MOLECULES
·
2020
·Vol. 25
·期 4
·897
·
IF 3.267
Qian-Chun Zhang,Guang-Ping Xia,Jun-Yi Liang,Xiao-Lan Zhang,Li Jiang,Yu-Guo Zheng,Xing-Yi Wang
In this study, a novel monolithic capillary column based on a NH2-MIL-53(Al) metal–organic framework (MOF) incorporated in poly (3-acrylamidophenylboronic acid/methacrylic acid-co-ethylene glycol dimethacrylate) (poly (AAPBA/MAA-co-EGDMA)) was prepared using an in situ polymerization method. The characteristics of the MOF-polymer monolithic column were investigated by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, Brunauer-Emmett-Teller analysis, and thermogravimetric analysis. The prepared MOF-polymer monolithic column showed good permeability, high extraction efficiency, chemical stability, and good reproducibility. The MOF-polymer monolithic column was used for in-tube solid-phase microextraction (SPME) to efficiently adsorb trace sulfonamides from food samples. A novel method combining MOF-polymer-monolithic-column-based SPME with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was successfully developed. The linear range was from 0.015 to 25.0 µg/L, with low limits of detection of 1.3–4.7 ng/L and relative standard deviations (RSDs) of < 6.1%. Eight trace sulfonamides in fish and chicken samples were determined, with recoveries of the eight analytes ranging from 85.7% to 113% and acceptable RSDs of < 7.3%. These results demonstrate that the novel MOF-polymer-monolithic-column-based SPME coupled with UHPLC-MS/MS is a highly sensitive, practical, and convenient method for monitoring trace sulfonamides in food samples previously extracted with an adequate solvent.Keywords:monolithic capillary column;metal-organic framework;sulfonamides;solid-phase microextraction;ultra-high performance liquid chromatography-tandem mass spectrometry
研究领域:
分析化学
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食品科学
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材料科学
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Zhe Zhao,Wuming Xie,Zijun Huang,Haiming Cai,Yuemeng Ji,Baocong Zhao
The antibiotic florfenicol (FF) discharged into the aquatic environment may cause serious water pollution. Therefore, an effective way to eliminate FF antibiotics from the water bodies should be proposed. Herein, MIL-53(Al)-supported nano zero-valent iron (NZVI@MIL-53(Al)) was synthesized and applied to activate hydrogen peroxide (H 2 O 2 ) to spark the Fenton reaction for FF antibiotics removal. The characterization results demonstrated the successful loading and good dispersion of NZVI onto MIL-53(Al). 100 % FF antibiotics degradation could be achieved under the optimal reaction conditions, including an initial FF antibiotics concentration of 20 mg L −1 , initial solution pH of 3.0, NZVI@MIL-53(Al) dose of 25 mg L −1 , and H 2 O 2 concentration of 0.2 mM. And after four cycles, the FF antibiotic degradation efficiency was still 81.18 %. The lowest tolerance for HCO 3 − was observed while the degradation activity was maintained at the presence of Cl − and HA. EPR measurement and free radical quenching experiment showed that ·OH was the main reactive specie in the NZVI@MIL-53(Al)/H 2 O 2 system. FF antibiotics degradation involved hydroxylation reactions (electrophilic substitution), dehalogenation, hydrolysis, and cleavage based on the UPLC-MS/MS analysis and DFT calculation. Noteworthy, 0.247 mg L −1 of F − and 1.2 mg L −1 of Cl − were detected in the solution after the reaction due to the breakage of the stable C–Cl bond and C–F bond. Finally, this work revealed that the NZVI@MIL-53(Al), with high stability and recyclability, could be a potential heterogeneous catalyst for treating antibiotic wastewater.
研究领域:
环境科学
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化学工程
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材料科学
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分析化学
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产品关联
DOI
高影响因子
TALANTA
·
2017
·
IF 4.162
Guihua Gao,Sijia Li,Shuo Li,Yudan Wang,Pan Zhao,Xiangyu Zhang,Xiaohong Hou
In this work, computational and experimental methods were used to study the adsorption of estrogens and glucocorticoids on metal–organic frameworks (MOFs). Computer-aided molecular simulation was applied to predict the adsorption of eight analytes on four MOFs (MIL-101(Cr), MIL-100(Fe), MIL-53(Al), and UiO-66(Zr)) by examining molecular interactions and calculating free binding energies. Subsequently, the four water-stable MOFs were synthesized and evaluated as adsorbents for the target hormones in aqueous solution. As the MOF exhibiting the highest adsorption capacity in both computations and experiments, MIL-53(Al) was chosen as a sorbent to develop a dispersive micro-solid-phase extraction procedure coupled to ultra-performance liquid chromatography tandem mass spectrometry for simultaneous determination of the target analytes in water and human urine samples. Experimental parameters affecting the extraction recoveries, including pH, ionic strength , MIL-53(Al) amount, extraction time, desorption time, and desorption solvent, were optimized. The optimized method provided a linear range of 0.005025–368.6 μg/L with good correlation coefficients (0.9982 ≤ r 2 ≤ 0.9992), and limits of detection (S/N = 3) and quantification (S/N = 10) of 0.0015–1.0 μg/L and 0.005–1.8 μg/L, respectively. The analyte recoveries were in the range of 80.6–98.4% in water samples and 88.4–93.2% in urine samples. Furthermore, MIL-53(Al) showed good stability over 10 extraction cycles (RSD < 10.0%). Good agreement between experimental measurements and computational results showed the potential of this approach for elucidating adsorption mechanisms and predicating extraction efficiencies for MOFs and targets, providing new directions for the development and utilization of MOFs.
研究领域:
环境科学
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分析化学
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计算化学
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DOI
PubMed
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Rehan Khan,Wei-Min Liu,Ihtisham Ul Haq,Hong-Gang Zhen,Heng Mao,Zhi-Ping Zhao
Pyridine is generally found in the effluents from the synthesis of paints, rubber chemicals, vitamins, and pesticides. This study focused on improving the pervaporation (PV) performance of polyether block-amide (PEBA-2533) membranes cast on polyvinylidene fluoride (PVDF) substrate, by incorporating the MIL-53 (Al) particles to prepare mixed matrix membranes (MMMs) for pyridine separation from the aqueous solution. MIL-53 (Al) has a larger aperture size (8.5 Å) than the molecular size of the pyridine (6.0 Å), which could allow pyridine molecules to efficiently pass through its channels. The coadjacent MIL-53 particles created relatively continuous permeation pathways for the penetrants in the MMMs, which substantially enhanced the separation performance. Impressively, the resultant MMMs displayed superior pyridine separation performance at complex conditions. At 65 °C and 0.5 wt% pyridine aqueous solution, the separation factor and pyridine flux of PEBA/PVDF membrane were 17.3 and 143.5 g m −2 h −1 , which were improved using MIL-53@PEBA/PVDF MMMs to 48.1 and 226.9 g m −2 h −1 , respectively. Owing to the enhanced pyridine affinity, hydrophobic property, and thermal robustness, the resultant MMMs overcame the inherent trade-off between selectivity and permeability, and also displayed the promising long-term stability. These findings may provide valuable insights for developing novel MMMs with superior separation performance.
研究领域:
材料科学
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化学工程
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膜技术
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分离过程
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DOI
高影响因子
TURKISH JOURNAL OF CHEMISTRY
·
2022
·Vol. 46
·期 4
·1281-1290
·
IF 1.151
WANG JI,WANG QINGYIN,WANG GONGYING
Poly(ethylene terephthalate) (PET) is one of the world's five major engineering plastics and is widely used in various fields. At present, the main catalysts used in the synthesis of PET are antimony, titanium, and aluminum metal compounds. Among them, antimony-based catalysts are poisonous and the titanium-based catalyst products are relatively yellow in hue. The aluminum-based catalyst has the advantages of low price and environmental friendliness, but current research shows that the organoaluminum catalyst has the problem of hydrolysis, and MIL-53 (Al) has good stability and will not affect the environment, so we add a catalyst before the esterification reaction, and uses thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscope (SEM), and N2 low-temperature physical adsorption characterizes the thermal stability and structure of MIL-53(Al). At the same time, the effects of different content, polycondensation time, before and after activation and polycondensation temperature on the properties of PET were investigated. The research results show that when the molar content of catalyst is 0.05% and the reaction temperature is 280 oC for 150 min, the product obtained is relatively excellent. The catalytic activity has almost no effect before and after activation, indicating that the polycondensation reaction is carried out on the surface of the catalyst. Therefore, MIL-53 (Al) has great potential in PET industrial catalysis.
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DOI
高影响因子
FOOD CHEMISTRY
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2021
·
IF 7.514
Kuiyu Yi,Lei Zhang
An ingenious nanoscale fluorescent sensor derived from Eu 3+ -postfunctionalized MIL-53 (Al) (Eu 3+ @MIL-53 [Al]) was fabricated though a simple and effective approach. Malachite green (MG) effectively turned off the luminescence of Eu 3+ @MIL-53 (Al) via fluorescence resonance energy transfer (FRET), thus enabling MG sensing. The developed probe exhibited instantaneous reusability after being cleaned with deionized water. The fluorescence intensity, quenching efficiency, and crystal structure of the recoverable sensor after five recycling processes were unchanged compared with those of the original sample. Moreover, the potential mechanism of MG detection was revealed in detail. This work represents the first attempt to determine MG in aquaculture water and products by using metal–organic frameworks (MOFs). The Eu 3+ @MIL-53 (Al) probe proved to be a remarkable fluorescence probe for MG with high selectivity, sensitivity, and excellent regeneration capability. It provides a promising functional platform for the recognition of illegal MG addition to aquaculture water and products.
研究领域:
材料科学
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环境科学
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分析化学
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产品关联
DOI
PubMed
高影响因子
BIOMEDICAL CHROMATOGRAPHY
·
2022
·Vol. 36
·期 11
·e5454
·
IF 1.911
Yong Zhang,Kaifang Wei,Litao Wang,Guihua Gao
In this work, MIL-53(Al), as an inorganic “filler” component, was embedded in polyvinylidene difluoride (PVDF) and polystyrene-block-polybutadiene (SBS) matrices to prepare two mixed-matrix membranes (MMMs), using a simpler method than that previously reported. The PVDF and SBS membranes retained much of the properties of PVDF, SBS, and native MIL-53(Al). The prepared MMMs were then placed in a vortex-stirred sample solution to develop a membrane solid-phase extraction method to extract estrogens and parabens, which were determined by high-performance liquid chromatography with fluorescence detection. The extraction efficiencies of the two membranes were compared, with the PVDF membrane exhibiting superior performance. In addition, the PVDF membrane was more freestanding and flexible, and its preparation method was also more facile and simple. The extraction conditions were optimized, and the analytical method showed low limits of detection (0.005–0.18 ng/mL), good linearity, and high accuracy, with recoveries ranging from 90.7% to 102.5%. As a result, this membrane solid-phase extraction method indicated its potential for application in aqueous sample pretreatment. For metal–organic framework–based MMM used in this method, in addition to being durable, freestanding, mechanically stable, and possessing a large area, it should also exhibit high metal–organic framework incorporation, good flexibility, and appropriate thickness and weight.
研究领域:
分析化学
·
环境科学
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产品关联
DOI
PubMed
高影响因子
CHEMISTRY OF MATERIALS
·
2022
·
IF 10.508
Dequan Jiang,Ting Wen,Yanzhen Guo,Jie Liang,Zimin Jiang,Chen Li,Ke Liu,Wenge Yang,Yonggang Wang
Anomalous compression behaviors such as negative linear compressibility (NLC) and negative area compressibility (NAC) are emerging functionalities essential for utilities under extreme conditions. Metal–organic frameworks (MOFs) present a large family of NLC/NAC materials under the well-recognized “wine-rack” mechanism. Nevertheless, the working pressure of MOFs is limited to typically no more than 3 GPa. Herein, we report the observation of a rare reentrant NLC behavior of MIL-53(Al) over an ultrawide pressure region up to 41.6 GPa. MIL-53(Al) with the classic wine-rack topology first exhibits an NLC behavior along the c-axis in the pressure region of 0–2.7 GPa, followed by a normal compression process between 2.7 and 12.9 GPa. After that, it is surprising to find that the reentrant NLC property remains at a record-high pressure (>40 GPa) among the previously reported MOFs. The mechanisms of the distinct compression behaviors of MIL-53(Al) in the three stages are studied by combining the X-ray diffraction analyses, Raman spectra, and DFT calculation. Particularly, the photoluminescence of Cr3+ is used as a unique probe for the subtle changes of the local coordination environments of Al3+ under compression. Both the absorption spectra and photoluminescence of Cr3+-doped MIL-53(Al) not only verify the three-stage compression processes but also reveal a hidden structural/electrical phase transition around 22.0 GPa. These findings provide an in-depth understanding of the structure–property relationship of abnormal compression behavior at the local-structure level.
研究领域:
材料科学
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高压物理
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无机化学
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金属有机框架（MOFs）
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凝聚态物理
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DOI
高影响因子
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
·
2026
·Vol. 109
·期 5
·e70833
·
IF 4.2
Jia-Min Wu,Wei-Hao Cai,Lin Guo,Zhi-Cong Luo,Guan-Xiao Ran,Zhi-Xiang Cai,Xiao-Feng Zeng,Zhao-Qing Li,Jing-Xian Zhang,Yu-Sheng Shi
Vat photopolymerization (VPP) has recently been applied to fabricate silicon nitride (Si 3 N 4 ) ceramics. To overcome limitations in Si 3 N 4 slurry curing performance, a multi-functional modification strategy utilizing the metal-organic framework MIL-53(Al) was proposed. The introduction of MIL-53(Al) simultaneously affects slurry photocuring performance and ceramic microstructural regulation. MIL-53(Al) serves as a fluorescent active filler acting as an in situ photon source under ultraviolet irradiation, thereby enhancing the curing depth by an average of 17.5 µm. During the debinding process, the decomposition of MIL-53(Al) leaves a pore structure and aluminum oxide that can assist sintering, facilitating phase transformation and forming a well-interlocked β-Si 3 N 4 microstructure. The sintered Si 3 N 4 ceramic exhibited a flexural strength of 269.2 ± 12.6 MPa, and a fracture toughness of 3.54 ± 0.21 MPa·m 1/2 at a porosity of 23.9%. This study demonstrates the multi-functional role of MOF-based additives for both enhancing slurry printability and tailoring ceramic microstructure in fabrication of porous Si 3 N 4 ceramics via VPP.
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DOI
高影响因子
Surfaces and Interfaces
·
2026
·
IF 6
Wuxiu Ding,Duo Sun,Lan Zhang,Hongyi Wang,Yang Zhao,Weiguo He,Zhigang Du,Yongyan Yan
Applying protective coatings to the surface of stone heritage is one of the most common methods for its preservation. To enhance the weathering resistance of the limestone heritages, MIL-53@FS, a hydrophobic metal-organic framework (MOF) composite, was prepared through fluorosilane modification of MIL-53-OH synthesized via a solvothermal method. Characterization analyses were conducted using SEM, XRD, TGA, and FTIR techniques. The results indicated that MIL-53@FS maintained its well-ordered framework structure and certain porosity, while forming a continuous and uniform hydrophobic coating, leading to a significant increase of water contact angle to 127.14° and enhanced thermal stability. It exhibited excellent corrosion resistance, anti-icing performance, and color compatibility in the application tests, holding a promising outlook for protecting limestone-based heritages.
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高影响因子
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2026
·
IF 4.8
Haozhe Yang,Mo Yang,Fangrong Hu,Mingzhu Jiang,Longhui Zhang,Shangjun Lin,Ziheng Zhi,Wanting Zhu,Chenxi Liu,Lei Li
A MIL-53(Al)-functionalized terahertz metasurface sensor was developed for the room-temperature detection of styrene, a potential volatile biomarker associated with lung cancer. The sensor combines the localized electromagnetic field enhancement of the terahertz metasurface with the adsorption enrichment capability of MIL-53(Al). Benefiting from the flexible one-dimensional channels, the size-compatible pore environment of MIL-53(Al), and the possible π–π and host–guest interactions between styrene molecules and the terephthalate linkers, the functionalized metasurface exhibits an enhanced sensing response toward styrene. APTES was introduced as an interfacial coupling layer to improve the immobilization and dispersion of MIL-53(Al) nanocrystallites on the metasurface. SEM and FTIR characterizations confirmed the formation of a nanocrystallite-stacked MIL-53(Al) coating and the successful introduction of both APTES and MIL-53(Al) onto the sensor surface. The optimized sensor achieved a sensitivity of 0.37 GHz/ppm and a limit of detection of 1 ppm within the concentration range of 1–100 ppm. In addition, the sensor showed good selectivity against several interfering VOCs, as well as acceptable repeatability and stability. This work provides a feasible strategy for integrating flexible MOF adsorbents with terahertz metasurfaces, offering a potential platform for rapid, label-free, and room-temperature detection of trace aromatic VOCs.
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DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 2
·121220
·
IF 7.2
Mengjiao Yu,Xiong-Fei Zhang,Mengjie Li,Jianan Song,Jianfeng Yao
The valorization of cellulose into valuable platform chemicals necessitates efficient and sustainable catalytic systems, where the acid-base properties of catalysts are critical for directing reaction pathways. This work presents the one-pot synthesis of a series of aluminum-based metal-organic frameworks (MIL-53) with tunable acid-base functionalities, achieved by modulating organic linkers. The successful formation of cooperative acid-base sites was confirmed by comprehensive characterization, including X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and pyridine adsorbed infrared spectra. Catalytic performance evaluations demonstrated that acid-base cooperative sites significantly enhance the oriented conversion of cellulose to 5-hydroxymethylfurfural (5-HMF). Under optimal conditions (190 °C, 8 h) in a tetrahydrofuran (THF)/NaCl-H 2 O biphasic system, MIL-53-NH 2 /SO 3 H yielded 63.8 % 5-HMF, 6.3 % levulinic acid (LA), and 23.9 % formic acid (FA). The catalytic transformation of cellulose is a cascade process encompassing hydrolysis of cellulose to glucose, isomerization of glucose to fructose, dehydration to 5-HMF, and rehydration of 5-HMF to LA and FA. These results provide a promising strategy for designing efficient acid-base bifunctional catalysts for biomass conversion.
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DOI
高影响因子
危险品化学品经营许可证（带存储）