JOURNAL OF HAZARDOUS MATERIALS
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2025
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IF 11.3
Renjie Pan,Zongchen Li,Tian-Yang Zhang,Qi Fu,Zheng-Xiong Zheng,Jun Shi,Jian Lu,Chen-Yan Hu,Yu-Lin Tang,Mohamed Gamal El-Din,Bin Xu
Peracetic acid-based advanced oxidation processes (PAA–AOPs), which generate various reactive radicals, have garnered substantial attention for degradation emerging contaminants (ECs). However, nonselective radical-based PAA–AOPs often suffer from interference by water matrix components, causing low contaminants removal efficiency. This study explores the use of amino-(NH 2 )-functionalized metal–organic frameworks (MIL-101(Fe)-NH 2 ) as heterogeneous catalysts for PAA activation, enabling the generation of high-valent iron- (Fe)–oxo species (Fe(IV)) capable of efficiently degrading ECs (80 −100 %, within 30 min). The Fe(II) clusters in MIL-101(Fe)-NH 2 , modulated by electron-donating −NH 2 groups, play a pivotal role in Fe(IV) generation. Scavenger and probe experiments confirmed Fe(IV) as the primary reactive species responsible for ECs degradation. Density functional theory calculations demonstrated that the four-electron transfer to generate Fe(IV) has lower free energy than the two-electron transfer to generate organic radicals (e.g., CH 3 COO • and CH 3 C(O)OO • ). Furthermore, thermodynamically unfavorable CH 3 COO • desorption further promotes Fe(IV) generation. The PAA/MIL-101(Fe)-NH 2 system efficiently degraded SMX ( k app = 121.2 −287.2 M −1 s −1 ) and other ECs ( k app = 40 −432 M −1 s −1 ) with minimal interference from water matrix components and excellent reusability. This study demonstrates that MIL-101(Fe)-NH 2 is a robust catalyst for PAA activation and provides a novel approach for selectively generating Fe(IV) for ECs degradation.
研究领域:
环境科学
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催化化学
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PubMed
高影响因子
TALANTA
·
2024
·
IF 5.6
Shengyuan Zhang,Haiyan Li,Dezhi Yang,Yaling Yang
In the present research, Fe-based metal-organic frameworks (MIL-101(Fe)–NH 2 ) nanoparticles were synthesized by simple solvothermal methods and used to assay Cr(Ⅵ). The MIL-101(Fe)–NH 2 performs dual functions: the 2-aminoterephthalic acid (NH 2 -BDC) ligand endows a strong fluorescence emission, and the Fe metal nodes are able to facilitate the oxidation of 3,3′,5,5′- tetramethylbenzidine (TMB) directly, resulting in the generation of oxidized-TMB (ox-TMB). Our research results showed that reducing agents such as ascorbic acid (AA) can collapse the structures of MIL-101(Fe)–NH 2 because of the reduction of Fe 3+ by AA, resulting in release of NH 2 -BDC. In the presence of Cr(Ⅵ), the fluorescence intensity of the MIL-101(Fe)–NH 2 + AA system will be decreased due to the competitive reduction of Fe 3+ and Cr(Ⅵ). Nevertheless, Cr(Ⅵ) can significantly accelerate the oxidation of TMB by MIL-101(Fe)–NH 2 as it boosts the electron transfer rate between Fe 3+ and Fe 2+ . Therefore, a fluorescent/colorimetric dual-mode platform was developed for the detection of Cr(Ⅵ) with an extensive linear range (7.5–750 μg/L and 13.3–1000 μg/L) as well as a remarkably low detection limit (0.99 μg/L and 1.98 μg/L). This MOF with the ability to release ligands not only provides inspiration for the design of new luminescent materials, but also offers a novel and reliable solution for the detection of Cr(Ⅵ).
研究领域:
分析化学
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环境科学
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材料科学
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高影响因子
Journal of Water Process Engineering
·
2023
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IF 7
Shuangli Li,Yu Zhang,Sen Qiao,Jiti Zhou
Although MIL-101(Fe) has a homogeneous distribution of active metal sites, the relatively low stability of its coordination bonds limits its potential for application, especially in harsh environments. Here, a novel lanthanum-doped MIL-101(Fe)-NH 2 @mesoporous SiO 2 yolk-shell (LMFN-YS) material, synthesized by green water-etching, has effectively improved the adsorption capacity and stability of MIL-101(Fe)-NH 2 . Compared to traditional acid-base etching methods, water etching offered a more co-friendly and cost-effective approach to producing yolk-shell structures. Due to the mesoporous protective shell of mesoporous SiO 2 and more exposed active sites, the yolk-shell materials showed a faster adsorption rate (30 min) and a larger uptake capacity (240.0 mg P/g) than those of MIL-101. The material also exhibited broad range of pH stability from 2 to 10 and displayed good cyclic regeneration ability, with a removal efficiency of 75.9 % after three cycles. Additionally, it demonstrated excellent selectivity towards various coexisting anions such as Cl − , NO 3 − , SO 4 2− , CO 3 2− and HCO 3 − at diverse ionic strengths ranging from 0.001 to 1 M. The superior performance of L 1 MFN-YS (yolk-shell materials of La: Fe = 1:1) was attributed to a combination of factors, including ligand exchange between La(Fe)-OH and phosphates, Lewis acid-base interaction and electrostatic attraction. Additionally, high phosphate removal performance was observed in the real petrochemical wastewater (initial concentrations of 5.48 mg P/g) with a residual effluent concentration of 0.05 mg P/L, which was below the A-level standard of phosphate effluent in China (0.5 mg/L). This work provides a green method for preparing yolk-shell materials with improved ability to treat phosphate wastewater.
研究领域:
环境科学
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材料科学
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化学工程
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废水处理
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高影响因子
CHEMOSPHERE
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2022
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IF 8.943
Lu Zheng,Yifan Gu,Baolv Hua,Jiarui Fu,Fengting Li
Metal-organic frameworks have been investigated in Fenton-like catalysis for tetracycline hydrochloride degradation, a widely used antibiotic which threatens the growth and health of creatures. However, powder phase and absence of large pores limit the materials’ degradation performance and application. In this work, a hierarchical macro-meso-microporous composite melamine sponge@MIL-101-Fe-NH 2 was firstly designed and constructed. While the micropores provided plenty of active sites to generate reactive oxygen species , the macropores and mesopores accelerated mass transfer. Besides, MIL-101-Fe-NH 2 particles dispersed on melamine sponge individually, exposing more catalytic sites and avoiding inactivation caused by aggregation compared to powder catalysts. Its catalysis performance for tetracycline hydrochloride degradation was evaluated through changing various influence factors like H 2 O 2 concentration, catalyst amount, pH and coexisting ions. Different from the preference of homogenous Fenton catalysts for pH 2–4, the composite displayed the most effective degradation at a subacid environment closer to nature with 77.24% in 30 min. Owing to the synergistic effect of hierarchical porous structure and monodispersed nanoparticles , the composite exhibited faster reaction rate and longer persistence compared to powder MIL-101-Fe-NH 2 . Easy recycling and less ion leaching made it advantages for practical application. •OH, •O 2 − and 1 O 2 active species contributed together to the degradation and two main possible degradation pathways were put forward based on 35 detected intermediates.
研究领域:
环境科学
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材料科学
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化学工程
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高影响因子
JOURNAL OF CHROMATOGRAPHY A
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2026
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IF 4
Xueyun Wei,Lanrui Yang,Zhuomin Zhang,Gongke Li
Trace disinfection by-products (DBPs) in aquatic products may have serious impact on human health via direct or indirect consumption. However, the accurate and sensitive quantification of trace chlorophenol DBPs in complex aquatic products still remains a great challenge. In this work, the defective MIL-101(Fe)-NH 2 enrichment medium was prepared for developing a selective membrane solid phase extraction (M-SPE) technology for quantifying trace chlorophenol DBPs in fish, coupled with high performance liquid chromatography-ultraviolet-visible spectroscopy (HPLC-UV). The established analytical method showed good selectivity, sensitivity and accuracy, achieving the limits of detection from 0.03 to 0.15 ng/mL and the recovery from 80.0% to 117%, achieving sensitivity comparable to that of HPLC-mass spectrometry (MS)-based methods. The validated method was successfully applied to quantify chlorophenol DBPs in grass carp and crucian carp, offering a selective and sensitive alternative for monitoring chlorophenol DBPs in fish, with practical advantages for routine analysis via compatibility with widely available HPLC-UV.
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高影响因子
CHEMICAL PAPERS
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2022
·Vol. 76
·期 7
·4379-4392
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IF 2.146
Zhang Huixian,Hu Xizhou,Xia Hong,Zhou Youxiang,Peng Lijun,Wu Jianyuan,Peng Xitian
Phenoxy carboxylic acid herbicides (PCAs) are widely used in agricultural production. However, due to their potential threat to human health, it is necessary to develop efficient analysis method for monitoring PCA concentration in environment and food samples. Based on dispersive micro-solid phase extraction (D-μ-SPE) with amine-functionalized metal–organic framework MIL-101(Fe)-NH 2 , a selective, sensitive, and cost-efficient method was proposed for the extraction of PCAs from environmental water and rice samples in this study. From the perspective of adsorption kinetics and isotherms, interaction mechanisms between MIL-101(Fe)-NH 2 and PCAs were investigated. Key parameters of D-μ-SPE procedure including adsorbent dosage, solution pH, ionic strength, eluting solution, and washing solutions were optimized. Using of small amount of MIL-101(Fe)-NH 2 could achieve desirable extraction effect due to its large surface area and multiple interactions with PCAs. Under the optimized D-μ-SPE conditions, calibration curves of 8 PCAs were linear within a concentration range of 0.05–5 ng/mL for water samples ( r 2 > 0.9898) and 0.5–50 ng/g for rice samples ( r 2 > 0.9879). Limits of detection of water and rice samples were as low as 0.004–0.008 ng/mL and 0.05–0.1 ng/g, respectively. The recoveries of 8 PCAs ranged from 83.0 to 109.3%. Both inter- and intra-day relative standard deviations were less than 10.3%. Our proposed method was successfully employed in actual environmental water and rice samples.
研究领域:
分析化学
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环境科学
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食品安全
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Zhiqiang Guo,Xinmiao Wu,Juanjuan Meng,Xinxin Li,Yuan Li,Liangliang Hu
MIL-101(Fe) has received more and more attention in wastewater treatment, and how to further improve its stability and sorption capacity has become a research focus. In this study, metal Mg was used to dope MIL-101(Fe) to construct Mg@MIL-101(Fe) with bimetallic sites, which was then mixed with NH 2 -MIL-125(Ti) to successfully fabricate Mg@MIL-101(Fe)/NH 2 -MIL-125(Ti) (MOM) bis-MIL composites. MOM not only contains a large number of sorption sites but also exhibits excellent stability and reusability, realizing efficient sorption of Pb(II) from aqueous solution. In addition, the sorption performance and mechanism of Pb(II) on MOM were investigated by the characterizations of SEM, BET, TG, XRD, FTIR and XPS, as well as the kinetic and thermodynamic analyses. The sorption of Pb(II) on MOM is in accordance with the Langmuir isothermal model and pseudo-second-order kinetic model. The maximum sorption capacity of Pb(II) on MOM derived from the Langmuir model fitting is 320.941 mg·g −1 . The sorption of Pb(II) on MOM is strongly affected by pH, but not by ionic strength, which indicates that MOM has good resistance to salt interferences. The strong complexation of carboxyl, hydroxyl and amino functional groups with Pb(II) is the main sorption mechanism of Pb(II) on MOM, and electrostatic interaction and ion exchange also contribute to the sorption. In conclusion, MOM has strong practical application prospects in the treatment of Pb(II)-containing wastewater.
研究领域:
环境科学
·
材料科学
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高影响因子
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