPs using an environmentally friendly approach.
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Cosméticos , Solventes , Titanio , Tungsteno , Titanio/química , Tungsteno/química , Catálisis , Solventes/química , Cosméticos/química , Fotólisis , Ciprofloxacina/química , Preparaciones Farmacéuticas/química , Tetraciclina/química , Procesos Fotoquímicos , Contaminantes Químicos del Agua/químicaRESUMEN
Bovine serum albumin (BSA) has been widely used in biosensors as a blocking agent. Herein, conformist BSA was first exploited as an ingenious operator to enhance the photocurrent response of (2Z,2'Z)-2,2'-(1,4-phenylene)bis(3-(4-(bis(4-methoxyphenyl)amino)phenyl)acrylonitrile) (TPDCN)-based photoelectrochemical (PEC) platform via manipulating the electron transfer process of the detection system. Concretely, the presence of target molecules triggered catalytic hairpin assembly reaction and subsequently powered terminal deoxynucleotidyl transferase-mediated signal amplification to produce the AgNP@BSA-DNA dendrimer nanostructure. After being treated with HNO3, a large amount of BSA could be released from the dendrimer nanostructure. When they were transferred to the TPDCN-based PEC platform, the photocurrent response of the biosensor was largely enhanced because BSA can manipulate the electrons of TPDCN via a well-matched energy level to form a new electron transfer track. Meanwhile, tryptophan (Trp) in BSA could be oxidized to quinone Trp-O under photoirradiation, which can facilitate the oxidation of ascorbate and generate more H+ to promote the migration of photogenerated electrons. As a result, the proposed PEC biosensor exhibits excellent analytical performance for detection of miRNA-21 (as a model target) over a wide linear range of 0.01 to 10,000 pM with detection limit as low as 4.7 fM. Overall, this strategy provides a new perspective on constructing efficient PEC biosensors, which expands the potential applications in bioanalysis and clinical diagnosis.
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Técnicas Biosensibles , Técnicas Electroquímicas , MicroARNs , Procesos Fotoquímicos , Albúmina Sérica Bovina , Albúmina Sérica Bovina/química , MicroARNs/análisis , Animales , Bovinos , Humanos , Electrones , Límite de DetecciónRESUMEN
SO2 derivatives, sulfite/bisulfite, are widely employed in both the food processing and drug synthesis industries. Despite their widespread application, excessive levels of sulfite/bisulfite can negatively impact human health. Most probes for detecting sulfite/bisulfite are restricted by their fluorescence within the visible spectrum range and poor solubility in aqueous solution, which limit their use in food testing and biological imaging. Herein, a near-infrared probe comprising of the cyanopyridine cyanine skeleton, 4-((Z)-2-((E)-2-chloro-3-(2-cyano-2-(1-methylpyridine-4(1H)-ylidene)ethylidene)cyclohex-1-en-1-yl)-1-cyanovinyl)-1-methylpyridin-1-ium (abbreviated as CCP), was developed. This probe enables precise quantification of bisulfite (HSO3-) in almost pure buffered solutions, showing a near-infrared fluorescence emission at 784 nm with an impressively low detection limit of 0.32 µM. The probe stands out for its exceptional selectivity, minimal susceptibility to interference, and strong adaptability. The probe CCP utilizes the CC bond to trigger a near-infrared fluorescence quenching reaction with HSO3- via nucleophilic addition, which effectively disrupts the large delocalization within the molecule for accurate HSO3- identification. Moreover, the probe has been successfully applied in detecting HSO3- in various food products and living cells, simplifying the measurement of HSO3- content in water samples. This advancement not only enhances the analytical capabilities but also contributes to ensuring food safety and environmental protection. ENVIRONMENTAL IMPLICATION: SO2 derivatives including sulfite/bisulfite, serving dual roles as preservatives and antioxidants, have widespread application across various sectors including food preservation, water sanitation, and the pharmaceutical industry. Despite their widespread application, excessive levels of sulfite/bisulfite can affect human health. Developing methods for precisely and sensitively detecting sulfite/bisulfite in food products and biological samples is important for ensuring food safety and environmental protection. Here, a sensitive near-infrared and multifunctional fluorescent probe in a 99.9 % buffered solution, along with water gel encapsulation, has been successfully applied for the detection of bisulfite in food, authentic water samples, and biological cells.
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Carbocianinas , Sulfitos , Espectroscopía Infrarroja Corta/métodos , Espectrometría de Fluorescencia/métodos , Piridinas/química , Carbocianinas/química , Sulfitos/análisis , Sulfitos/química , Estructura Molecular , Humanos , Células HeLa , Procesos Fotoquímicos , Límite de Detección , Hidrogeles/química , Análisis de los AlimentosRESUMEN
Lanthanum nickelate (LaNiO3), known for its high visible-light absorption, is a promising photocatalyst for water purification. However, the low conduction band position and high photogenerated carrier complexation rate of pure LaNiO3 limit its photocatalytic activity. To address this issue, we investigated the synergistic effects of doping and constructing heterojunctions. A La0.9Sr0.1NiO3 (20%)/g-C3N4 (L2CN8) heterojunction was successfully created. In addition, various characterisation techniques were then employed to analyse the structure-performance relationships of these heterojunction photocatalysts in degrading organic dyes. Results revealed that at a 10% Sr doping level, the oxygen vacancy content was 0.68, which is significantly higher than that of LaNiO3 (0.05). The increased number of oxygen vacancies enhanced the electron capture ability and improved the separation efficiency of photogenerated carriers. Furthermore, the optimised L2CN8 (20 mg) achieved 81.2% and 73.8% removal of methylene blue (50.0 mL, 10 mg L-1) and tetracycline (50.0 mL, 10 mg L-1) under simulated visible-light irradiation (λ > 420 nm). Furthermore, an active species capture experiment confirmed the significant role of superoxide radicals (·O2-) in the degradation process. Based on these experimental findings, we proposed a rational Z-type charge transfer mechanism. This study holds great importance for water pollution control and environmental protection.
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Lantano , Luz , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis , Catálisis , Lantano/química , Níquel/química , Azul de Metileno/química , Fotólisis , Procesos Fotoquímicos , Compuestos de Nitrógeno/química , Tetraciclina/química , Nitrilos/química , GrafitoRESUMEN
This study aims to improve the photocatalytic properties of titanium dioxide nanorods (TNRs) and other related nanostructures (dense nanorods, needle-like nanorods, nanoballs, and nanoflowers) by modifying them with silver nanoparticles (AgNPs). This preparation is carried out using a two-step method: sol-gel dip-coating deposition combined with hydrothermal crystal growth. Further modification with AgNPs was achieved through the photoreduction of Ag+ ions under UV illumination. The investigation explores the impact of different growth factors on the morphological development of TiO2 nanostructures by modulating (i) the chemical composition, the water:acid ratio, (ii) the precursor concentration involved in the hydrothermal process, and (iii) the duration of the hydrothermal reaction. Morphological characteristics, including the length, diameter, and nanorod density of the nanostructures, were analyzed using scanning electron microscope (SEM). The chemical states were determined through use of the X-ray photoelectron spectroscopy (XPS) technique, while phase composition and crystalline structure analysis was performed using the Grazing Incidence X-ray Diffraction (GIXRD) method. The results indicate that various nanostructures (dense nanorods, needle-like nanorods, nanoballs, and nanoflowers) can be obtained by modifying these parameters. The photocatalytic efficiency of these nanostructures and Ag-coated nanostructures was assessed by measuring the degradation of the organic dye rhodamine B (RhB) under both ultraviolet (UV) irradiation and visible light. The results clearly show that UV light causes the RhB solution to lose its color, whereas under visible light RhB changes into rhodamine 110, indicating a successful photocatalytic transformation. The nanoball-like structures' modification with the active metal silver (TNRs 4 Ag) exhibited high photocatalytic efficiency under both ultraviolet (UV) and visible light for different chemical composition parameters. The nanorod structure (TNRs 2 Ag) is more efficient under UV, but under visible-light photocatalyst, the TNRs 6 Ag (dense nanorods) sample is more effective.
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Nanopartículas del Metal , Plata , Titanio , Titanio/química , Plata/química , Nanopartículas del Metal/química , Catálisis , Nanoestructuras/química , Rodaminas/química , Procesos Fotoquímicos , Nanotubos/química , Rayos Ultravioleta , Fotólisis , Difracción de Rayos X , Espectroscopía de FotoelectronesRESUMEN
Graphitic carbon nitride (g-C3N4)-based photocatalysts have garnered significant interest as a promising photocatalyst for hydrogen generation under visible light, to address energy and environmental challenges owing to their favorable electronic structure, affordability, and stability. In spite of that, issues such as high charge carrier recombination rates and low quantum efficiency impede its broader application. To overcome these limitations, structural and morphological modification of the g-C3N4-based photocatalysts is a novel frontline to improve the photocatalytic performance. Therefore, we briefly summarize the current preparation methods of g-C3N4. Importantly, this review highlights recent advancements in crafting high-performance g-C3N4-based photocatalysts, focusing on strategies like elemental doping, nanostructure design, bandgap engineering, and heterostructure construction. Notably, sophisticated doping techniques have propelled hydrogen production rates to a 104-fold increase. Ingenious nanostructure designs have expanded the surface area by a factor of 26, concurrently extending the fluorescence lifetime of charge carriers by 50%. Moreover, the strategic assembly of heterojunctions has not only elevated charge carrier separation efficiency but also preserved formidable redox properties, culminating in a dramatic hundredfold surge in hydrogen generation performance. This work provides a reliable and brief overview of the controlled modification engineering of g-C3N4-based photocatalyst systems, paving the way for more efficient hydrogen production.
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Grafito , Hidrógeno , Compuestos de Nitrógeno , Procesos Fotoquímicos , Hidrógeno/química , Catálisis , Grafito/química , Compuestos de Nitrógeno/química , Luz , Nanoestructuras/químicaRESUMEN
Singlet oxygen generation has long been considered the key feature that allows genetically encoded fluorescent tags to produce polymeric contrast agents for electron microscopy. Optimization of the singlet oxygen sensitization quantum yield has not included the effects of electron-rich monomers on the sensitizer's photocycle. We report that at monomer concentrations employed for staining, quenching by electron transfer is the primary deactivation pathway for photoexcitations. A simple photochemical model including contributions from both processes reproduces the observed reaction rates and indicates that most of the product is driven by pathways that involve electron transfer with monomersânot by the sensitization of singlet oxygen. Realizing the importance of these competing reaction pathways offers a new paradigm to guide the development of genetically encodable tags and suggests opportunities to expand the materials scope and growth conditions for polymeric contrast agents (e.g., biocompatible monomers, O2 poor environments).
Asunto(s)
Medios de Contraste , Polimerizacion , Transporte de Electrón , Medios de Contraste/química , Oxígeno Singlete/química , Flavoproteínas/química , Flavoproteínas/metabolismo , Fármacos Fotosensibilizantes/química , Procesos FotoquímicosRESUMEN
In this computational study, density functional theory (DFT) and time-dependent DFT methods (TD-DFT) were employed to study the optical properties of six families of molecules with donor (D), bridge (B), and acceptor (A) fragments that have potential for use as fluorescent molecular probes for the early detection of Alzheimer's disease. After validating our computational method against experimental data, using X-ray and absorption data, the equilibrium geometries and wave functions of the ground and first singlet excited states were systematically studied. Our simulations demonstrate that the S1 states of these rod-like D-B-A fluorescent probes are twisted intramolecular charge transfer states with a predominant highest occupied molecular orbital-least unoccupied molecular orbital (HOMO-LUMO) character, the former localized primarily at the donor, whereas the latter at the acceptor site. Moreover, the influence of the bridge, donor, and acceptor fragments on molecules' absorption energies is explored, highlighting the influence of double and triple bonds and some specific modifications on the acceptor side, including the addition of electronegative atoms, pyranone derivatives, and their functionalization. By having the absorption energies of 324 probes in hand, machine learning models were trained to predict the absorption energies of molecules. The models were found to be predictive, which suggests a potential that predictive models for other crucial properties, such as emission and quantum yield, can also be trained if suitable training data sets are made available.
Asunto(s)
Péptidos beta-Amiloides , Teoría Funcional de la Densidad , Péptidos beta-Amiloides/química , Colorantes Fluorescentes/química , Estructura Molecular , Procesos Fotoquímicos , Aprendizaje AutomáticoRESUMEN
Fabricating metal oxide nanoparticles has garnered much attention lately because creating safe chemicals, sustainable materials, economic processes, and renewable resources is becoming increasingly important. This research shows how TiO2 nanoparticles (NPs) could be generated in an ecologically responsible way using waste coconut husk with the help of tender coconut. This extract functions as both a reducing agent and a sealing agent. The investigation of TiO2 NPs exploited ultraviolet (UV), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and field-emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray (EDX) methods. The germicidal properties of TiO2 NPs against food-borne pathogenic strains were studied using the agar well method. Employing Congo red pigment, the photodecomposition behavior was investigated. The TiO2 NPs produced had a crystallite size measuring 16.2 nm. The average grain size of the sample, as measured by FE-SEM inspection, falls within the range of 15 to 25 nm. Impressive anti-germ effects against food-borne germs like Gram-positive (Staphylococcus aureus and Listeria monocytogenes), Gram-negative (Salmonella typhimurium and Escherichia coli) bacteria, and fungi (Candida albicans and Aspergillus niger) have been proved by the sustainable fabrication of TiO2 NPs. The catalytic effectiveness of Congo red decreased by 88% after 90 min. The findings suggest that sustainable synthesis of TiO2 NPs is an effective tool for food-borne germicides and photodecomposition behaviors.