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The construction of semiconductor heterojunction is an effective way for charge separation in photocatalytic degradation of pollutants. In this study, a novel MoS2@MoO3/(Cu+/g-C3N4) ternary composites (MMCCN) was prepared via a simple calcination method. The as-prepared composites exhibited exceptional performance in activating peroxymonosulfate (PMS) for the degradation of rhodamine B (RhB). The activity testing results indicated that 99.41 % of RhB (10 mg·L-1, 10 mL) was effectively removed by the synergistic effect of composites photocatalyst (0.1 g·L-1) and PMS (0.1 g·L-1) under visible light irradiation for 40 min. Its reaction rate constant exceeded that of Cu+/g-C3N4, MoO3 and MoS2 by a factor of 3.56, 17.30 and 11.73 times, respectively. The crystal structure, band gap and density of states (DOS) of the semiconductors were calculated according to the density functional theory (DFT). Free radical trapping tests and electron spin resonance spectroscopy validated that 1O2, O2- and h+ are primary reactive species participating in the decomposition of RhB. The ternary composites demonstrated good stability and maintained excellent degradation efficiency even across four reaction cycles. Furthermore, the activation mechanism and the intermediates produced during the decomposition course of RhB by MMCCN/PMS/vis system were analyzed and elucidated. A double S-scheme heterojunctions was responsible for efficient separation of photo-induced electron-hole pairs. This work presents a novel method in the construction of double S-scheme heterojunctions for PMS activation which is expected to find wide applications in wastewater treatment and environmental remediation.
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Poly(butylene succinate-co-furandicarboxylate) (PBSF) and poly(butylene adipate-co-furandicarboxylate) (PBAF) are novel furandicarboxylic acid-based biodegradable copolyesters with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene succinate-co-terephthalate) (PBST) and poly(butylene adipate-co-terephthalate) (PBAT). In this study, quantum chemistry techniques after molecular dynamics simulations are employed to investigate the degradation mechanism of PBSF and PBAF catalyzed by Candida antarctica lipase B (CALB). Computational analysis indicates that the catalytic reaction follows a four-step mechanism resembling the ping-pong bibi mechanism, with the initial two steps being acylation reactions and the subsequent two being hydrolysis reactions. Notably, the first step of the hydrolysis is identified as the rate-determining step. Moreover, by introducing single-point mutations to expand the substrate entrance tunnel, the catalytic distance of the first acylation step decreases. Additionally, energy barrier of the rate-determining step is decreased in the PBSF system by site-directed mutations on key residues increasing hydrophobicity of the enzyme's active site. This study unprecedently show the substrate binding pocket and hydrophobicity of the enzyme's active site have the potential to be engineered to enhance the degradation of copolyesters catalyzed by CALB.
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Proteínas Fúngicas , Lipase , Poliésteres , Lipase/metabolismo , Lipase/química , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/química , Poliésteres/química , Poliésteres/metabolismo , Biodegradação Ambiental , Simulação de Dinâmica Molecular , Hidrólise , Modelos QuímicosRESUMO
2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV328) is a commonly used benzotriazole ultraviolet stabilizers (BUVs) with bioaccumulative properties. Since it's stubbornly degraded in the environment, it poses significant environmental risks in soil. However, the removal of UV328 from soil is challenging, and existing treatment methods have low efficiency. This study focuses on UV328 in soil and proposes an efficient method for its removal using persulfate (PS) activated by iron sulfide (FeS). The research demonstrates that with FeS and PS dosages of 20 and 100 mM respectively, and a soil-to-water ratio of 5:1, 12 h-removal efficiency of UV328 with an initial concentration of 12 mg/kg reaches 93.0%. Furthermore, employing electron paramagnetic resonance spectroscopy and quenching experiments, key reactive oxygen species (ROSs) are identified. SO4â¢-, â¢OH, 1O2 and â¢O2- contribute 31.76%, 28.77%, 26.52% and 12.95%, respectively. Four main reaction pathways of amination, hydroxylation, sulfate substitution, and bond cleavage, are identified with 14 transformation products characterized. Calculated energy profiles based on density functional theory (DFT) identify the most susceptible reaction sites for different ROSs. Five different types of agricultural soils were selected to explore the impact of soil characteristics on UV328 removal. The degradation performance of natural mackinawite demonstrates the effectiveness and accessibility of raw materials. Toxicity assessments of transformation products confirm the environmental friendliness of this system. This study proposes an efficient degradation method for UV328-contaminated soil, providing scientific insights and theoretical guidance for addressing environmental removal of BUVs from soil.
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High valent metal species, including Mn(III), Fe(IV) and Cu(III), have been identified as key intermediates in the degradation of pollutants in many advanced oxidation processes. However, unlike Mn(III) and Fe(IV), the current exploration of the reaction activity and selective oxidation mechanism of Cu(III) towards pollutants with different structures is still quite limited. Herein, the copper(III) periodate was synthesized to investigate the reactivity towards six sulfonamide antibiotics (SAs) including typical two pentacyclic structures (sulfamethoxazole (SMX) and sulfathiazole (STZ)) and four hexacyclic structures (sulfadiazine (SDZ), sulfamerazine (SMR), sulfamonomethoxine (SMM) and sulfapyridine (SPD)). The results indicated that all SAs almost completely removed by Cu(III) system after 10 min with the molar ratio of approximately 3:1 (Cu(III):SAs) and Cu(III) direct oxidation played the most important role. SAs with 6-ring substituents were more readily degraded by Cu(III) than SAs with 5-ring substituents, and the presence of electron-rich group such as -CH3 and -S in ring substituent increased the reactivity towards Cu(III). The introduction of coexisting anions (Cl-, SO42- and HCO3-) hardly affected the degradation of SAs by Cu(III) oxidation, while the addition of HA to some extent inhibited SAs degradation. The solution pH greatly affected the degradation of SAs by Cu(III) and the removal efficiencies of SAs roughly followed the rule of neutral > acidic > alkaline. The degradation mechanism of SAs with 5-ring and 6-ring substituents in Cu(III) system mainly included amino nitration, self-coupling, hydroxylation, S-N cleavage in SAs with 5-ring substituents and SO2 extrusion in SAs with 6-ring substituents. Although the real water matrix inhibited the degradation of SAs to varying degrees, Cu(III) still played a satisfactory performance on SAs degradation especially for electron-rich structure.
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Co-contamination of ciprofloxacin (CIP) and Cu(II) is common in marine aquaculture water. However, the transmission and transformation of these substances in natural water matrices are often overlooked. This study sought to assess the impact of Cu(II) on CIP degradation in distilled (DI) and simulated (SI) mariculture water, as well as to develop a relationship between Cu(II), CIP, and its degradation products. First, complexation assays and analog computations revealed that Cu (II) forms complexes by binding to the oxygen atoms of the carbonyl (C=O) and carboxyl (COOH) groups in the CIP molecule. Second, photodegradation experiments showed that Cu(II) significantly hindered the degradation effect of CIP in DI water, while Cu(II) did not significantly hinder the degradation of CIP in SI water. Furthermore, the effect of Cu(II) on the degradation mechanism of CIP was determined by combining quenching and EPR experiments, Materials Studio software calculations, and UPLC-MS results. It was demonstrated that Cu(II) enhanced the production of singlet oxygen (1O2), hydroxyl radicals (â¢OH), and superoxide radicals (â¢O2-) in DI water. In the presence of Cu(II), CIP undergoes hydroxylation and decarbonylation reactions, forming hydroxylated and nitroxylated products. Additionally, direct defluorination and cleavage of the piperazine ring occur, followed by complexation reactions with Cu(II). However, in SI water, the production of 1O2 depends on the indirect action of Cu(II) and the excited state transformation of organic matter. Experimental evidence has shown that CIP can create intermediate compounds that include O-O peroxide rings, with or without the presence of Cu(II). When Cu(II) is present, the cyclopropyl group of the CIP molecule is more prone to transformation and so degradation. Finally, the toxicity assessment results indicated that both Cu(II) and SI water increased the toxicity of the degradation products.
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Non-steroidal anti-inflammatory drugs (NSAIDs) are widespread pollutants in aquatic environments, posing significant risks to both ecosystems and human health due to their persistence and bioaccumulation. Effective and sustainable degradation methods are urgently required to address this environmental challenge. This study aims to design and optimize a cytochrome P450BM3-based biocatalyst for the rapid and efficient degradation of NSAIDs by direct chemical intervention and protein engineering. The novel biocatalyst achieved efficient biodegradation of four common NSAIDs. Notably, the F87I/T268D mutant achieved 99.22 % degradation of diclofenac (DCF) within 10 min, and degraded meloxicam (MEL) and phenylbutazone (PBZ) at rates of 98.86 % and 90.51 % within 5 min, respectively. Furthermore, the F87G mutant accomplished 99.08 % degradation of acetaminophen (APAP) within just 2 min. The catalytic properties of P450BM3 and its mutants were evaluated through kinetic studies, and potential degradation pathways of the four NSAIDs were proposed in conjunction with UPLC-MS. This study provides a novel biocatalytic approach for the rapid degradation of NSAIDs in aquatic systems, offering considerable environmental benefits for pollution mitigation.
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Cathode prelithium agent is regarded as the most applicable approach to compensate the initial capacity loss in lithium ion batteries (LIBs). Li2NiO2 (LNO) has attracted numerous attention due to its superior environmental stability and reliable synthesis approach. To promote the commercial application of LNO, the understanding of the degradation mechanism induced by air-exposure and finding reliable strategies to improve the air stability are necessary. Herein, by preserving the LNO in different environments (relative humidity of 70% and 40%), the surface chemistry evolution of LNO is subtly investigated, which shows Li2CO3 and LiOH cover the surface of the LNO, which decline the Li+ diffusion kinetics as well as the charge capacity. What's more, the slurry turns gel when the LNO exposed to the environment of 70% relative humidity for 2 days and 40% relative humidity for 5 days. Facile approaches, including washing the deteriorative LNO with ethanol, reacting the alkali components with H3BO3, and coating the LNO with Al2O3 are conducted to recover the disabled LNO, which retains 84.2% of initial capacity. In addition, a coating approach is proposed for the fresh LNO to effectively improve the air stability. This work provides guideline to the commercial application of the LNO.
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In this study, vacuum ultraviolet (VUV) was first proposed to activate ferrate (Fe(VI)) for degrading micropollutants (e.g., carbamazepine (CBZ)). Results indicated that VUV/Fe(VI) could significantly facilitate the CBZ degradation, and the removal efficiencies of VUV/Fe(VI) were 30.9-83.4% higher than those of Fe(VI) at pH = 7.0-9.0. Correspondingly, the degradation rate constants of VUV/Fe(VI) were 2.3-36.0-fold faster than those of Fe(VI). Free radical quenching and probe experiments revealed that the dominant active species of VUV/Fe(VI) were â¢OH and Fe(V)/Fe(IV), whose contribution ratios were 43.3 to 48.6% and 48.2 to 46.6%, respectively, at pH = 7.0-9.0. VUV combined with Fe(VI) not only effectively mitigated the weak oxidizing ability of Fe(VI) under alkaline conditions (especially pH = 9.0) but also attenuated the deteriorating effect of background constituents on Fe(VI). In different real waters (tap water, river water, WWTPs effluent), VUV/Fe(VI) retained a remarkably enhanced effect on CBZ degradation compared to Fe(VI). Moreover, VUV/Fe(VI) exhibited outstanding performance in the debasement of CBZ and sulfamethoxazole (SMX), as well as six other micropollutants, displaying broad-spectrum capability in degrading micropollutants. Overall, this study developed a novel oxidation process that was efficient and energy-saving for the rapid removal of micropollutants.
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In salt lake areas, the cast-in-situ concrete structure has been corroded by the combination of sulfate and chloride for a long time. The incorporation of basalt fiber materials into concrete helps to improve the durability of concrete. In this paper, experiments were conducted to study the corrosion deterioration mechanisms of basalt fiber-reinforced cast-in-situ concrete under sulfate, chloride, and combined attack. The appearance, size, mass, flexural, and compressive strength of specimens were investigated during the immersion period to determine the changes in the physical and mechanical properties of specimens. Moreover, the microstructure and mineral changes of specimens during the immersion period were observed by Scanning Electron Microscope (SEM), Energy Dispersive Spectrometer (EDS), X-ray diffraction (XRD), and Thermogravimetric (TG)/ Derivative Thermogravimetric (DTG) analyses. Results show that premixed chloride has a significant detrimental influence on the strength development of cast-in-situ concrete, with concrete powder spalling occurring on the surface of the specimen. Severe corrosion degradation of specimens occurs under the external sulfate and internal chloride combined attack, resulting in lower flexural and compressive strength. The compressive strength and flexural strength of the corroded specimens decreased by 15.4% and 24.8%, respectively, compared with the control group at 28 days. Moreover, premixed basalt fiber has a beneficial influence on cast-in-situ concrete. When the basalt fiber content is 0.5%, the flexural strength of the specimen is increased by 16.2%. The filling and bridging effect of basalt fiber alleviates the negative effects caused by corrosion. In addition, increasing fiber content is beneficial for enhancing its effectiveness when the fiber content is less than 0.5%. This paper provides a valuable reference for the application of basalt fiber-reinforced cast-in-situ concrete under the condition of sulfate-chloride compound corrosion.
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The enantioselective mechanism of the esterase QeH against the two enantiomers of quizalofop-ethyl (QE) has been primitively studied using computational and experimental approaches. However, it is still unclear how the esterase QeH adjusts its conformation to adapt to substrate binding and promote enzyme-substrate interactions in the catalytic kinetics. The equilibrium processes of enzyme-substrate interactions and catalytic dynamics were reproduced by performing independent molecular dynamics (MD) runs on the QeH-(R)/(S)-QE complexes with a newly developed residue-specific force field (RSFF2C). Our results indicated that the benzene ring of the (R)-QE structure can simultaneously form anion-π and cation-π interactions with the side-chain group of Glu328 and Arg384 in the binding cavity of the QeH-(R)-QE complex, resulting in (R)-QE being closer to its catalytic triplet system (Ser78-Lys81-Tyr189) with the distances measured for the hydroxyl oxygen atom of the catalytic Ser78 of QeH and the carbonyl carbon atom of (R)-QE of 7.39 Å, compared to the 8.87 Å for (S)-QE, whereas the (S)-QE structure can only form an anion-π interaction with the side chain of Glu328 in the QeH-(S)-QE complex, being less close to its catalytic site. The computational alanine scanning mutation (CAS) calculations further demonstrated that the π-π stacking interaction between the indole ring of Trp351 and the benzene ring of (R)/(S)-QE contributed a lot to the binding stability of the enzyme-substrate (QeH-(R)/(S)-QE). These results facilitate the understanding of their catalytic processes and provide new theoretical guidance for the directional design of other key enzymes for the initial degradation of aryloxyphenoxypropionate (AOPP) herbicides with higher catalytic efficiencies.
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Esterases , Simulação de Dinâmica Molecular , Esterases/química , Esterases/metabolismo , Estereoisomerismo , Especificidade por Substrato , Domínio Catalítico , CinéticaRESUMO
Microplastics (MPs) in the aquatic environment are difficult to degrade naturally due to their hydrophobicity and structure. A variety of engineered degradation methods were developed to treat MPs contamination in the aquatic environment. Current reviews of MPs degradation methods only provided an inventory but lacked systematic comparisons and application recommendations. However, selecting suitable degradation methods for different types of MPs contamination may be more effective. This work examined the present engineered degradation methods for MPs in the aquatic environment. They were categorized into chemical degradation, biodegradation, thermal degradation and photodegradation. These degradation methods were systematically summarized in terms of degradation efficiency, technical limitations and production of environmental hazards. Also, the potential influences of different environmental factors and media on degradation were analyzed, and the selection of degradation methods were suggested from the perspectives of contamination types and degradation mechanisms. Finally, the development trend and challenges for studying MPs engineered degradation were proposed. This work will contribute to a better selection of customized degradation methods for different types of MPs contamination scenarios in aquatic environments.
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Loxoprofen has been widely used as a non-steroidal anti-inflammatory drug globally and it can also persist in the environment. Although it is known to be a non-toxic drug, its presence may still pose a potential risk to organisms in the environment. Here, the hyper lignin-degrading fungus Phanerochaete sordida YK-624 was used to study the degradation of loxoprofen. This fungus showed excellent loxoprofen biodegradation ability with 90.4% and 93.4% after one day of incubation at lower concentrations of 0.01 and 0.005 mM, respectively. And at a higher concentration of 0.1 mM, a significant removal of 94.2% was also observed after 10 days of incubation. In this study, four metabolites were isolated and determined by HR-ESI-MS and NMR. Furthermore, LC/MS analysis suggested the presence of intermediate hydroxy loxoprofen. In addition, loxoprofen-OH was also identified as a metabolite of loxoprofen through comparison with the synthesized compounds. In this metabolism of loxoprofen, cytochrome P450 may play a significant role. Interestingly, P. sordida YK-624 showed enantioselectivity in the degradation process of loxoprofen. By these results, three degradation pathways of loxoprofen by P. sordida YK-624 were hypothesized. To the best of our knowledge, this is the first report describing the potential degradation mechanisms of loxoprofen by a white-rot fungus.
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Anti-Inflamatórios não Esteroides , Biodegradação Ambiental , Lignina , Phanerochaete , Fenilpropionatos , Fenilpropionatos/metabolismo , Anti-Inflamatórios não Esteroides/metabolismo , Phanerochaete/metabolismo , Lignina/metabolismoRESUMO
Domoic acid (DA) is a compound generated as a secondary metabolite during harmful algal blooms, has historically received attention as the potent neurotoxicity in marine environment. However, the aerobic degradation mechanism of DA and the DA-degrader remain largely unknown. Here, we revealed the mechanism of aerobic degradation of DA by a ubiquitous marine Pseudoalteromonas sp., and more importantly, we confirmed that the degradation of DA is mediated by biogenic reactive oxygen species (ROS), rather than direct enzyme-mediated as traditionally conceived. Results indicated that DA degradation was caused by biogenic O2- and OH, where DA underwent reactions of decarboxylation, hydroxylation, and oxidation to yield the detoxification terminal product. Besides, whole genome sequencing and RT-qPCR analysis revealed that the genes conferring to encoding leucine dehydrogenase (ldh) and Na+-translocated NADH-quinone oxidoreductase (nqrA, nqrF) are responsible for biogenic ROS production. Finally, we found through comparative proteomic analysis that biogenic ROS mediated the DA degradation may be prevalent in the environment. Overall, this work not only reveals aerobic biotransformation mechanism of DA, but also identifies a novel mechanism of DA degradation, which provides new perspective into the environmental fate of DA and the artificial bioremediation of DA.
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Ácido Caínico , Toxinas Marinhas , Espécies Reativas de Oxigênio , Toxinas Marinhas/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Ácido Caínico/análogos & derivados , Ácido Caínico/metabolismo , Biodegradação Ambiental , Pseudoalteromonas/metabolismo , Pseudoalteromonas/genética , Poluentes Químicos da Água/metabolismoRESUMO
2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV328) is an emerging persistent organic pollutant ubiquitously found in environmental matrices. Though some advanced oxidation processes have been tested to degrade UV328 in waste streams, the degradation mechanisms are largely unknown. In this study, the degradation of UV328 by ozone (O3) and peroxymonosulfate (PMS) was systemically investigated. At neutral pH, 97.0% UV328 was removed in 5 min with 6.4 mg/min O3 and 2 mM PMS, and the degradation rate was positively correlated with the concentration of oxidants. Hydroxyl radical (â¢OH), sulfate radical (SO4â¢-) and singlet oxygen (1O2) participated in the degradation of UV328, in which 1O2 played a key role. Based on the identified transformation intermediates and density functional theory simulations, three degradation pathways of dehydrogenation, cycloaddition and hydroxylation were proposed. â¢OH and SO4â¢- radicals could attack UV328 through hydrogen atom abstraction channel. 1O2-mediated cycloaddition reaction is favorable, and â¢OH could react with UV328 via radical adduct formation pathway. Toxicity assessment indicated that O3/PMS treatment mitigated the ecological risks of UV328.
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Radical Hidroxila , Oxirredução , Ozônio , Peróxidos , Poluentes Químicos da Água , Ozônio/química , Peróxidos/química , Poluentes Químicos da Água/química , Radical Hidroxila/química , Oxigênio Singlete/química , Fenóis/químicaRESUMO
Antibiotics with pseudo-persistence in water have been regarded as emerging pollutants, which have obvious biological toxicity even at trace levels. On account of high reactivity, heterogeneous catalytic ozonation has been widely applied to remove antibiotics. Among the heterogeneous catalysts, with well-developed pores and regulable surface defects, carbon-based materials can act as both adsorbents and catalysts. Metal cations, surface hydroxyl (-OH) groups and oxygen vacancies (OVs) serve as primary active sites in metal oxides. However, composites (perovskite, apatite, etc.) with special crystalline structure have more crystallographic planes and abundant active sites. The unsaturated bonds and aromatic rings which have dense structure of the electron cloud are more likely to be attacked by ozone (O3) directly. Sulfonamides (SAs) can be oxidized by O3 directly within a short time due to the structure of activated aromatic rings and double bonds. With the existence of catalysts, almost all antibiotics can attain fair removal effects. The presence of water matrix can greatly influence the removal rate of pollutants via changing the surface properties of catalysts, competing active sites with O3, etc. Correspondingly, the application of diverse heterogeneous catalysts was introduced in details, based on modification including metal/non-metal doping, surface modification and carrier composite. The degradation pathways of SAs, fluoroquinolones (FQNs), tetracyclines (TCs) and ß-lactams were summarized founded on the functional group structures. Furthermore, the effects of water matrix (pH, coexisting ions, organics) for catalytic ozonation were also debated. It is expected to proffer advanced guidance for researchers in catalytic ozonation of antibiotics.
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Mining industries have long relied on cyanidation as the primary method for gold extraction, but this process generates thiocyanates as a problematic byproduct, posing challenges for wastewater treatment and recycling. The stability of thiocyanates makes their reduction or elimination in mining wastewater difficult. In this study, a p-n heterojunction of ZnO and BiOI was created and evaluated for its ability to photodegrade thiocyanate ions under simulated solar conditions. Various analytical techniques revealed a highly porous structure with a sponge-like morphology and agglomeration in the synthesized heterojunction. The compound exhibited crystalline patterns without impurity peaks, a slight red shift in absorbance, and Type IV isotherm adsorption. The synthesized heterostructure achieved the complete destruction of thiocyanate ions in less than 30 min. The investigation of different process parameters indicated that the destruction of the contaminant by the heterostructure was influenced by the initial thiocyanate concentration, which decreased as the thiocyanate concentration increased. The peak photodestruction reaction was observed at pH 7. By applying a pseudo-first-order kinetic model, it was found that increasing the catalyst mass to 15 mg raised the rate constant from 0.188 to 0.420 min-1, while increasing the pH to 10 led to a 3.5-fold reduction. The strong correlation between the observed data and the predicted values of the pseudo-first-order kinetic model was indicated by the observed (R2) values. The findings of this study hold potential significance for mining industries, as it offers a potential solution for eliminating cyanide and thiocyanates from mining wastewater. The elimination of thiocyanate generation in the cyanidation process is crucial for mining companies, making this study valuable for the industry.
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Since enormous amounts of antibiotics are consumed daily by millions of patients all over the world, tons of pharmaceutical residuals reach aquatic bodies. Accordingly, our study adopted the Fenton catalytic degradation approach to conquer such detrimental pollutants. (Ce0.33Fe) MIL-88A was fabricated by the hydrothermal method; then, it was supported on the surface of g-C3N4 sheets using the post-synthetic approach to yield a heterogeneous Fenton-like (Ce0.33Fe) MIL-88A/10%g-C3N4 catalyst for degrading the tetracycline hydrochloride drug. The physicochemical characteristics of the catalyst were analyzed using FT-IR, SEM-EDX, XRD, BET, SEM, and XPS. The pH level, the H2O2 concentration, the reaction temperature, the catalyst dose, and the initial TC concentration were all examined as influencing factors of TC degradation efficiency. Approximately 92.44% of the TC was degraded within 100 min under optimal conditions: pH = 7, catalyst dosage = 0.01 g, H2O2 concentration = 100 mg/L, temperature = 25 °C, and TC concentration = 50 mg/L. It is noteworthy that the practical outcomes revealed how the Fenton-like process and adsorption work together. The degradation data were well-inspected by first-order and second-order models to define the reaction rate. The synergistic interaction between the (Ce0.33Fe) MIL-88A/10%g-C3N4 components produces a continuous redox cycle of two active metal species and the electron-rich source of g-C3N4. The quenching test demonstrates that â¢OH is the primary active species for degrading TC in the H2O2-(Ce0.33Fe) MIL-88A/10%g-C3N4 system. The GC-MS spectrum elucidates the yielded intermediates from degrading the TC molecules.
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Polyanionic A3V2(PO4)3 (A = Li+, Na+) with open channels have been extensively utilized as cathode materials for aqueous zinc-metal batteries (AZMBs), whereas suffering from severe capacity fading and rapid operation voltage decay during cycling. when used as In this work, it is disclosed that the rapid degradation is induced by an irreversible phase change from electrochemical active Li3V2(PO4)3 to nonactive monoclinic LiZnPO4, as well as active Na3V2(PO4)3 to nonactive rhombic Zn3(PO4)2(H2O)4. Subsequently, a rational dual-cation (Al-Fe) doping strategy is proposed to suppress these detrimental transformations. Such dual-cation doping entails stronger P-O and V-O bonds, thus stabilizing the initial polyanionic structures. Consequently, the optimized member of Li3V1.775Al0.075Fe0.225(PO4)3 (LVAFP) exhibits desirable cycling stability (1000 cycles, 68.5% capacity retention) and notable rate capability (92.1% of the initial capacity at 10 C). Moreover, the dual-cation doping methodology is successfully extended to improve the stability of Na3V2(PO4)3 cathode in aqueous dual-ion batteries, signifying the versatility and feasibility of this strategy. The comprehensive identification of local structural evolution in these polyanions will broaden the scope of designing high-performance alkali-vanadyl-phosphates for multivalent aqueous batteries.
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To recycle the nutrients in spiramycin (SPM) fermentation residue (SFR) through biological methods, acid hydrothermal treatment (AHT) was employed as pretreatment to enhance SFR biodegradability. The results showed that the degradation rate of residual SPM in SFR reached 100% after 120 min at 100â and 0.30 M acid with a 30.5% and 89.7% increase in proteins and polysaccharides, respectively. The SPM degradation was faster at higher acidity and temperature. However, elevated SPM concentration and the presence of protein, humic acid, and polysaccharide inhibited SPM degradation. The disintegration of SFR was evidenced by changes in its microstructure and could be predicted through the release of dissolved organic matter. Eight major SPM intermediates were identified with lower mutagenicity and antibacterial activity testing against Staphylococcus aureus. These results demonstrate that AHT not only disintegrates SFR but also degrades the residual SPM antibiotics, which implies the possibility for practical applications.
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Antibacterianos , Fermentação , Espiramicina , Antibacterianos/farmacologia , Antibacterianos/química , Espiramicina/farmacologia , Espiramicina/química , Staphylococcus aureus/efeitos dos fármacos , Temperatura , Água/química , Concentração de Íons de Hidrogênio , Ácidos/química , Biodegradação AmbientalRESUMO
This study presents a pioneering synthesis of a direct Z-scheme Y2TmSbO7/GdYBiNbO7 heterojunction photocatalyst (YGHP) using an ultrasound-assisted hydrothermal synthesis technique. Additionally, novel photocatalytic nanomaterials, namely Y2TmSbO7 and GdYBiNbO7, were fabricated via the hydrothermal fabrication technique. A comprehensive range of characterization techniques, including X-ray diffractometry, Fourier-transform infrared spectroscopy, Raman spectroscopy, UV-visible spectrophotometry, X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray energy-dispersive spectroscopy, fluorescence spectroscopy, photocurrent testing, electrochemical impedance spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance, was employed to thoroughly investigate the morphological features, composition, chemical, optical, and photoelectric properties of the fabricated samples. The photocatalytic performance of YGHP was assessed in the degradation of the pesticide acetochlor (AC) and the mineralization of total organic carbon (TOC) under visible light exposure, demonstrating eximious removal efficiencies. Specifically, AC and TOC exhibited removal rates of 99.75% and 97.90%, respectively. Comparative analysis revealed that YGHP showcased significantly higher removal efficiencies for AC compared to the Y2TmSbO7, GdYBiNbO7, or N-doped TiO2 photocatalyst, with removal rates being 1.12 times, 1.21 times, or 3.07 times higher, respectively. Similarly, YGHP demonstrated substantially higher removal efficiencies for TOC than the aforementioned photocatalysts, with removal rates 1.15 times, 1.28 times, or 3.51 times higher, respectively. These improvements could be attributed to the Z-scheme charge transfer configuration, which preserved the preferable redox capacities of Y2TmSbO7 and GdYBiNbO7. Furthermore, the stability and durability of YGHP were confirmed, affirming its potential for practical applications. Trapping experiments and electron spin resonance analyses identified active species generated by YGHP, namely â¢OH, â¢O2-, and h+, allowing for comprehensive analysis of the degradation mechanisms and pathways of AC. Overall, this investigation advances the development of efficient Z-scheme heterostructural materials and provides valuable insights into formulating sustainable remediation strategies for combatting AC contamination.