Уточнить поиск
Результаты 1-10 из 78
Strategies for improving the catalytic activity of metal-organic frameworks and derivatives in SR-AOPs: Facing emerging environmental pollutants
2022
Jiang, Danni | Fang, Di | Zhou, Yu | Wang, Zhiwei | Yang, Zihao | Zhu, Jian | Liu, Zhiming
As persulfate activator, Metal organic frameworks (MOFs) and derivatives are widely concerned in degradation of emerging environmental pollutants by advanced oxygen technology dominated by sulfate radical (▪) (SR-AOPs). However, the poor stability and low catalytic efficiency limit the performance of MOFs, requiring multiple strategies to further enhance their catalytic activity. The aim of this paper is to improve the catalytic activity of MOFs and their derivatives by physical and chemical enhancement strategies. Physical enhancement strategies mainly refer to the activation strategies including thermal activation, microwave activation and photoactivation. However, the physical enhancement strategies need energy consumption and require high stability of MOFs. As a substitute, chemical enhancement strategies are more widely used and represented by optimization, modification, composites and derivatives. In addition, the identification of reactive oxygen species, active site and electron distribution are important for distinguishing radical and non-radical pathways. Finally, as a new wastewater treatment technology exploration of unknown areas in SR-AOPs could better promote the technology development.
Показать больше [+] Меньше [-]Dichlorodiphenyltrichloroethane metabolites inhibit DNMT1 activity which confers methylation-specific modulation of the sex determination pathway
2021
Hu, Junjie | Yang, Yan | Lv, Xiaomei | Lao, Zhilang | Yu, Lili
Dichlorodiphenyltrichloroethane (DDT) poses a significant health risk to humans which is associated with genomic DNA hypomethylation. However, the mechanism and biological consequences remain poorly understood. In vitro assays confirmed that the DDT metabolites 2,2-bis(p-chlorophenyl)-acetic acid (DDA) and 1-chloro-2,2-bis-(p-chlorophenyl)ethylene (DDMU), but not other DDT metabolites, significantly inhibited DNA methyltransferase 1 (DNMT1) activity, leading to genomic hypomethylation in cell culture assays. DNMT1 as a target for DNA hypomethylation induced by DDT metabolites was also confirmed using cell cultures in which DNMT1 was silenced or highly expressed. DDA and DDMU can modify methylation markers in the promoter regions of sexual development-related genes, and change the expression of Sox9 and Oct4 in embryonic stem cells. Molecular docking indicated that DDA and DDMU bound to DNMT1 with high binding affinity. Molecular dynamic simulation revealed that DDA and DDMU acted as allosteric modulators that reshaped the conformation of the catalytic domain of DNMT1. These findings provide a new insight into DDT-induced abnormalities in sexual development and demonstrate that selective binding to DNMT1 by DDA and DDMU can interfere with human DNMT1 activity and regulate the expression of the Sox9 and Oct4 genes.
Показать больше [+] Меньше [-]Biomaterial functionalized cerium nanocomposite for removal of fluoride using central composite design optimization study
2020
Nehra, Sapna | Raghav, Sapna | Kumar, Dinesh
Excess fluoride concentration in drinking water is a global issue, as this has an adverse effect on human health. Several adsorbents have been synthesized from natural raw material to remove fluoride from water. Reported adsorbents have some problems with the leaching of metal ions, fewer adsorption sites, and low adsorption capacity. Therefore, to address this, an effective biomaterial derived from the Luffa cylindrica (LC), containing many active sites, was integrated with a nano form of cerium oxide to form a robust, biocompatible, highly porous, and reusable LC–Ce adsorbent. This synthesized biosorbent offers better interaction between the active sites of LC–Ce and fluoride, resulting in higher adsorption capacity. Several factors, influence the adsorption process, were studied by a central composite design (CCD) model of statistical analysis. Langmuir’s and Freundlich’s models well describe the adsorption and kinetics governed by the pseudo–second–order model. The maximum monolayer adsorption capacity was found to be 212 and 52.63 mg/g for LC–Ce and LC, respectively determined by the Langmuir model. Detailed XPS and FTIR analyses revealed the underlying mechanism of fluoride adsorption via ion-exchange, electrostatic interaction, H–bonding, and ion-pair formation. All the results indicate that LC–Ce could serve as a suitable adsorbent for efficient fluoride removal (80–85%).
Показать больше [+] Меньше [-]Nanoporous bimetallic metal-organic framework (FeCo-BDC) as a novel catalyst for efficient removal of organic contaminants
2019
Li, Huanxuan | Zhang, Jian | Yao, Yuze | Miao, Xiangrui | Chen, Jiale | Tang, Junhong
In this work, we report on the synthesis and characterization of nanoporous bimetallic metal-organic frameworks (FeCo-BDC). Effects of synthesis time and temperature on the structures, morphology, and catalytic performance of FeCo-BDC were investigated. Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) were used to reveal the morphological and textural characteristics. The crystal structure and chemical composition of FeCo-BDC were determined by means of X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) measurements. Interestingly, FeCo-BDC grew into the same crystal structure with different morphology in the temperature of 110–150 °C with 12–48 h. The heterogeneous catalytic activity of FeCo-BDC was tested to activate peroxydisulfate (PDS) and peroxymonosulfate (PMS) for removal of methylene blue (MB). The results found that FeCo-BDC synthesized at 150 °C with 24 h exhibited the best catalytic performance for PMS and obtained 100% of MB removal within 15 min. The abundant unsaturated metal active sites of Fe(II) and Co(II) in the skeleton of FeCo-BDC made a great contribution to the generation of sulfate (▪) and hydroxyl radicals (OH), which resulted in the excellent performance for MB degradation.
Показать больше [+] Меньше [-]Electrocatalytical oxidation of arsenite by reduced graphene oxide via in-situ electrocatalytic generation of H2O2
2019
Li, Xuheng | Liu, Feng | Zhang, Weifang | Lü, Hongbo | Zhang, Jing
Preoxidation of As(III) to As(V) is required for the efficient removal of total arsenic in the treatment of wastewater. In this work, the electro-Fenton oxidation of As(III) with a high efficiency was successfully achieved by using the system of the stainless steel net (SSN) coating with reduced graphene oxide (RGO@SSN) as the cathode and stainless steel net (SSN) as the sacrificial anode. The RGO@SSN was synthesized by electrophoretic deposition-annealing method. The carbon disorder and defects of RGO resulted from the remained oxygen-containing functional groups facilitated the electrocatalytically active sites for two-electron oxygen reduction reaction (ORR). A high concentration (up to 1000 μmol/L) of H₂O₂ was in-situ produced through two-electron oxygen reduction reaction of electro-catalysis, and then served as the electro-Fenton reagent for the oxidation of As(III). HO generated by H₂O₂ participating the electro-Fenton reaction or decomposed at the surface of RGO@SSN cathode at acid condition endowed the strong oxidizing ability for As(III). The electro-Fenton equipped with RGO@SSN cathode has a promising application in the oxidation and removal of organic or inorganic pollutants in wastewater.
Показать больше [+] Меньше [-]17β-estradiol as precursors of Cl/Br-DBPs in the disinfection process of different water samples
2018
During chlorine disinfection process, reactions between the disinfectant and 17β-estradiol (E2) lead to the formation of halogenated disinfection byproducts (DBPs) which can be a risk to both ecosystem and human health. The degradation and transformation products of E2 in sodium hypochlorite (NaClO) disinfection processes of different water samples were investigated. The reaction kinetics research showed that the degradation rates of E2 were considerably dependent on the initial pH value and the types of water samples. In fresh water, synthetic marine aquaculture water and seawater, the reaction rate constant was 0.133 min−1, 2.067 min−1 and 2.592 min−1, respectively. The reasons for the above phenomena may be due to the different concentrations of bromide ions (Br−) in these three water samples which could promote the reaction between NaClO and E2. Furthermore, Br− could also cause the formation of brominated DBPs (Br-DBPs). The main DBPs, reaction centers and conceivable reaction pathways were explored. Seven halogenated DBPs have been observed including three chlorinated DBPs (Cl-DBPs) and four Br-DBPs. The active sites of E2 were found to be the pentabasic cyclic ring and the ortho position of the phenol moiety as well as C9-C10 position. The identified Cl/Br-DBPs were also confirmed in actual marine aquaculture water from a shrimp pond. The comparison of bio-concentration factors (BCF) values based on calculation of EPI-suite showed that the toxicities of the Br-DBPs were stronger than that of their chloride analogues. The absorbable organic halogens (AOX) analysis also suggested that the DBPs produced in the marine aquaculture water were more toxic than that in the fresh water system.
Показать больше [+] Меньше [-]Rational design of carbonaceous nanofiber/Ni-Al layered double hydroxide nanocomposites for high-efficiency removal of heavy metals from aqueous solutions
2018
Yu, Shujun | Liu, Yang | Ai, Yuejie | Wang, Xiangxue | Zhang, Rui | Chen, Zhongshan | Chen, Zhe | Zhao, Guixia | Wang, Xiangke
Heavy metal pollution of water sources has raised global environmental sustainability concerns, calling for the development of high-performance materials for effective pollution treatment. Herein, we report a facile approach to synthesize carbonaceous nanofiber/NiAl layered double hydroxide (CNF/LDH) nanocomposites for high-efficiency elimination of heavy metals from aqueous solutions. The CNF/LDH nanocomposites were characterized by three-dimensional architectures formed by the gradual self-assembly of flower-like LDH on CNF. The nanocomposites exhibited excellent hydrophilicity and high structural stability in aqueous solutions, guaranteeing the high availability of active sites in these environments. High-efficiency elimination of heavy metal ions by the CNF/LDH nanocomposites was demonstrated by the high uptake capacities of Cu(II) (219.6 mg/g) and Cr(VI) (341.2 mg/g). The sorption isotherms coincided with the Freundlich model, most likely because of the presence of heterogeneous binding sites. The dominant interaction mechanisms consisted of surface complexation and electrostatic interaction, as verified by a combination of X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy analyses and density functional theory calculations. The results presented herein confirm the importance of CNF/LDH nanocomposites as emerging and promising materials for the efficient removal of heavy metal ions and other environmental pollutants.
Показать больше [+] Меньше [-]Phase transformation-driven persulfate activation by coupled Fe/N–biochar for bisphenol a degradation: Pyrolysis temperature-dependent catalytic mechanisms and effect of water matrix components
2022
Wang, Yujiao | Wang, Li | Cao, Yuqing | Bai, Shanshan | Ma, Fang
Fe–N co-doped biochar is recently an emerging carbocatalyst for persulfate activation in situ chemical oxidation (ISCO). However, the involved catalytic mechanisms remain controversial and distinct effects of coexisting water components are still not very clear. Herein, we reported a novel N-doped biochar-coupled crystallized Fe phases composite (Fe@N-BC₈₀₀) as efficient and low-cost peroxydisulfate (PDS) activators to degrade bisphenol A (BPA), and the underlying influencing mechanism of coexisting inorganic anions (IA) and humic constituent. Due to the formation of graphitized nanosheets with high defects (AI index>0.5, ID/IG = 1.02), Fe@N-BC₈₀₀ exhibited 2.039, 5.536, 8.646, and 23.154-fold higher PDS catalytic activity than that of Fe@N-BC₆₀₀, Fe@N-BC₄₀₀, N-BC, BC. Unlike radical pathway driven by carbonyl group and pyrrolic N of low/mid-temperature Fe@N–BCs. The defective graphitized nanosheets and Fe-Nx acted separately as electron transfer and radical pathway active sites of Fe@N-BC₈₀₀, where π-π sorption assisted with pyrrolic N and pore-filling facilitated BPA degradation. The strong inhibitory effects of PO₄³⁻ and NO₂⁻ were ascribed to competitive adsorption of phosphate (61.11 mg g⁻¹) and nitrate (23.99 mg g⁻¹) on Fe@N-BC₈₀₀ via electrostatic attraction and hydrogen bonding. In contrast, HA competed for the pyrrolic-N site and hindered electron delivery. Moreover, BPA oxidation pathways initiated by secondary free radicals were proposed. The study facilitates a thorough understanding of the intrinsic properties of designed biochar and contributes new insights into the fate of degradation byproducts formed from ISCO treatment of micropollutants.
Показать больше [+] Меньше [-]Selective production of singlet oxygen from zinc-etching hierarchically porous biochar for sulfamethoxazole degradation
2021
Sun, Chen | Chen, Tong | Huang, Qunxing | Duan, Xiaoguang | Zhan, Mingxiu | Ji, Longjie | Li, Xiaodong | Yan, Jianhua
Porous carbons are appealing low-cost and metal-free catalysts in persulfate-based advanced oxidation processes. In this study, a family of porous biochar catalysts (ZnBC) with different porous structures and surface functionalities are synthesized using a chemical activation agent (ZnCl₂). The functional biochars are used to activate persulfate for sulfamethoxazole (SMX) degradation. ZnBC-3 with the highest content of ketonic group (CO, 1.25 at%) exhibits the best oxidation efficiency, attaining a rate constant (kₒbₛ) of 0.025 min⁻¹. The correlation coefficient of the density of CO to kₒbₛ (R² = 0.992) is much higher than the linearity of the organic adsorption capacity to kₒbₛ (R² = 0.694), implying that CO is the intrinsic active site for persulfate activation. Moreover, the volume of mesopore (R² = 0.987), and Zeta potential (R² = 0.976) are also positive factors in PS adsorption and catalysis. In the mechanistic study, we identified that singlet oxygen is the primary reactive oxygen species. It can attack the –NH₂ group aligned to the benzene ring to form dimer products which could be adsorbed on the biochar surface to reach complete removal of the SMX. The optimal pH range is 4–6 which will minimize the electrostatic repulsion between ZnBCs and the reactants. The SMX degradation in ZnBC/PS system was immune to inorganic anions but would compete with organic impurities in the real wastewater. Finally, the biochar catalysts are filled in hydrogel beads and packed in a flow-through packed-bed column. The continuous system yields a high removal efficiency of over 86% for 8 h without decline, this work provided a simple biochar-based persulfate catalyst for complete antibiotics removal in salty conditions.
Показать больше [+] Меньше [-]Application of docking and active site analysis for enzyme linked biodegradation of textile dyes
2019
Srinivasan, Shantkriti | Sadasivam, Senthil Kumar | Gunalan, Seshan | Shanmugam, Gnanendra | Kothandan, Gugan
Growth of textile industries led to production of enormous dye varieties. These textile dyes are largely used, chemically stable and easy to synthesize. But they are recalcitrant and persist as less biodegradable pollutants when discharged into waterbodies. Potential use of enzyme-linked bioremediation of textile dyes will control their toxicity in waterbodies. Bioinformatics and Molecular docking tool provides an insight into remediation mechanism by predicting susceptibility of dye degradation using oxidoreductive enzymes. In this study, six dyes, Reactive Red F3B, Remazol Red RGB, Joyfix Red RB, Joyfix Yellow MR, Remazol Blue RGB and Turquoise CL-5B of azo, anthraquinone and phthalocyanine molecular class were identified as potential targets for degradation by laccase and azoreductase of Aeromonas hydrophila in addition to Lysinibacillus sphaericus through in silico docking tool BioSolveIT-FlexX. Azoreductase breaks azo bonds by ping-pong mechanism whereas laccase decolorizes dyes by free radical mechanism which is not specific in nature. Results were analyzed based on parameters like stability, catalytic action and selectivity for enzyme-dye interactions. Amino acids of enzymes interacted with several dyes substantiating variations in active site for enzyme-ligand binding affinity. This suggests the role of enzymes in decolorizing an extensive variety of textile dyes, thereby, aiding in understanding the enzyme mechanisms in Bioremediation.
Показать больше [+] Меньше [-]