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1.
Anal Chem ; 96(23): 9704-9712, 2024 06 11.
Artigo em Inglês | MEDLINE | ID: mdl-38819721

RESUMO

Due to the commonly low content of biomarkers in diseases, increasing the sensitivity of electrochemiluminescence (ECL) systems is of great significance for in vitro ECL diagnosis and biodetection. Although dissolved O2 (DO) has recently been considered superior to H2O2 as a coreactant in the most widely used luminol ECL systems owing to its improved stability and less biotoxicity, it still has unsatisfactory ECL performance because of its ultralow reactivity. In this study, an effective plasmonic luminol-DO ECL system has been developed by complexing luminol-capped Ag nanoparticles (AgNPs) with plasma-treated Fe single-atom catalysts (Fe-SACs) embedded in graphitic carbon nitride (g-CN) (pFe-g-CN). Under optimal conditions, the performance of the resulting ECL system could be markedly increased up to 1300-fold compared to the traditional luminol-DO system. Further investigations revealed that duple binding sites of pFe-g-CN and plasmonically induced hot holes that disseminated from AgNPs to g-CN surfaces lead to facilitate significantly the luminous reaction process of the system. The proposed luminol-DO ECL system was further employed for the stable and ultrasensitive detection of prostate-specific antigen in a wide linear range of 1.0 fg/mL to 1 µg/mL, with a pretty low limit of detection of 0.183 fg/mL.


Assuntos
Técnicas Eletroquímicas , Ferro , Medições Luminescentes , Luminol , Nanopartículas Metálicas , Oxigênio , Prata , Luminol/química , Catálise , Oxigênio/química , Nanopartículas Metálicas/química , Ferro/química , Prata/química , Humanos , Antígeno Prostático Específico/metabolismo , Antígeno Prostático Específico/química , Grafite/química , Limite de Detecção , Domínio Catalítico , Compostos de Nitrogênio/química
2.
Anal Chem ; 96(31): 12838-12845, 2024 08 06.
Artigo em Inglês | MEDLINE | ID: mdl-39052979

RESUMO

MicroRNA (miRNA) detection is a critical aspect of disease diagnosis, and recent studies indicate that miRNA-622 could be a potential target for lung cancer. Herein, Cu single atoms were anchored on graphitic carbon nitride (Cu SAs@CN) as a coreaction accelerator applied in luminol-H2O2 system, thereby establishing an efficient and sensitive electrochemiluminescence (ECL) biosensor for miRNA-622 detection. Cu SAs@CN was explored to possess excellent enzyme-like activities that promote the generation of abundant reactive oxygen species, which amplified ECL emission. Meanwhile, in order to improve the accuracy and sensitivity for miRNA-622 detection, the highly specific trans-cleavage ability of CRISPR/Cas12a was combined with a catalytic hairpin assembly strategy. Therefore, an ECL biosensor for miRNA-622 detection was systematically constructed as a proof of concept, achieving an ultralow limit of detection of 1.09 fM, and the feasibility was demonstrated in human serum samples. The findings of this research provide a promising strategy to enhance the ECL response using versatile single-atom catalysts, thus advancing the development of ECL biosensing applications.


Assuntos
Técnicas Biossensoriais , Cobre , Técnicas Eletroquímicas , Grafite , Medições Luminescentes , Luminol , MicroRNAs , Técnicas Biossensoriais/métodos , Humanos , MicroRNAs/análise , MicroRNAs/sangue , Cobre/química , Grafite/química , Luminol/química , Limite de Detecção , Peróxido de Hidrogênio/química , Compostos de Nitrogênio/química , Catálise , Proteínas Associadas a CRISPR , Sistemas CRISPR-Cas , Proteínas de Bactérias , Endodesoxirribonucleases
3.
Phys Chem Chem Phys ; 26(32): 21677-21687, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39091182

RESUMO

In recent years, great progress has been made on the study of nanozymes with enzyme-like properties. Here, bimetallic Fe and Ni nanoclusters were anchored on the nanosheets of nitrogen-rich layered graphitic carbon nitride by one-step pyrolysis at high temperature (Fe/Ni-CN). The loading content of Fe and Ni on Fe/Ni-CN is as high as 8.0%, and Fe/Ni-CN has a high specific surface area of 121.86 m2 g-1. The Fe/Ni-CN can effectively oxidize 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2, and exhibits efficient peroxidase-like activity, leading to a 17.2-fold increase compared to pure graphitic carbon nitride (CN). Similar to the natural horseradish peroxidase (HRP), the Fe/Ni-CN nanozyme follows catalytic kinetics. The Michaelis-Menten constant (Km) value of the Fe/Ni-CN nanozyme for TMB is about 8.3-fold lower than that for HRP, which means that the Fe/Ni-CN nanozyme has better affinity for TMB. In addition, the catalytic mechanism was investigated by combination of free radical quenching experiments and density-functional theory (DFT) calculations. The results show that the high peroxidase-like activity is due to the easy adsorption of H2O2 after bimetal loading, which is conducive to the production of hydroxyl radicals. Based on the extraordinary peroxidase-like activity, the colorimetric detection of p-phenylenediamine (PPD) was constructed with a wide linear range of 0.2-30 µM and a low detection limit of 0.02 µM. The sensor system has been successfully applied to the detection of residual PPD in real dyed hair samples. The results show that the colorimetric method is sensitive, highly selective and accurate. This study provides a new idea for the efficient enhancement of nanozyme activity and effective detection of PPD by a bimetallic synergistic strategy.


Assuntos
Colorimetria , Grafite , Ferro , Níquel , Compostos de Nitrogênio , Fenilenodiaminas , Grafite/química , Fenilenodiaminas/química , Colorimetria/métodos , Compostos de Nitrogênio/química , Níquel/química , Ferro/química , Peróxido de Hidrogênio/análise , Peróxido de Hidrogênio/química , Nitrilas/química , Limite de Detecção , Catálise , Benzidinas/química
4.
Phys Chem Chem Phys ; 26(18): 14018-14036, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38683598

RESUMO

In this study, the potential of aluminum nitride (h-AlN), boron nitride (h-BN) and silicon carbide (h-SiC) nanosheets as the drug delivery systems (DDS) of isoniazid (INH) was scrutinized through density functional theory (DFT) and molecular dynamic (MD) simulations. We performed DFT periodic calculations on the geometry and electronic features of nanosheets adsorbed with INH by the DFT functional (DZP/GGA-PBE) employed in the SIESTA code. In the energetically favorable model, an oxygen atom of the C-O group of the INH molecule interacts with a Si atom of the h-SiC at 2.077 Å with an interaction energy of -1.361 eV. Charge transfer (CT) calculation by employing the Mulliken, Hirshfeld and Voronoi approaches reveals that the monolayers and drug molecules act as donors and acceptors, respectively. The density of states (DOS) calculations indicate that the HOMO-LUMO energy gap (HLG) of the h-SiC nanosheet declines significantly from 2.543 to 1.492 eV upon the adsorption of the INH molecule, which causes an electrical conductivity increase and then produces an electrical signal. The signal is linked to the existence of INH, demonstrating that h-SiC may be an appropriate sensor for INH sensing. The decrease in HLG for the interaction of INH and h-SiC is the uppermost (up to 41%) representing the uppermost sensitivity, whereas the sensitivity trend is σ(h-SiC) > σ(h-AlN) > σ(h-BN). Quantum theory of atoms in molecules (QTAIM) investigations is employed to scrutinize the nature of the INH/nanosheet interactions. The QTAIM analysis reveals that the interaction of the INH molecule and h-SiC has a partially covalent nature, while INH/h-AlN model electrostatic interaction occurs in the system and noncovalent and electrostatic interaction for the INH/h-BN model. Finally, the state-of-the-art DFT-MD simulations utilized in this study can mimic ambient conditions. The results obtained from the MD simulation show that it takes more time to bond the INH drug and h-SiC, and the INH/h-SiC system becomes stable. The results of the current research demonstrate the potential of h-SiC as a suitable sensor and drug delivery platform for INH drugs to remedy tuberculosis.


Assuntos
Compostos de Boro , Compostos Inorgânicos de Carbono , Teoria da Densidade Funcional , Isoniazida , Simulação de Dinâmica Molecular , Compostos de Silício , Isoniazida/química , Compostos de Silício/química , Compostos Inorgânicos de Carbono/química , Compostos de Boro/química , Sistemas de Liberação de Medicamentos , Nanoestruturas/química , Antituberculosos/química , Compostos de Nitrogênio/química , Portadores de Fármacos/química , Compostos de Alumínio
5.
Bioorg Chem ; 147: 107418, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38703441

RESUMO

A key approach in developing green chemistry involves converting solar energy into chemical energy of biomolecules through photocatalysis. Photocatalysis can facilitate the regeneration of nicotinamide cofactors during redox processes. Nicotinamide cofactor biomimetics (NCBs) are economical substitutes for natural cofactors. Here, photocatalytic regeneration of NADH and reduced NCBs (NCBsred) using graphitic carbon nitride (g-C3N4) was developed. The process involves g-C3N4 as the photocatalyst, Cp*Rh(bpy)H2O2+ as the electron mediator, and Triethanolamine as the electron donor, facilitating the reduction of NAD+ and various oxidative NCBs (NCBsox) under light irradiation. Notably, the highest reduction yield of 48.32 % was achieved with BANA+, outperforming the natural cofactor NAD+. Electrochemical analysis reveals that the reduction efficiency and capacity of cofactors relies on their redox potentials. Additionally, a coupled photo-enzymatic catalysis system was explored for the reduction of 4-Ketoisophorone by Old Yellow Enzyme XenA. Among all the NCBsox and NAD+, the highest conversion ratio of over 99 % was obtained with BANA+. After recycled for 8 times, g-C3N4 maintained over 93.6 % catalytic efficiency. The photocatalytic cofactor regeneration showcases its outstanding performance with NAD+ as well as NCBsox. This work significantly advances the development of photocatalytic cofactor regeneration for artificial cofactors and its potential application.


Assuntos
Biocatálise , Oxirredução , Processos Fotoquímicos , Materiais Biomiméticos/química , Materiais Biomiméticos/metabolismo , Estrutura Molecular , NAD/química , NAD/metabolismo , Biomimética , Niacinamida/química , Niacinamida/metabolismo , Compostos de Nitrogênio/química , Grafite
6.
Environ Res ; 249: 118358, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38325777

RESUMO

Increasing the electron-hole recombination rate in g-C3N4 can effectively improve its photocatalytic performance. In this work, NiCoP/g-C3N4 (NCP/PCN) composites with ohmic junction were formed by embedding granular NiCoP in irregularly porous g-C3N4. There was almost no barrier between the metal and the semiconductor in ohmic junction, which made it easier for electrons to slip from PCN to NCP along the curved energy band, and NCP acted as an electron collector to rapidly capture the slipping electrons. In addition, porous g-C3N4 prepared by supramolecular self-assembly could provide a shorter diffusion path for electrons. Thus, the electron-hole was effectively separated and the photocatalytic performance was improved. The band electronic structure and existence of ohmic junction in 7-NCP/PCN composite were demonstrated by XPS, ESR and DFT calculation. Finally, a reasonable photocatalytic degradation mechanism and possible tetracycline degradation path were proposed. This work has significant potential for providing an effective method for the design of non-precious metal photocatalysts.


Assuntos
Luz , Tetraciclina , Tetraciclina/química , Catálise , Poluentes Químicos da Água/química , Compostos de Nitrogênio/química , Processos Fotoquímicos , Grafite/química
7.
Environ Res ; 258: 119484, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38914250

RESUMO

The present research utilizes a sol-gel approach to create a CoFe2O4/g-C3N4 nanocomposite (NC) and explored several analytical methods to evaluate physical, chemical and optical based characteristics via XRD, FTIR, UV-vis, SEM/EDS and XPS for the prepared pure CoFe2O4, g-C3N4, and CoFe2O4/g-C3N4 NC. The XRD results show that the prepared g-C3N4, CoFe2O4, exhibits hexagonal and cubic phases respectively, whereas the g-C3N4/CoFe2O4 NC exhibit mixing of two phases. The energy band gaps for pure g-C3N4, CoFe2O4 and g-C3N4/CoFe2O4 NC values are viz., 2.75, 1.3, and 2.4 eV. As photocatalysts, synthesized materials were utilized for the decomposition of Rhodamine-B (RhB) dye. Finally, the CoFe2O4/g-C3N4 NC showed good performance of photocatalysis for RhB dye disintegration under the stimulus of visible light. According to the induced visible light, the rate at which the photocatalytic degradation occurs for the CoFe2O4/g-C3N4 NC was found to be 57% in 120 min and this is greater when compared with pure catalysts like CoFe2O4 (28%) and g-C3N4 (10%). These outcomes suggest that the prepared NC have efficiently worked during the photocatalytic process compared with its pure materials.


Assuntos
Cobalto , Compostos Férricos , Grafite , Rodaminas , Cobalto/química , Rodaminas/química , Compostos Férricos/química , Grafite/química , Compostos de Nitrogênio/química , Fotólise , Nanocompostos/química , Catálise , Nitrilas/química
8.
Environ Res ; 254: 119163, 2024 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-38759770

RESUMO

The hydrothermal approach was used in the design and construction of the SnWO4 (SW) nanoplates anchored g-C3N4 (gCN) nanosheet heterostructures. Morphology, optical characteristics, and phase identification were investigated. The heterostructure architect construction and successful interface interaction were validated by the physicochemical characteristics. The test materials were used as a photocatalyst in the presence of visible light to break down the antibiotic tetracycline (TC) and the organic Rhodamine B (RhB). The best photocatalytic degradation efficiency of TC (97%) and RhB (98%) pollutants was demonstrated by the optimized 15 mg of gCNSW-7.5 in 72 and 48 min, respectively, at higher rate constants of 0.0409 and 0.0772 min-1. The interface contact between gCN and SW, which successfully enhanced charge transfer and restricted recombination rate in the photocatalyst, is responsible for the enhanced performance of the gCNSW heterostructure photocatalyst. In addition, the gCNSW heterostructure photocatalyst demonstrated exceptional stability and reusability over the course of four successive testing cycles, highlighting its durable and dependable function. Superoxide radicals and holes were shown to be key players in the degradation of contaminants through scavenger studies. The charge transfer mechanism in the heterostructure is identified as Z-scheme mode with the help of UV-vis DRS analysis. Attributed to its unique structural features, and effective separation of charge carriers, the Z-scheme gCNSW-7.5 heterostructure photocatalyst exhibits significant promise as an exceptionally efficient catalyst for the degradation of pollutants. This positions it as a prospective material with considerable potential across various environmental applications.


Assuntos
Luz , Rodaminas , Tetraciclina , Rodaminas/química , Tetraciclina/química , Catálise , Poluentes Químicos da Água/química , Fotólise , Compostos de Nitrogênio/química , Processos Fotoquímicos , Antibacterianos/química , Grafite
9.
Environ Res ; 258: 119390, 2024 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-38879105

RESUMO

Photocatalysis is recognized to be one of the most promising ways to address energy and environmental issues by utilizing visible light. Graphitic carbon nitride (g-C3N4), with a moderate band gap (∼2.7 eV) has been the flashpoint in environmental photocatalysis as it can work better under visible light, can be synthesized by a facile synthesis process using low-cost materials, thermally and chemically stable. Still the photocatalytic performance of g-C3N4 is not satisfactory because of certain limitations such as insufficient visible light absorption capacity, low electron-hole separation efficiency, high recombination rate, poor surface area. Introduction of doping, band structure engineering, defecting and designing of heterojunction, composites etc. were investigated to amplify its applications. Among all these modifications, elemental doping is a suitable and successful alternative for the enhancement of the photocatalytic activity by changing the optical and electronic properties. This review emphasizes on advancement and trends of elemental doping and its application on photocatalytic organic pollutant remediation in aqueous medium. The fundamental photocatalytic activity of heterogeneous photocatalysis and specifically g-C3N4-based photocatalysis have been discussed. The benfits of non-metal doping, enhanced photocatalytic performance by doping element, mechanism invloved in doping, advantages of co-doping has been explained. Mono, bi, and tri non-metal doped g-C3N4 and their application for the removal of organic pollutants from water medium by visible light photocatalysis has been summerized. Life cycle assessment (LCA) of photocatalytic system has been highlighted. Future research should focus on the large-scale application of the photocatalysis process considering the economic aspects. A rigorous life cycle assessment for deploying the non-metal doped g-C3N4-based photocatalysis technology for successful commercial application is recommended.


Assuntos
Grafite , Catálise , Grafite/química , Recuperação e Remediação Ambiental/métodos , Compostos de Nitrogênio/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Processos Fotoquímicos , Luz , Nitrilas/química
10.
Environ Res ; 252(Pt 3): 119043, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38692422

RESUMO

It is of great significance to establish an effective method for removing Cr(VI) from wastewater. Herein, Fe-doped g-C3N4 (namely Fe-g-C3N4-2) was synthesized and then employed as photocatalyst to conduct the test of Cr(VI) reduction. Notably, the embedding of Fe ion in g-C3N4 can offer the Fe2+/Fe3+ redox couples, so reducing the interfacial resistance of charge transfer and suppressing the recombination of photogenerated electrons and holes. The impurity energy levels will form in g-C3N4 after the introduction of Fe ion, thereby boosting the light absorption capacity of catalyst. Thus, Fe-g-C3N4-2 showed good performance in photocatalytic Cr(VI) reduction, and the reduction efficiency of Cr(VI) can reach 39.9% within 40 min. Different with many previous studies, current work unexpectedly found that the addition of p-benzoquinone (BQ) can promote the Cr(VI) reduction, and the reduction efficiency of Cr(VI) over Fe-g-C3N4-2 was as high as 93.2% in the presence of BQ (1.5 mM). Further analyses showed that BQ can be reduced to hydroquinone (HQ) by photogenerated electrons, and UV light can also directly induce BQ to generate HQ by using H2O as the hydrogen donor. The HQ with reducing ability can accelerate the Cr(VI) reduction. In short, current work shared some novel insights into photocatalytic Cr(VI) reduction in the presence of BQ. Future research should consider possible reactions between photogenerated electrons and BQ. For the UV-induced photocatalysis, the suitability of BQ as the scavenger of O2•‒ must be given carefully consideration.


Assuntos
Benzoquinonas , Cromo , Ferro , Oxirredução , Benzoquinonas/química , Cromo/química , Catálise , Ferro/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/efeitos da radiação , Processos Fotoquímicos , Compostos de Nitrogênio/química , Compostos de Nitrogênio/efeitos da radiação , Grafite
11.
Environ Res ; 256: 119184, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38782344

RESUMO

The remarkable application of tin oxide in various domains is indebted to its photoelectronic merits. However, significant efforts to discover its photocatalytic potential were restricted through arduous challenges, which were the amelioration of light-harvesting and -utilizing. In fact, the uncommon light absorption energy has drawn veil over the brilliance of astounding oxidation potential, which is much more than that of TiO2. Herein, our attention was focused on the taking advantages of self-template structure for simultaneously enjoying the two sides of photoelectronic justification as well as the S-step system for eminent charge dissociation. In this regard, the optimized Cu-modified SnO2 yolk-shell ((5)YS-CuSnO) spheres were engineered through the copper modulation into glycerate-assisted metal-organic structure. As a result, the exceptional light-harvesting was achieved through desirable defects and oxygen vacancy resulted from Cu-doping, and also efficient light-utilization was obtained by the multi-scattering/reflection effect resulted from multi-shell configuration. After the effectual incorporation (40 wt⁒) of (5)YS-CuSnO was encapsulated into the V2O5-decorated wrinkled g-C3N4 lamella (VO-WCN), the dual S-step VO-WCN@(5)YS-CuSnO introduced unprecedented levofloxacin (LFC) decontamination performance, which was kinetically 5.2 and 30.2-times greater than of the (5)YS-CuSnO and bare SnO2 yolk-shell. The conspicuous fulfillment of nanocomposite was manifested in the LFC mineralization, pharmaceutical effluent treatment within 360 min, and successive cycling reactions. The fusion of the extraordinary architecture of YS-CuSnO with S-Step system not only initiates the facile and practical photocatalytic exploitation, but shade light on some undeveloped side of tin oxide.


Assuntos
Antibacterianos , Cobre , Fotólise , Compostos de Estanho , Compostos de Estanho/química , Cobre/química , Antibacterianos/química , Compostos de Nitrogênio/química , Grafite
12.
Environ Res ; 260: 119779, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39142459

RESUMO

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.


Assuntos
Lantânio , Luz , Poluentes Químicos da Água , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Catálise , Lantânio/química , Níquel/química , Azul de Metileno/química , Fotólise , Processos Fotoquímicos , Compostos de Nitrogênio/química , Tetraciclina/química , Nitrilas/química , Grafite
13.
Environ Res ; 257: 119293, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-38838749

RESUMO

Recently, photocatalysis combined peroxydisulfate activation under visible light (PC-PDS/Vis) was developed as a promising technology for removing antibiotics in water. Herein, Mn doped FeOOH (Mn-FeOOH) nanoclusters were grown in-situ on the surface of graphitic carbon nitride nanosheets (CNNS) using a wet chemical method, which served as a visible-light-driven photocatalyst for peroxydisulfate (PDS) activation. Photovoltaic property characterizations revealed that Mn-FeOOH/CNNS owned superior light capture ability and carrier separation efficiency. According to DFT calculations, the synergistic effect between Mn and Fe species was proved to enhance the adsorption and activation of PDS. 99.7% of tetracycline (TC) was rapidly removed in 50 min in the PC-PDS/Vis system. In addition, Mn-FeOOH/CNNS exhibited high recycling stability with low iron leaching, attributed to the interaction between Mn-FeOOH clusters and carbon species. Quenching experiments and electron spin resonance (ESR) tests unveiled that •O2- played a significant role in TC removal, while •OH and SO4•- acted as additional roles contributing to the overall process. These findings given a new strategy for antibiotics degradation by photocatalysis, offering deeper insights for the advancement of sustainable and cutting-edge wastewater treatment technologies.


Assuntos
Grafite , Luz , Tetraciclina , Poluentes Químicos da Água , Tetraciclina/química , Poluentes Químicos da Água/química , Grafite/química , Catálise , Antibacterianos/química , Manganês/química , Sulfatos/química , Compostos de Nitrogênio/química , Ferro/química , Processos Fotoquímicos
14.
Environ Res ; 251(Pt 1): 118566, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38447606

RESUMO

Both g-C3N4 and Bi2O2CO3 are good photocatalysts for the removal of antibiotic pollutants, but their morphological modulation and catalytic performance need to be further improved. In this study, the calcination-hydrothermal method is used to prepare a O-g-C3N4@Bi2O2CO3 (CN@BCO) composite photocatalyst from dicyandiamide and bismuth nitrate. The prepared catalyst is characterized through various methods, including X-ray diffraction (XRD) and transmission electron microscopy (TEM). Further, the effects of different parameters, such as catalyst concentration and initial pH of the reaction solution, on its photocatalytic activity are investigated. The results show that the CN@BCO sample achieves an optimal degradation rate of 98.1% for tetracycline hydrochloride (TCH) with a concentration of 20 mg/L and a removal rate of 69.4% for total organic carbon (TOC) at 40 min. The quenching experiments show that ·O2-, h+, and ·OH participate in the photocatalytic process, with ·O2- being the most dominant active species. The toxicity of the predicted TCH degradation intermediates is analyzed using Toxicity Estimation Software Tool (TEST). Overall, the CN@BCO composite exhibits excellent photocatalytic performance, making it a promising candidate for environmental purification and wastewater treatment.


Assuntos
Bismuto , Tetraciclina , Águas Residuárias , Poluentes Químicos da Água , Tetraciclina/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Águas Residuárias/química , Bismuto/química , Catálise , Antibacterianos/química , Nanofios/química , Compostos de Nitrogênio/química , Nitrilas/química , Porosidade , Grafite
15.
Environ Res ; 256: 119202, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38782343

RESUMO

A rational design of heterojunctions with high-quality contacts is essential for efficiently separating photogenerated charge carries and boosting the solar-driven harvesting capability. Herein, we fabricated a novel heterojunction of SnO2 quantum dots-anchored CdS-CdCO3 with g-C3N4 nanosheets as a superior photocatalyst. SnO2 quantum dots (SQDs) with positively charged surfaces were tightly anchored on the negatively charged surface of CdS nanosheets (NSs). The resulting CdS@SnO2 was finally decorated with g-C3N4 NSs, and a new crystalline phase of CdS-CdCO3 was formed during the hydrothermal decoration process, g-C3N4 decorated CdS-CdCO3@SnO2 (CdS-CdCO3@SnO2@g-C3N4). The as-synthesized photocatalysts were evaluated for the degradation of methyl orange dye under solar light conditions. The CdS-CdCO3@SnO2@g-C3N4 exhibited 7.7-fold and 2.3-fold enhancements in photocatalytic activities in comparison to those of the bare CdS and CdS@SnO2 NSs, respectively. The optimal performance of CdS-CdCO3@SnO2@g-C3N4 is primarily attributed to the cascade-type conduction band alignments between 2D/0D/2D heterojunctions, which can harvest maximum solar light and effectively separate photoexcited charge carriers. This work provides a new inspiration for the rational design of 2D/0D/2D heterojunction photocatalyst for green energy generation and environmental remediation applications.


Assuntos
Compostos de Cádmio , Nanocompostos , Pontos Quânticos , Compostos de Estanho , Pontos Quânticos/química , Compostos de Cádmio/química , Compostos de Estanho/química , Nanocompostos/química , Catálise , Sulfetos/química , Luz Solar , Processos Fotoquímicos , Grafite/química , Compostos Azo/química , Nitrilas/química , Compostos de Nitrogênio/química
16.
Environ Res ; 252(Pt 4): 119121, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38734291

RESUMO

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 µA mM-1 cm-2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed.


Assuntos
Carcinógenos , Ouro , Grafite , Nanopartículas Metálicas , Poluentes Químicos da Água , Ouro/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/química , Nanopartículas Metálicas/química , Grafite/química , Carcinógenos/análise , Atrazina/análise , Atrazina/química , Enxofre/química , Enxofre/análise , Técnicas Eletroquímicas/métodos , Hidrazinas/análise , Hidrazinas/química , Compostos de Nitrogênio/química , Compostos de Nitrogênio/análise , Nitrilas/química , Nitrilas/análise , Monitoramento Ambiental/métodos
17.
Environ Res ; 252(Pt 2): 118886, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38583659

RESUMO

In photo-Fenton technology, the narrower pH range limits its practical application for antibiotic wastewater remediation. Therefore, in this study, a Z-scheme heterojunction photo-Fenton catalyst was constructed by Fe-doped graphite-phase carbon nitride in combination with bismuth molybdate for the degradation of typical antibiotics. Fe doping can shorten the band gap and increase visible-light absorption. Simultaneously, the constructed Z-scheme heterojunction provides a better charge transfer pathway for the photo-Fenton reaction. Within 30 min, Fe3CN/BMO-3 removed 95.54% of tetracycline hydrochloride (TC), and its remarkable performance was the higher Fe3+/Fe2+ conversion efficiency through the decomposition of H2O2. The Fe3CN/BMO-3 catalyst showed remarkable photo-Fenton degradation performance in a wide pH range (3.0-11.0), and it also had good stability in the treatment of TC wastewater. Furthermore, the order of action of the active species was h+ > ·O2- > 1O2 > ·OH, and the toxicity assessment suggested that Fe3CN/BMO-3 was effective in reducing the biotoxicity of TC. The catalyst proved to be an economically feasible and applicable material for antibiotic photo-Fenton degradation, and this study provides another perspective on the application of elemental doping and constructed heterojunction photo-Fenton technology for antibiotic water environmental remediation.


Assuntos
Antibacterianos , Bismuto , Peróxido de Hidrogênio , Ferro , Molibdênio , Poluentes Químicos da Água , Bismuto/química , Antibacterianos/química , Antibacterianos/toxicidade , Concentração de Íons de Hidrogênio , Ferro/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/toxicidade , Peróxido de Hidrogênio/química , Molibdênio/química , Catálise , Grafite/química , Grafite/toxicidade , Compostos de Nitrogênio/química , Compostos de Nitrogênio/toxicidade , Nitrilas/química , Nitrilas/toxicidade , Águas Residuárias/química
18.
Ecotoxicol Environ Saf ; 282: 116701, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-39018731

RESUMO

Herein, we reported the dual functions of molybdenum disulfide/sulfur-doped graphitic carbon nitride (MoS2/SGCN) composite as a sensing material for electrochemical detection of 4-NP and a catalyst for 4-NP degradation. The MoS2 nanosheet, sulfur-doped graphitic carbon nitride (SGCN) and MoS2/SGCN were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of these materials with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 mM K4[Fe(CN)6]3-/4- show that the composite has the lowest charge transfer resistance and the best electrocatalytic activity. The limit of detection (LOD) and the linear range of 4-nitrophenol at MoS2/SGCN modified glassy carbon electrode (MoS2/SGCN/GCE) were computed as 12.8 nM and 0.1 - 2.6 µM, respectively. Also, the percentage recoveries of 4-NP in spiked tap water samples ranged from 97.8 - 99.1 %. The electroanalysis of 4-NP in the presence of notable interferons shows that the proposed electrochemical sensor features outstanding selectivity toward 4-NP. Additionally, the results of the catalytic degradation of 4-NP at MoS2/SGCN show that the nanocatalyst catalyzed the transformation of 4-NP to 4-aminophenol (4-AP) with a first-order rate constant (k) estimated to be 4.2 ×10-2 s-1. The results of this study confirm that the MoS2/SGCN nanocatalyst is a useful implement for electroanalytical monitoring and catalytic degradation of the hazardous 4-NP in water samples.


Assuntos
Dissulfetos , Técnicas Eletroquímicas , Grafite , Limite de Detecção , Molibdênio , Nitrofenóis , Poluentes Químicos da Água , Molibdênio/química , Molibdênio/análise , Nitrofenóis/análise , Nitrofenóis/química , Técnicas Eletroquímicas/métodos , Dissulfetos/química , Catálise , Poluentes Químicos da Água/análise , Grafite/química , Compostos de Nitrogênio/química , Compostos de Nitrogênio/análise , Eletrodos
19.
Luminescence ; 39(9): e4873, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39192766

RESUMO

In this study, we present the development and analysis of electrochemical sensors utilizing graphitic carbon nitride copper-tungsten nanoparticles (g-C3N4 @Cu-W Nps) capped with various cationic surfactants of differing chain lengths and counter ions. The fabricated nanoparticles underwent thorough characterization to assess their morphological, structural, and compositional attributes, revealing their uniformity, spherical morphology, and monoclinic crystal phases. Subsequently, these nanoparticles were employed in the fabrication of electrochemical sensors for hydrazine detection. A comprehensive comparison of the electrochemical responses, evaluated via cyclic voltammetry, was conducted between sensors utilizing bare nanoparticles and those capped with surfactants.


Assuntos
Cobre , Dopamina , Técnicas Eletroquímicas , Grafite , Nanopartículas Metálicas , Cobre/química , Dopamina/análise , Dopamina/química , Nanopartículas Metálicas/química , Grafite/química , Compostos de Nitrogênio/química , Hidrazinas/química , Tamanho da Partícula
20.
Mikrochim Acta ; 191(7): 411, 2024 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-38900245

RESUMO

Ratiometric fluorescence and colorimetric strategies for detecting activity of butyrylcholinesterase (BChE) in human serum were developed by using g-C3N4 nanosheets, silver ion (Ag+) and o-phenylenediamine (OPD) as chromogenic agents. The oxidation-reduction reaction of OPD and Ag+ generates 2,3-diaminophenazine (oxOPD). Under exciation at 370 nm, g-C3N4 nanosheets and oxOPD emit fluorescence at 440 nm (F440) and 560 nm (F560), respectively. Additionally, oxOPD exhibits quenching ability towards g-C3N4 nanosheets via photoinduced electron transfer (PET) process. Thiocholine (TCh), as a product of BChE-catalyzed hydrolysis reaction of butylthiocholine iodide (BTCh), can coordinate with Ag+ intensively, and consequently diminish the amount of free Ag+ in the testing system. Less amount of free Ag+ leads to less production of oxOPD, resulting in less fluorescence quenching towards g-C3N4 nanosheets as well as less fluorescence emission of oxOPD. Therefore, by using g-C3N4 nanosheets and oxOPD as fluorescence indicators, the intensity ratio of their fluorescence (F440/F560) was calculated and employed to evaluate the activity of BChE. Similarly, the color variation of oxOPD indicated by the absorbance at 420 nm (ΔA420) was monitored for the same purpose. These strategies were validated to be sensitive and selective for detecting BChE activity in human serum, with limits of detection (LODs) of 0.1 U L-1 for ratiometric fluorescence mode and 0.7 U L-1 for colorimetric mode.


Assuntos
Butirilcolinesterase , Colorimetria , Nanoestruturas , Fenilenodiaminas , Prata , Espectrometria de Fluorescência , Humanos , Colorimetria/métodos , Prata/química , Fenilenodiaminas/química , Butirilcolinesterase/sangue , Butirilcolinesterase/química , Espectrometria de Fluorescência/métodos , Nanoestruturas/química , Compostos de Nitrogênio/química , Limite de Detecção , Nitrilas/química , Grafite , Fenazinas
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