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MIL-101
MICROCHIMICA ACTA · 2016 ·Vol. 183 ·期 7 ·2235-2240 · IF 4.831

Urea-modified metal-organic framework of type MIL-101(Cr) for the preconcentration of phosphorylated peptides

Yang Xiaoqing,Xia Yan

Mass spectrometry (MS) is the most powerful tool in phosphoproteomics research. However, phosphopeptides usually are present in low concentrations and their preconcentration therefore is highly desired. We describe a two-step method for the synthesis of a metal organic framework of the type MIL-101(Cr) that is modified with urea (then designated as MIL-101(Cr)-UR 2 ). It possesses large surface area, good solvent stability and high affinity for some phosphates. Due to the presence of modified urea functions, this material allows for selective and effective enrichment of phosphorylated peptides. It was successfully applied to the enrichment of phosphopeptides from non-fat-milk. The method was applied to the detection of phosphopeptides in a tryptic digest of β-casein where is showed a detection sensitivity as low as 10 −10  M. A two step method was designed to synthesis MIL-101(Cr)-UR 2 and the prepared green solid was successfully applied to recognize phosphopeptides. (Amino functionalized metal-organic framework (MOF-NH 2 ); urea modified metal-organic framework (MOF-UR 2 ); matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS))

CAS / MDL: 68-12-2 144-48-9
研究领域: 分析化学 · 蛋白质组学 · 生物医学
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Catalysts · 2020 ·Vol. 10 ·期 7 ·772 · IF 3.52

A Polyoxometalate Composite Based on Hierarchical MIL-101 with Enhanced Catalytic Activity in Methanolysis of Styrene Oxide

Tian Zhao,Hexin Zhu,Ming Dong

A new efficient polyoxometalate composite catalyst of hierarchical MIL-101 and phosphotungstic acid (PTA) was facilely prepared by the immersion method. The material was thoroughly characterized by powder x-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductively coupled plasma‒optical emission spectrometry (ICP-OES). Compared to the pristine nonhierarchical MIL-101 composite, the hierarchical composite demonstrated much higher catalytic performance in methanolysis of styrene oxide, such as catalytic activity and reusability.Keywords:hierarchical MIL-101;higher catalytic activity;phosphotungstic acid;styrene oxide

研究领域: 催化 · 材料科学 · 化学工程
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2024 ·Vol. 25 ·期 18 ·9855 · IF 4.9

Preparation of NH2-MIL-101(Fe) Metal Organic Framework and Its Performance in Adsorbing and Removing Tetracycline

Yiting Luo,Rongkui Su

Tetracycline’s accumulation in the environment poses threats to human health and the ecological balance, necessitating efficient and rapid removal methods. Novel porous metal–organic framework (MOF) materials have garnered significant attention in academia due to their distinctive characteristics. This paper focuses on studying the adsorption and removal performance of amino-modified MIL-101(Fe) materials towards tetracycline, along with their adsorption mechanisms. The main research objectives and conclusions are as follows: (1) NH2-MIL-101(Fe) MOF materials were successfully synthesized via the solvothermal method, confirmed through various characterization techniques including XRD, FT-IR, SEM, EDS, XPS, BET, and TGA. (2) NH2-MIL-101(Fe) exhibited a 40% enhancement in tetracycline adsorption performance compared to MIL-101(Fe), primarily through chemical adsorption following pseudo-second-order kinetics. The adsorption process conformed well to Freundlich isotherm models, indicating multilayer and heterogeneous adsorption characteristics. Thermodynamic analysis revealed the adsorption process as a spontaneous endothermic reaction. (3) An increased adsorbent dosage and temperature correspondingly improved NH2-MIL-101(Fe)’s adsorption efficiency, with optimal performance observed under neutral pH conditions. These findings provide new strategies for the effective removal of tetracycline from the environment, thus holding significant implications for environmental protection.

CAS / MDL: 64-75-5
研究领域: 环境科学 · 材料科学
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Journal of Inorganic and Organometallic Polymers and Materials · 2024 · IF 3.9

Fast and Efficient Removal of Anionic Dyes from Water by Hierarchical Porous MIL-101(Cr)

Li Mengke,Cao Panpan,Dong Wenwen,Zhao Jun,Li Dongsheng

Organic dyes pollution has caused significant threat to flora, fauna and humans because the toxic of dyes. In this work, with the help of acetic acid as a defect initiator, the hierarchical porous MIL-101(HP-MIL-101) has been synthesized and used for removing anionic dyes Eosin y (EY), Methyl orange (MO), Congo red (CR) and Acid fuchsin (AF) from water. Due to its positive surface charge, larger specific surface area, well-matched pore structure, and the charge, size, and diameter of dyes, HP-MIL-101 showed rapid adsorption and an excellent maximum adsorption capacity of 425 and 336 mg⋅g − 1 for CR and AF, respectively. A series of batch experiments were carried out to investigate the impact of various key factors, including adsorption duration, initial dye concentration, and temperature. In addition, the kinetics, isotherm, and thermodynamics about the adsorption properties were also discussed. In addition, HP-MIL-101 showed stable and high reusability for at least three cycles, with an efficiency of over 95% without significant structural changes. This study highlights the potential of hierarchical porous MOF for mitigating dye pollution and advancing sustainable water treatment methodologies.

研究领域: 环境科学 · 材料科学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2019 · IF 4.084

Co-Fe/MIL-101(Cr) hybrid catalysts: Preparation and their electrocatalysis in oxygen reduction reaction

Guoru Li,Xiaobo He,Fengxiang Yin,Biaohua Chen,Huaqiang Yin

The development of highly efficient electrocatalysts with low cost for oxygen reduction reaction (ORR) is urgently required for metal-air batteries and fuel cells. In this work, Fe Co/MIL-101(Cr) with various molar ratios of Fe/Co as hybrid catalysts was prepared by a facile and mild impregnation method. MIL-101(Cr) increased the specific surface areas of the hybrid catalysts, thus improving the dispersion of Fe and Co species at their surfaces. The effects of Fe and Co species on ORR activity of the hybrid catalysts were investigated. It is found that the synergistic effects between the well-dispersed Fe and Co species contribute mainly to ORR activity. More specifically, Fe species exert a partial-charge-transfer-activation effect on Co ones, which reduces the charge transfer resistance and thus improves the catalytic activity . As a result, Fe Co/MIL-101(Cr) showed the excellent ORR activity, in which Co 50 Fe 50 /MIL-101(Cr) exhibited the superior ORR activity to the other prepared hybrid catalysts.

研究领域: 材料科学 · 电化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Engineering linker-defects of MIL-101 series metal organic frameworks for boosted Yb(III) adsorption

Yi Zhang,Chengyu Sun,Yihao Ji,Kaicheng Bi,Haipeng Tian,Bin Wang

Developing the highly efficient adsorbents for improved recovery of rare earth elements from industrial wastewater is significant. Therefore, two defective MIL-101 series, named as MIL-101(Cr)-D and MIL-101(Fe)-D, were fabricated by introducing benzoic acid as the second ligand to coordinate with metal clusters. The controlled samples were characterized by XRD, ATR-IR, TGA, EPR, and BET tests, verifying the presence of oxygen-vacancy sites and the integrity of crystalline structure. In addition, the adsorption kinetics, the adsorption isotherms, the influences of pH and different REE ions on adsorption performance, and the cycling stability of defective and normal MIL-101s were carefully discussed and compared. The results showed that the adsorption capacities of MIL-101(Fe)-D10 and MIL-101(Cr)-D20 were 27.88 and 37.45 mg·g −1 respectively for Yb(III) capture at 30 °C and pH = 6, were much higher than those of the corresponding normal MIL-101. Furthermore, the adsorption mechanisms of two defective MIL-101s have been analyzed by EDS, mapping and XPS, confirming the surface complexation interactions between Yb(III) and O-vacancy sites originated from Cr-O and Fe-O clusters. Meanwhile, the excellent reusability of MIL-101(Cr)-D10 was validated by the successive twelve adsorption recycles and XRD analysis. Hence, this work supplies the feasible and facile strategy for manufacturing the missing-linker defective MOFs, endowing these adsorbents with the enhanced adsorption performance towards Yb(III) from aqueous solution.

研究领域: 材料科学 · 环境工程
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JOURNAL OF RARE EARTHS · 2024 · IF 5.2

Poly(ionic liquids-acrylic acid)-modified MIL-101(Cr) metal−organic frameworks: Preparation and efficient adsorption of europium☆

Xiayu Liang,Aylin M. Deliormanlı,Qingle Zeng

A novel composite material, Poly(IL-AA)@MIL-101(Cr), combining metal-organic framework, polymeric ionic liquid and acrylic acid, was synthesized for the selective and efficient adsorption of rare earths europium(III) (Eu 3+ ). Characterization of the materials was carried out using techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET). The results demonstrate successful incorporation of the polymeric ionic liquid onto the material surface while preserving the crystal structure and morphology of MIL-101(Cr). Adsorption experiments were conducted to explore parameters including solution pH, initial Eu 3+ concentration, and duration, with comprehensive analyses of adsorption kinetics, isotherms, and mechanisms. Findings reveal that Poly(IL1-AA)@MIL-101(Cr), Poly(IL3-AA)@MIL-101(Cr), and Poly(IL5-AA)@MIL-101(Cr) achieve adsorption equilibrium for Eu 3+ at approximately 9 h with an equilibrium pH of 6.2. The adsorption of Eu 3+ predominantly follows a pseudo-second-order kinetic model and Langmuir isotherm adsorption model. Moreover, the prepared composite material exhibits superior adsorption selectivity for Eu 3+ over other metal ions in the mixture (K + , Mg 2+ , Ni 2+ , Co 2+ , Zn 2+ , La 3+ , and Nd 3+ ). Even after five adsorption-desorption cycles, the composite material maintains satisfactory adsorption performance.

研究领域: 材料科学 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Recyclable CMC/PVA/MIL-101 aerogels with tailored network and affinity sites for efficient heavy metal ions capture

Chen Yang,Hua-Rong Yang,Qing-Da An,Zuo-Yi Xiao,Shang-Ru Zhai

A novel CMC/PVA/MIL-101(Cr) aerogel bead (CPMB) was prepared by the green polymer matrix of CMC and PVA and nanofiller of MIL-101(Cr) through the simple complexing with the ionic crosslinking agent, which could be an adsorptive platform for effectively capturing of Co(II) and Ni(II) ions in wastewater. The morphology, surface chemistry, and textural characteristics were investigated by varied characterization methods to reveal behind mechanisms for the dissimilarity in adsorption performance. The optimal modifying dosage of MIL-101(Cr) nanoparticles was determined to form an optimal tailored network with abundant MIL-101 clusters and hydroxyl/carboxyl groups inside the network that greatly achieved the most accessible heavy metals to CPMB-1. Meanwhile, the influences of temperature, adsorption dosage, pH, and interfering cations on the capacity of CPMB-1 were investigated, while adsorption behaviors of adsorbents were also explored. Analytic results indicated that the capture of two targeted ions by CPMB-1 could favorably comply with the Pseudo-second-order kinetic model and Freundlich isothermal adsorption model. The maximum adsorption capacities of two targeted ions calculated by data were 180.3 mg/g and 261.9 mg/g, respectively. According to the results of XPS and FTIR analysis, the electrostatic attraction and chelating effect could be the main mechanisms for improved performance, and contributing groups were the hydroxyl and carboxylic acid introduced into CPMB-1. Moreover, the as-designed CPMB-1 exhibited excellent recyclability and stability in eight cycles. The encouraging results exhibited by CPMB-1 might bring a new idea for integrating multiple functionalities of MOFs and biomass components for designing functional composites for efficient remediations of wastewater.

CAS / MDL: 9004-32-4 100-21-0
研究领域: 环境科学 · 材料科学
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CHEMICAL ENGINEERING & TECHNOLOGY · 2022 ·Vol. 46 ·期 4 ·738-746 · IF 2.215

Deactivation of Pd6Cr4@NH2-MIL-101 Catalyst in Dehydrogenation of Formic Acid

Youhua Zhang,Linhai Duan,Ping Yang,Dan Zhang,Xiuhong Meng

Deactivation of Pd-Cr bimetallic nanopaticles supported on NH 2 -functionalized MIL-101 in dehydrogenation of formic acid is studied. Results show that the catalyst cannot be reused more than three times because the concentration of carbon monoxide in the gaseous product will exceed 10 ppm. When the catalyst is used for the first time, the turnover frequency of the active metal Pd is the highest. With an increase of catalyst utilization times, the turnover frequency decreases. The reason for the reduction in catalyst activity is agglomeration of Pd and Cr atoms on the outer surface of the catalyst, not because the active component, Pd, is being lost.

CAS / MDL: 7789-02-8 100-21-0
研究领域: 化学工程 · 催化科学
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LANGMUIR · 2025 · IF 3.9

Renewable Magnetic NH2-MIL-101(Fe) for the Efficient Removal of Bisphenol A from Aqueous Solutions

Mingyang Xiong,Yao Zeng,Ruisi Qiu,Hongxing He,Yi Zhang,Zhifeng Nie,Bing Wang

Bisphenol A (BPA) is extensively utilized as an industrial chemical in the production of certain plastics and epoxy resins. They are frequently found in environmental water and have the potential to cause risks to both the environment and human health. To efficiently remove the endocrine disruptor BPA from aqueous solutions, sea urchin-like magnetic material Fe3O4@PDA@NH2-MIL-101 (Fe) was synthesized via hydrothermal methods. Fe3O4@PDA@NH2-MIL-101 (Fe) has excellent adsorption performance, with a theoretical maximum adsorption capacity of 300.47 mg/g for BPA. The adsorption kinetics of BPA by Fe3O4@PDA@NH2-MIL-101 (Fe) followed the pseudo-second-order kinetic model and Liu’s isotherm model. Magnetic separation experiments reveal a high recovery efficiency, maintaining 94.82% of its initial adsorption capacity after five cycles. The primary adsorption mechanisms of Fe3O4@PDA@NH2-MIL-101 (Fe) on BPA included pore filling, hydrogen bonding, π–π interaction, and Lewis acid–base interaction. Additionally, the material showed excellent removal performance of BPA, with a maximum adsorbed amount of 135.27 mg/g for total organic carbon (TOC) in the shale gas fracturing flowback fluid. These findings suggest that Fe3O4@PDA@NH2-MIL-101 (Fe) holds significant potential as an adsorbent for BPA removal from actual wastewater, offering promising prospects for practical applications.

CAS / MDL: 51-61-6 7705-08-0
研究领域: 环境科学 · 材料科学
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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

MIL-101(Cr) based d-SPE/UPLC-MS/MS for determination of neonicotinoid insecticides in beverages

Yueting Liao,Yaohai Zhang,Qiyang Zhao,Wei Xiang,Bining Jiao,Xuesu Su

Metal organic framework MIL-101(Cr) was successfully synthesized as a selective adsorbent by a facile self-assembly technique and combined with UPLC-MS/MS for enrichment and determination of neonicotinoids in fruit juices and tea beverages. Therein, MIL-101(Cr) was characterized by Fourier transform infrared spectrometry, scanning electron microscopy, X-ray diffraction, and N 2 adsorption–desorption isotherms. Box-Behnken design was applied to optimize the significant variables including the sorbent amount, pH of the matrix, eluant volume, extraction time and desorption time. The optimized conditions were sorbent amount of 20 mg, eluent volume of 1 mL, extraction time of 5 min and desorption time of 4 min. Under the optimized conditions, excellent sensitivity was achieved with the limit of detection of 0.0019–0.02 μg/L and limit of quantification of 0.0063–0.067 μg/L. Good linearity (R 2  ≥ 0.9988) was obtained within the range of 1–1000 μg/L, and the recovery was 71.04%-101.64% with relative standard deviations (RSDs) of 1.25%-8.82% in spiked samples. The inter- and intra-day RSDs were both<8.54%. The adsorption isotherms investigated for acetamiprid, thiacloprid, and imidacloprid pesticides better fitted with the Freundich adsorption isotherm with bimolecular adsorption capacity of 71.43, 68.49, and 50.38 mg/g, respectively. These results indicate that the nanocomposite is feasible for adsorption of the target analytes at trace amounts from fruit juices and tea beverages.

研究领域: 分析化学 · 环境科学 · 食品科学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

Preparation of N and Ce Co-doped MIL-101(Fe) Heterogeneous Catalysts for Efficient Electro-Fenton Oxidation

Jiakang Wan,Ling Wang,Wentao Xu,Zehai Xu,Junsheng Yuan,Guoliang Zhang

Design and synthesis of high-efficiency and stable heterogeneous catalysts for the electro-Fenton process remain challenging. In this study, a co-doped Ce and N metal–organic framework MIL-101(Fe) heterogeneous catalyst (Ce/N-MIL-101(Fe) was synthesized by a facile one-step solvothermal method. Polyvinyl pyrrolidone played dual roles during the fabrication process, which not only acted as a nitrogen source for doping but also prevented MIL-101(Fe) molecules from aggregating and reinforcing the formation crystal with a complete polyhedral crystal shape. The introduction of Ce significantly enhanced the density of active sites and promoted the Fe3+/Fe2+ cycle of the reaction system. Owing to the specific structure and properties, the rate of electron transfer in the catalytic process was significantly promoted. The synthesized Ce/N-MIL-101(Fe) catalyst exhibited a high degradation rate for dyes (>98%) with competitive stability and reusability. Moreover, compared with common electro-Fenton catalysts usually operated in a limited pH range of 3.0–6.0, the working pH range of Ce/N-MIL-101(Fe) was widened up to 10.0. The design concept for producing abundant active sites with co-doping into frameworks can be extended to more heterogeneous electro-Fenton catalysts constituted by other porous materials.

研究领域: 环境科学 · 材料科学
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