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MIL-68(Al)
CHEMICAL ENGINEERING JOURNAL · 2015 · IF 4.321

Synthesis of CNT@MIL-68(Al) composites with improved adsorption capacity for phenol in aqueous solution

Tongtong Han,Yuanlong Xiao,Minman Tong,Hongliang Huang,Dahuan Liu,Luyan Wang,Chongli Zhong

A series of CNT@MIL-68(Al) composites with different carbon nanotubes (CNTs) loadings have been synthesized and characterized by SEM, TEM, PXRD, FT-IR, TGA, and N 2 adsorption. As evidenced from SEM and TEM images, the incorporation of CNTs can result in better dispersity of MIL-68(Al) in composites and smaller particle size than pure MIL-68(Al). Adding appropriate amounts of CNTs increases both the BET surface areas and the total volume of small micorpores (<16   Å), leading to largely improved performance of adsorptive removal of phenol from aqueous solution. In the industrial concentration range of phenol, the adsorption capacity of 0.75% CNT@MIL-68(Al) was improved up to 188.7% compared with the pristine MIL-68(Al), possibly due to the increase of small micropores introduced by the incorporation of CNTs. Regeneration experiments demonstrated that the composites are stable with good regenerability for at least five cycles. This work shows that the composites formed by the combination of CNTs and MOFs may find promising applications in liquid phase adsorption.

CAS / MDL: 7784-13-6 108-95-2
研究领域: 材料科学 · 环境科学 · 化学工程
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WATER SCIENCE AND TECHNOLOGY · 2017 ·Vol. 75 ·期 12 ·2800-2810 · IF 1.197

Adsorption behavior of methyl orange onto an aluminum-based metal organic framework, MIL-68(Al)

Wu Shi-chuan,You Xia,Yang Cao,Cheng Jian-hua

MIL-68(Al), a powdered aluminum-based metal organic framework (MOF), was synthesized and used to explore its adsorption behavior toward methyl orange (MO). The adsorption isotherm, thermodynamics, kinetics, and some key operating factors as well as changes in the material's structure were investigated. The adsorption isotherm conformed to the Langmuir isotherm model and the maximum equilibrium adsorption capacity was 341.30 mg g −1 . Thermodynamic data demonstrated that the adsorption process was spontaneous, endothermic and showed positive entropy. For kinetics, the process of MO adsorption onto MIL-68(Al) was more suitably described by a pseudo-second-order model. Electrostatic and hydrogen-bonding interactions contributed to dye adsorption, with electrostatic interactions considered to be the principal binding force between adsorbent and adsorbate. Furthermore, MIL-68(Al) maintained a stable structure after adsorption. From these results, MIL-68(Al) was suggested here to be a stable MOF adsorbent for removing MO from aqueous solution.

研究领域: 环境化学 · 材料科学 · 物理化学 · 污染控制 · 吸附科学
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Materials Today Communications · 2024 · IF 3.7

Preparation of MIL-68(Al) embedded in SBA-15 functionalized with carboxyl groups as a catalyst for 4-nitrophenol to 4-aminophenol

Peihang Shen,Zelong Liu,Yibo Zhang,Zelin Meng,Mingyang Song,Heming Zhao,Jianglei Hu,Fengwei Shi

Vinyl-functionalized SBA-15 was synthesised using a one-pot co-condensation method followed by carboxylation via nitric acid, with the intermediate product named SBA-15C. MIL-68 was then synthesised in-situ by adsorption of Al 3 + ions via carboxylate groups on SBA-15C to give the composite xMIL-68(Al)@SBA-15C. A series of characterizations were conducted by Fourier transform infrared spectroscopy, Brunner-Emmet-Teller measurements, X-ray diffraction, X-ray photoelectron spectroscopy, Scanning electron microscope, and Transmission Electron Microscope. xMIL-68(Al)@SBA-15C maintained robust catalytic performance in the NaBH 4 -mediated reduction of 4-nitrophenol to 4-aminophenol, with no significant decrease in activity after five cycles of reuse.

研究领域: 材料科学 · 催化化学
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ACS Omega · 2023 · IF 4.1

Preparation of a Multifunctional and Multipurpose Chitosan/Cyclodextrin/MIL-68(Al) Foam Column and Examining Its Adsorption Properties for Anionic and Cationic Dyes and Sulfonamides

Jing Wang,Yong Zhang,Fubin Liu,Ying Liu,Litao Wang,Guihua Gao

A multifunctional cylindrical hybrid foam column, referred to as the chitosan/cyclodextrin/MIL-68(Al) (CS/CD/MIL-68(Al)) foam column, was prepared for the first time. The prepared foam column could be used for the adsorption/removal of hydrophilic and hydrophobic contaminants by different forms. Here, it was placed in hydrophilic dye solutions to investigate the adsorption behavior of methylene blue and trypan blue. The adsorption process followed the pseudo-second-order kinetic model with R2 ranging from 0.9983 to 0.9998 for methylene blue and from 0.9993 to 1.0000 for trypan blue, and the adsorption process was consistent with the Langmuir isothermal model with R2 greater than 0.96. The RL values for methylene blue and trypan blue were 0.8871 and 0.5366, respectively, which were present between 0 and 1, indicating that the adsorption behaviors of the two dyes onto the CS/CD/MIL-68(Al) foam column were favorable. The maximum adsorption capacities (Qm) of methylene blue and trypan blue were 60.61 and 454.55 mg/g at 298 K, respectively. Also, the CS/CD/MIL-68(Al) foam column was spun into a syringe and used to adsorb trace hydrophobic sulfonamides from water in the form of filtration. The porous structure impeded the need for any external force and equipment, allowing the water sample to pass through the foam column smoothly. The conditions of the CS/CD/MIL-68(Al) foam column were optimized. The adsorption was carried out under the condition of pH = 4, the amount of the adsorbent was two foam columns, and no salt was added. It was found that the removal rate of the CS/CD/MIL-68(Al) foam column for six sulfonamides was 100%, and it could be reused at least five times. Therefore, this CS/CD/MIL-68(Al) foam column had a simple preparation method, offered a flexible and diverse form of use, was nonpolluting, biodegradable, and reusable, and could have a wider application in the field of environmental pollutant removal and adsorption.

研究领域: 环境科学 · 材料科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2019 · IF 5.107

A new MOFs/polymer hybrid membrane: MIL-68(Al)/PVDF, fabrication and application in high-efficient removal of p-nitrophenol and methylene blue

Yuanming Tan,Zhongqiao Sun,Hao Meng,Yide Han,Junbiao Wu,Junli Xu,Yan Xu,Xia Zhang

MOFs/polymer hybrid membranes combine the special surface activity of MOFs and the excellent carries nature of porous polymer and thus exhibit unexpected adsorption/separation performances in the solid-phase extraction. In this paper, a new kind of MOFs/polymer composite membrane , MIL-68(Al)/PVDF have been fabricated for the first time through blending the MIL-68(Al) nanoparticles and polyvinylidene fluoride (PVDF) casting solution and following the lyotropic phase transition. Some means such as SEM, XRD and FT-IR are used to character the structure of these hybrid membranes. The membrane performances including the hydrophilic/hydrophobic properties, membrane porosity and membrane water flux are also measured. The effects of doping amount of MIL-68(Al) on the structure and performances of MIL-68(Al)/PVDF hybrid membranes are discussed. Two persistent organic pollutants : p -nitrophenol (PNP) and methylene blue (MB) are chosen as main adsorption objects to evaluate the adsorption activity of MIL-68(Al)/PVDF hybrid membranes. The influences of various conditions on the adsorption activities are investigated in detail and the optimum adsorption conditions are determined. All the MIL-68(Al)/PVDF hybrid membranes exhibit enhanced adsorption capacity compared to pristine PVDF, and the adsorption activities of hybrid membranes are promoted continually with the increasing doping contents of MIL-68(Al). The adsorption thermodynamics analysis indicates that the adsorption process is mainly characterized by Langmuir monolayer adsorption and chemical adsorption . The coordination bonding formed between NO 2 of PNP and Al(III) of MIL-68(Al), and the acid-base interaction between the sulfur of MB and Al(III) of MIL-68(Al) may be responsible to the highest removal efficiency of PNP and MB. The good dynamics adsorption and regeneration performances indicate the prospect applications of these MOFs/PVDF hybrid membranes in the separation of organic contaminants from industrial waste water.

CAS / MDL: 100-21-0
研究领域: 材料科学 · 环境科学 · 化学工程
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JOURNAL OF CHROMATOGRAPHY A · 2024 · IF 3.8

Preparation of cylindrical Chitosan/β-Cyclodextrin/MIL-68(Al) foam column for solid-phase extraction of sulfonamides in water, urine, and milk

Yong Zhang,Jing Wang,Fubin Liu,Litao Wang,Guihua Gao

This study describes the preparation of a cylindrical polymer foam column termed Chitosan/β-Cyclodextrin/MIL-68(Al) (CS/β-CD/MIL-68(Al)). An ice template-freeze drying technique was employed to prepare the CS/β-CD/MIL-68(Al) foam column by embedding MIL-68(Al) in a polymer matrix comprising cross-linked chitosan (CS) and β-cyclodextrin (β-CD). The cylindrical CS/β-CD/MIL-68(Al) foam was subsequently inserted into a syringe to develop a solid phase extraction (SPE) device. Without the requirement for an external force, the sample solution passed easily through the SPE column thanks to the porous structure of the CS/β-CD/MIL-68(Al) foam column. Moreover, the CS/β-CD/MIL-68(Al) foam column was thought to be a superior absorbent for SPE since it included the adsorptive benefits of CS, β-CD, and MIL-68(Al). The SPE was utilized in conjunction with high-performance liquid chromatography to analyze six sulfonamides found in milk, urine, and water. With matrix effects ranging from 80.49 % to 104.9 % with RSD values of 0.4–14.0 %, the method showed high recoveries ranging from 80.6 to 107.4 % for water samples, 93.4–105.2 % for urine, and 87.4–100.9 % for milk. It also demonstrated good linearity in the range of 10–258 ng·mL -1 with the limits of detection ranging from 1.88 to 2.58 ng·mL -1 . The cylindrical CS/β-CD/MIL-68(Al) foam column prepared in this work offered several advantages, including its simple fabrication, excellent water stability, absence of pollutants, biodegradability, and reusability. It is particularly well-suited for SPE. Furthermore, the developed SPE method, employing CS/β-CD/MIL-68(Al) foam column, is straightforward and precise, and its benefits, including affordability, ease of preparation, lack of specialized equipment, and solvent economy, underline its broad applicability for the pretreatment of aqueous samples.

研究领域: 分析化学 · 环境科学 · 食品科学
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TALANTA · 2020 · IF 5.339

One-step fabrication of hydrophilic MIL-68(Al)/Chitosan-coated melamine sponge for vortex-assisted solid-phase extraction of parabens in water samples

Yanxiao Jiang,Bo Zhang,Jingkang Li,Ying Sun,Xinghua Wang,Pinyi Ma,Daqian Song

A novel vortex-assisted solid-phase extraction method based on MIL-68(Al)/Chitosan-melamine sponge column (or V-MIL-68(Al)/CS-SC-SPE) is presented in this paper. The MIL-68(Al)/Chitosan-sponge column was prepared by a simple infiltration method and a preparation process that does not consume organic solvents. Scanning electron microscopy was used to characterize the functionalized sponge columns, and the skeleton and pores of the melamine sponge were successfully modified with the coating material (MIL-68(Al) and chitosan). Chitosan was used successfully not only as an adsorption adjuvant material, but also as an adhesive in the preparation of MIL-68(Al)/CS coating sponge materials. The presented method was further combined with high performance liquid chromatography (HPLC) and used in the determination of trace parabens (including methyl-, ethyl-, propyl- and butyl-parabens) in environmental water samples. Several important factors that affect the extraction performance were investigated. Under the optimum conditions, the method was successfully used to detect the four kinds of parabens in different water samples (domestic water, lake water and river water). The limits of detection ranged between 0.21 and 0.50 ng/mL, and the relative standard deviations for all parabens were below 10.8%.

CAS / MDL: 9012-76-4
研究领域: 环境科学 · 分析化学
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OPTICS EXPRESS · 2022 ·Vol. 30 ·期 8 ·12409-12419 · IF 3.833

Mid-infrared optical switches enabled by metal-organic frameworks for compact high-power nanosecond laser sources at 3 µm

Le Zheng,Chen Wei,Hongrong Zhou,Fanxi Sun,Ang Gao,Dongsheng Wang,Dongsheng Wang,Yong Liu

Pulsed lasers operating in the mid-infrared are of great importance for numerous applications in spectroscopy, medical surgery, laser processing, and communications. In spite of recent advances with mid-infrared gain platforms, the lack of a capable pulse generation mechanism hinders the development of compact mid-infrared pulsed laser source. Here we show that MIL-68(Al) and MIL-68(Fe), which are aluminum- and iron- based metal-organic frameworks (MOFs) with ordered atoms distribution and periodic mesoporous structure, constitute exceptional optical switches for the mid-infrared. We fabricated the MIL-68(Al) and MIL-68(Fe) via hydrothermal method and prepared reflection-type MIL-68(Al)- and MIL-68(Fe)- saturable absorber mirrors (SAMs). By employing the as-prepared SAMs in the laser cavities, we achieved high-power nanosecond Q-switched fiber lasers at 2.8 µm. Especially, the average output power and pulse duration of the MIL-68(Al) Q-switched fiber laser reached 809.1 mW and 567 ns, respectively. To the best of our knowledge, this is the first time to demonstrate that MIL-68(M) can be efficient optical switches for 3-µm mid-IR laser pulses generation. Our findings reveal that MIL-68(M) is promising saturable absorber for compact and high-performance mid-infrared pulsed lasers.

研究领域: 光学 · 材料科学
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JOURNAL OF SEPARATION SCIENCE · 2025 ·Vol. 48 ·期 5 ·e70141 · IF 2.8

Materials Institute Lavoisier-68(Al)-coated Frosted Glass Rods for Enhanced Detection of Tetracyclines in Food Samples by Suspended Bar Sorptive Extraction

Tao Bao,Jiao Long,Jina Wang,Meng Sun,Xinglong Zheng,Sicen Wang

Herein, we present a sensitive analytical method utilizing Materials Institute Lavoisier (MIL)-68(Al)-coated frosted glass rods (MIL-68(Al)@FGR) coupled with ultra-high-performance liquid chromatography for detecting trace tetracycline (TC) antibiotics in food matrices. The synthesized coating was thoroughly characterized through field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Systematic optimization of critical parameters, including extraction time, sample pH, formic acid concentration, and desorption time achieved optimal extraction efficiency. The developed method exhibited a wide linear range (3–70 ng/mL) with low detection limits (0.1–0.3 ng/mL) for target analytes. Practical application to spiked food samples demonstrated satisfactory recoveries of 75.2%–115.1% across milk, chicken, and egg matrices, accompanied by precise relative standard deviations of ≤8.4%. The MIL-68(Al)@FGR-based approach shows exceptional resistance to matrix interference and detection sensitivity, establishing an effective strategy for monitoring TC residues in complex food samples.

研究领域: 分析化学 · 食品安全
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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

In-situ synthesis of SiO2@MOF composites for high-efficiency removal of aniline from aqueous solution

Tongtong Han,Caifeng Li,Xiangyu Guo,Hongliang Huang,Dahuan Liu,Chongli Zhong

A series of SiO 2 @aluminum-MOF(MIL-68) composites with different SiO 2 loadings have been synthesized by a simple and mild compositing strategy for high-efficiency removal of aniline. As evidenced from SEM and TEM images as well as the particle size distribution , the incorporation of SiO 2 can improve the dispersity of MIL-68(Al) in composites, and result in the smaller particle size than that of pristine MIL-68(Al). Besides, the adsorption of aniline over SiO 2 , MIL-68(Al), the physical mixture of these two materials, and SiO 2 @MIL-68(Al) composites was investigated comparatively, demonstrating a relatively high adsorption capacity (531.9   mg   g −1 ) of 7% SiO 2 @MIL-68(Al) towards aniline. Combining the ultrafast adsorption dynamics (reaching equilibrium within 40   s) and great reusability, 7% SiO 2 @MIL-68(Al) shows excellent adsorption performance. This indicates that the SiO 2 @MIL-68(Al) composites possess great potential applications as a kind of fascinating adsorbent in water pollution protection.

CAS / MDL: 7784-13-6
研究领域: 环境科学 · 材料科学
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