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MIL-53 (Al)
NEW JOURNAL OF CHEMISTRY · 2024 · IF 2.7

Preparation of MIL-53(Al) with different ligands for application in the glucose transformation to 5-hydroxymethylfurfural

Yongzhao Zhang,Xuzheng Chen,Yunlei Zhou,Tao Feng,Luping Lyu,Zhenya Zhu,Yifan Liu

The efficient transformation of glucose into 5-hydroxymethylfurfural (5-HMF) is crucial for sustainable bio-refinery processes, but achieving high production efficiency remains challenging. In this study, we presented the preparation of Al-containing metal-organic frameworks (MOFs), specifically MIL-53(Al), MIL-53(Al)-NO2, and MIL-53(Al)-NH2, using different ligands as catalysts to enhance the production of 5-HMF from glucose. Comprehensive characterization provided valuable insights into the properties of the synthesized MOFs. The synthesized MOFs exhibited varied MIL-53(Al) states, morphologies, and thermal stabilities based on the different ligands employed, which in turn affected their catalytic performance. Among the Al-containing MOFs synthesized, MIL-53(Al)-NH2 demonstrated remarkable catalytic capabilities for the conversion of glucose to 5-HMF. This MOF achieved an impressive 5-HMF yield of 53% and a reaction selectivity of 54%. The catalytic efficiency was further enhanced by leveraging the synergistic effect of MIL-53(Al)-NH2 in combination with Amberlyst-36, resulting in a 5-HMF yield of 59% and a reaction selectivity of 60%.

CAS / MDL: 100-21-0
研究领域: 化学工程 · 催化 · 材料科学 · 可持续化学
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Science of Advanced Materials · 2023 ·Vol. 15 ·期 6 ·754-760 · IF 0.9

Preparation of Morphologically and Dimensionally Controlled MIL-53(Al)

Chen Lin,Zhang Hang,Fouad Hassan,Akhtar M. S.,Wang Zhihong

This study presents a straightforward hydrothermal synthesis technique for modifying the crystal size and shape of MIL-53(Al) via the use of a mixed solvent solution consisting of water and DMF. Without the use of coordination inhibitors or surfactants, a sequence of nanosized MIL-53(Al) crystals was efficiently synthesized. The lowest crystal size we were able to achieve in this work was 100 nm, but present technologies are not suited to creating nanoscale crystals of this size. Large crystallinity and yield were attained, and the samples’ very large specific surface areas expanded the usefulness of this MOF material for gas adsorption and storage. X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, nitrogen gas adsorption/desorption, and infrared spectroscopy were all used to characterize the samples. Finally, the effect of moisture concentration on crystal size and shape was investigated.

研究领域: 材料科学 · 化学工程
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MOLECULES · 2024 · IF 4.2

Enhanced Cataluminescence Sensor Based on SiO2/MIL-53(Al) for Detecting Isobutylaldehyde

Qianchun Zhang,Xixi Long,Shan Tang,Li Jiang,Zhaoru Ban,Yanju Chen,Runkun Zhang

A simple, rapid, and reliable method for detecting harmful gases is urgently required in environmental security fields. In this study, a highly effective cataluminescence sensor based on SiO 2 /MIL-53(Al) composites was developed to detect trace isobutylaldehyde. The sensor was designed using isobutylaldehyde to generate an interesting cataluminescence phenomenon in SiO 2 /MIL-53(Al). Under optimized conditions, a positive linear relationship was observed between the signal intensity of the cataluminescence and isobutylaldehyde concentration. The isobutylaldehyde concentration range of 1.55–310 ppm responded well to the sensing test, with an excellent correlation coefficient of 0.9996. The minimum detectable concentration signal-to-noise ratio ( S/N = 3) was found to be 0.49 ppm. In addition, the sensor was effectively utilized for analyzing trace isobutylaldehyde; the analysis resulted in recoveries ranging from 83.4% to 105%, with relative standard deviations ( RSDs ) of 4.8% to 9.4%. Furthermore, the mechanism of cataluminescence between SiO 2 /MIL-53(Al) and isobutylaldehyde was explored using GC–MS analysis and density functional theory. We expect that this cataluminescence methodology will provide an approach for the environmental monitoring of isobutylaldehyde.

研究领域: 环境科学 · 材料科学 · 化学
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RSC Advances · 2015 ·Vol. 5 ·期 89 ·73068-73076 · IF 3.84

Mixed matrix membranes containing MIL-53(Al) for potential application in organic solvent nanofiltration

Lifang Zhu,Hongwei Yu,Huijuan Zhang,Jiangnan Shen,Lixin Xue,Congjie Gao,Bart van der Bruggen

Aromatic poly(m-phenyleneisophthalamide) (PMIA) and the metal-organic framework (MOF) MIL-53(Al) were employed as the polymer matrix and additive, respectively, to develop mixed matrix membranes (MMMs) via non-solvent induced phase separation for potential application in organic solvent nanofiltration. The prepared membranes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and water contact angle measurements. The membrane water permeance enhanced when MIL-53(Al) was incorporated into the membrane structure while the rejection had no significant change. The optimum MMM (with 0.5 wt% MOF concentration) passes mono and bivalent inorganic salts but rejects larger charged organic molecules and has a mean effective pore size of 0.7 nm. The influence of organic solvents on MMM performance was also investigated and the result shows that the performance shifts towards a lower pure water permeance and a higher rejection after exposure to organic solvents (ethyl acetate or methanol). The membrane performance in organic solvent nanofiltration was evaluated on the basis of the permeance and rejection of brilliant blue G in ethanol, and the result showed that the permeance of MMMs significantly increased (by 289%) while the rejection slightly reduced by 4% in contrast to the pure membrane.

研究领域: 材料科学 · 化学工程
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COMPOSITES COMMUNICATIONS · 2024 · IF 6.5

Facile synthesis of NH2-MIL-53(Al)@BiOBr@CQDs ternary heterostructure photocatalyst for degradation of ciprofloxacin in water

Xinyue Yang,Yong Li,Deyun Yue,Rui Li,Haojie Song

The construction of ternary heterojunction photocatalysts can achieve multi-gradient transfer of charges and accurate control the position of photogenerated electrons which has received increasing attention. In this paper, NH 2 -MIL-53(Al)@BiOBr@CQDs-10 % (ABCQDs-10 %) was prepared via a facile hydrothermal and chemical synthesis processes. Three-dimensional serration of NH 2 -MIL-53(Al) as a platform for irregular BiOBr nanosheets, CQDs promote interfacial contact and act as electron transport channels between BiOBr and NH 2 -MIL-53(Al) and constitute Z-type heterojunctions with high redox properties. ABCQDs-10 % shows the best photocatalytic removal efficiency (94.24 %) of CIP, the reaction rate constants (0.045 min −1 ) were 1.2 and 64 times higher than BiOBr and NH 2 -MIL-53(Al), respectively. The excellent degradation performance is attributed to the construction of Z-type heterojunction of NH 2 -MIL-53(Al)@BiOBr@CQDs which improve electron-hole separation and transfer efficiency. The main active species was •O 2 - . The photocatalytic activity of ABCQDs-10 % had not obvious loss after cycle experiments and the crystal structure had no significant changes, means high stable photocatalytic activity.

研究领域: 材料科学 · 环境科学 · 化学工程
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CRYSTENGCOMM · 2012 ·Vol. 14 ·期 17 ·5487-5492 · IF 3.842

Growth of preferential orientation of MIL-53(Al) film as nano-assembler

Feng Zhang,Xiaoqin Zou,Fuxing Sun,Hao Ren,Yuan Jiang,Guangshan Zhu

A thin film of MIL-53(Al) on the activated Al slice has been prepared successfully. The crystals in the films exhibit high phase purity and a preferential orientation with straight channel network (or (h0l) planes) of the crystals parallel to the support surface, which are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The loading of organic (2-(2-hydroxyphenyl)-pyridine) (PP) fluorescent molecules in the film has been accomplished. The behaviours of the fluorescent molecules assembled in the pores of the oriented crystals are probed by Fourier transform infrared (FT-IR) and fluorescence spectroscopies.

研究领域: 材料科学 · 纳米技术 · 生物医学工程 · 药物递送 · 表面科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Interfacial engineering in MIL-53(Al)/PEBA mixed matrix membranes for efficient n-butanol/water separation

Xin-Ru Chen,Heng Mao,Qiu-Ying Zhang,Wei-Min Liu,Shen-Hui Li,Qian-Qian Li,Li-Hao Xu,Yan-Mei Zhang,Xin-Yue Zhang,Jun-Jie Liu,Ao Kou,Zhi-Ping Zhao

Interfacial engineering in mixed matrix membranes (MMMs) is essential to attain superior separation performance and ensure long-term operational stability. In this research, a range of novel MMMs were designed and fabricated for pervaporation (PV) separation of n-butanol/water solution by introducing the MIL-53(Al) particles and three variants (i.e., MIL-53(Al)–NH 2 , MIL-53(Al)–NO 2 , MIL-53(Al)–OH) into PEBA polymer matrix. These four MIL-53(Al) counterparts were synthesized via a microwave-assisted solvothermal method by selectively functionalizing the terephthalic acid linkers with different chemical groups. The functional MIL-53(Al) variants were employed to explore the relationship between membrane microstructures and PV performance by manipulating the interfacial interactions with PEBA matrix. The findings reveal that incorporating MIL-53(Al) variants not only displayed excellent interfacial compatibility and uniform dispersion within PEBA matrix, but also constructed the preferential transport pathways for n-butanol over water molecules. Impressively, in a 1 wt% n-butanol aqueous solution at 40 °C, the resultant membrane attained a permeation flux of 1483.3 g·m -2 ·h -1 and a separation factor of 18.1. Compared to the PEBA/PVDF membrane, the total flux was enhanced by 17.1 %, and the separation factor was improved by 46.4 %. Moreover, the embedding MIL-53(Al) variants boosted thermal and mechanical properties of the membrane, endowing it with considerable potential for practical applications.

CAS / MDL: 71-36-3 7784-13-6
研究领域: 材料科学 · 化学工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2016 · IF 2.567

Fabrication of a MIL-53(Al) Nanocomposite Membrane and Potential Application in Desalination of Dye Solutions

Huimin Ruan,Changmeng Guo,Hongwei Yu,Jiangnan Shen,Congjie Gao,Arcadio Sotto,Bart Van der Bruggen

This study reports the fabrication of mixed matrix membranes (MMMs) using immersion precipitation phase inversion for promising application in desalination of dye solutions. Aromatic poly(m-phenylene isophthalamide) is used as the polymer material, and the metal–organic framework MIL-53(Al) is added to develop integrally skinned asymmetric membranes. Successful dispersion of MIL-53(Al) particles into the membrane-separating layer is confirmed by scanning electron microscopy. The optimum performance of the membranes is obtained at 0.5 wt % MIL-53(Al) concentration. In particular, the M-0.5 membrane is planned for use in separating dye/salt aqueous mixtures. It is observed that the M-0.5 membrane has a rejection for NaCl and Na2SO4 below 11% and 37%, respectively, in mixed salt/dye solutions. Additionally, the M-0.5 membrane is found to have a rejection rate of 83.9%, 98.3%, and 99.8% for nitroso-R salt, xylenol orange, and ponceau S, respectively, in mixed Na2SO4/dye solutions. The rejection rate for Na2SO4 is lower than that of some commercial nanofiltration membranes (NF90, NF270, and DK). The membrane is promising for dye desalination in industrial-scale applications.

研究领域: 材料科学 · 环境工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Immobilized lipase on MIL-53(Al)-AM11 with regulatable hydrophobic surface for flavor ester synthesis

Le Zhong,Yuxiao Feng,Zichen Wang,Tian Tian,Yali Bi,Jiandong Cui

Enzymatic synthesis of flavor esters is crucial for applications in food, beverage, and cosmetics industries. However, the poor activity and stability of free lipase hinder these reaction. Inspired by the concept of lipase interface activation, MIL-53(Al)-NH 2 was modified with alkyl acid anhydrides of varying chain lengths to tailor its hydrophobicity, and Candida Rugosa lipase (CRL) was subsequently immobilized on this surface to achieve efficient interface activation. The resulting CRL@MIL-53(Al)-AM11 exhibited 3.5 times higher activity than the unmodified CRL@MIL-53(Al)-NH 2 . Moreover, CRL@MIL-53(Al)-AM11 enabled one-step purification of crude CRL via selective adsorption. It also showed enhanced storage and thermal stability as well as higher resistance to protease degradation and denaturants than free CRL. CRL@MIL-53(Al)-AM11 retained 75 % of its initial activity after 30 min treatment at 55 °C, whereas the free CRL retained only 41 %. After 11 days of storage, CRL@MIL-53(Al)-AM11 maintained 70 % of its initial activity, in contrast to 36 % for the free lipase. Notably, CRL@MIL-53(Al)-AM11 achieved a 97 % conversion rate in the esterification synthesis of the flavoring substance (butyl butyrate) within 24 h and retained over 40 % conversion after five consecutive cycles. Therefore, this strategy offers a feasible approach for constructing high-performance immobilized lipases for flavor ester synthesis.

CAS / MDL: 109-21-7
研究领域: 生物化学 · 食品科学 · 酶工程
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INORGANIC CHEMISTRY · 2024 · IF 4.3

Freeze-Cast MIL-53(Al) Porous Materials with High Thermal Insulation and Flame Retardant Properties

Yuhao Che,Wenhui Li,Chunqi Wang,Xuemin Zhang,Zilei Guo,Aziz Bakhtiyarovich Ibragimov,Junkuo Gao

The development of materials with superior thermal insulation and flame retardancy is critical for industrial applications and daily life. Metal–organic framework (MOF)@poly(vinyl alcohol) (PVA) (MOF@PVA) aerogel composites have demonstrated remarkable thermal insulation and flame retardancy properties. In this work, MIL-53(Al) was directly mixed with PVA and formed by freeze-drying, and the influence of the pore structure on the thermal insulation and flame retardancy properties of the materials was investigated. The incorporated MIL-53(Al) nanoparticles introduced abundant micro- and mesopores, enhancing the complexity of the pore structure and improving the thermal insulation and flame retardancy properties of the aerogels. The directionally freeze-cast aerogel achieved a thermal conductivity of 0.040 W·mK–1, and maintained excellent thermal insulation ability even at 220 °C. Furthermore, the aerogel exhibited nonflammable and self-extinguishing characteristics. This environmentally friendly manufacturing method provides new ideas for the design of MOF-based composites, thereby expanding their application areas.

研究领域: 材料科学 · 化学工程 · 热能工程
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ANALYTICAL CHEMISTRY · 2013 · IF 5.695

Fluorescent Metal–Organic Framework MIL-53(Al) for Highly Selective and Sensitive Detection of Fe3+ in Aqueous Solution

Cheng-Xiong Yang,Hu-Bo Ren,Xiu-Ping Yan

Fluorescent metal–organic frameworks (MOFs) have received great attention in sensing application. Here, we report the exploration of fluorescent MIL-53(Al) for highly selective and sensitive detection of Fe3+ in aqueous solution. The cation exchange between Fe3+ and the framework metal ion Al3+ in MIL-53(Al) led to the quenching of the fluorescence of MIL-53(Al) due to the transformation of strong-fluorescent MIL-53(Al) to weak-fluorescent MIL-53(Fe), allowing highly selective and sensitive detection of Fe3+ in aqueous solution with a linear range of 3–200 μM and a detection limit of 0.9 μM. No interferences from 0.8 M Na+; 0.35 M K+; 11 mM Cu2+; 10 mM Ni2+; 6 mM Ca2+, Pb2+, and Al3+; 5.5 mM Mn2+; 5 mM Co2+ and Cr3+; 4 mM Hg2+, Cd2+, Zn2+, and Mg2+; 3 mM Fe2+; 0.8 M Cl–; 60 mM NO2– and NO3–; 10 mM HPO42–, H2PO4–, SO32–, SO42–, and HCOO–; 8 mM CO32–, HCO3–, and C2O42–; and 5 mM CH3COO– were found for the detection of 150 μM Fe3+. The possible mechanism for the quenching effect of Fe3+ on the fluorescence of MIL-53(Al) was elucidated by inductively coupled plasma-mass spectrometry, X-ray diffraction spectrometry, and Fourier transform infrared spectrometry. The specific cation exchange behavior between Fe3+ and the framework Al3+ along with the excellent stability of MIL-53(Al) allows highly selective and sensitive detection of Fe3+ in aqueous solution. The developed method was applied to the determination of Fe3+ in human urine samples with the quantitative spike recoveries from 98.2% to 106.2%.

研究领域: 材料科学 · 分析化学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

High-Efficient removal of mercury in water by the flexible NH2-MIL-53(Al): Exploiting the gate opening effect

Meipeng Jian,Xiaoqin Yang,Congxin Huang,Chaochun Tang,Xiwang Zhang,Ruiping Liu,Haiyan Li

Flexible metal–organic frameworks (MOFs) with the gate opening feature can optimize the removal efficiency on the adsorption behavior by accommodating to the specific target molecules. In this study, a flexible MOF denoted as NH 2 -MIL-53(Al) was investigated to remove Hg(II) from water, in which the adsorption capacities of large-pore NH 2 -MIL-53(Al) (NH 2 -MIL-53(Al)-LP) for Hg(II) reached 433.20 mg/g, which is about 4 times higher than narrow-pore NH 2 -MIL-53(Al) (112.75 mg/g). Further, the kinetic experiment also revealed that nearly 90 % Hg(II) can be captured within 60 min for NH 2 -MIL-53(Al)-LP. Advanced characterizations and density functional theory calculations demonstrated that the strong coordination of the amino and oxygen centers on NH 2 -MIL-53(Al)-LP to Hg(II). Importantly, molecular dynamic simulation verified the gate opening effect of NH 2 -MIL-53(Al)-LP, as the faster diffusivity of Hg(II) ions in NH 2 -MIL-53(Al)-LP was observed. This work provides another opportunity in designing the pore geometry of porous materials for water remediation.

研究领域: 环境科学 · 材料科学
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