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MIL-101
FOOD CHEMISTRY · 2023 · IF 8.8

A fluorescence and SERS dual-mode sensing on tetracycline antibiotics based on Ag@NH2-MIL-101(Al) nanoprobe

Junjie Qi,Jingkun Li,Yuqi Wan,Yu Li,Fuwei Pi

Antibiotic residues are becoming more and more concern due to the increasingly serious resistance from bacteria to organism. On-site and accurate evaluation on antibiotics is necessary and urgent to effectively solve such public issue. To provide point-of-care-test (POCT) ideas for antibiotic accurate evaluation, a fluorescence (FL)-surface-enhanced Raman scattering (SERS) dual-mode detection of tetracycline antibiotic (TCs) was realized for the first time. Based on the inner filter effect in Ag@NH 2 -MIL-101(Al) nanoprobe, the fluorescence quenching was induced and the SERS signal was swiftly turn on through π-π interaction and hydrogen bonding in the presence of TCs. This FL-SERS dual mode sensor displayed excellent detection limits (FL in ∼10 −3 ppm, SERS in ∼10 −5 ppm), and achieved a reliable detection of TCs in honey with a recovery rate of 84.45%−112.08%. This method combines the advantages of FL and SERS detection, meanwhile, two techniques verified against each other to achieve highly sensitive and specific FL-SERS dual-mode sensor for TCs. We believe that such antibody-or aptamer-independent FL and SERS complementary nanoprobe can be applied to fast, direct and multiple sensing in environment and food hazards.

CAS / MDL: 10312-55-7
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Greenhouse Gases-Science and Technology · 2021 ·Vol. 11 ·期 6 ·1234-1244 · IF 2.013

Cu nanoparticles anchored in MIL-101 metal-organic frameworks for the selective hydrogenation of CO2-derived ethylene carbonates

Ting Lei,Dong Wei,Dongya Feng,Hao Chen,Hairong Yue

The Cu-based catalysts have been widely employed in the hydrogenation of CO 2 -derived ethylene carbonate (EC) to ethylene glycol (EG) and other derivatives, but still suffered from some problems such as unsatisfactory selectivity and catalyst stability. Herein, a Cu@MIL-101 catalyst was prepared via a two-solvent method to anchor copper (Cu) nanoparticles into the MIL-101 metal organic frameworks, which exhibited superior catalytic performance with ∼100% conversion, 2-hydroxyethyl formate (2-HEF) selectivity of 82% at 160°C, or EG selectivity of ∼92% at 180°C. The characterization results showed that the Cu 0 and Cr 3+ species play a key role on the dissociation of H 2 and activation of C-O and C=O bonds in the esters, and thus exhibited an excellent catalytic performance of the EC hydrogenation. In addition, the strong interaction between Cu 0 species and unsaturated coordination Cr 3+ species in the MIL-101 framework resulted in the high stability. Since the product of methanol was not generated on the Cu@MIL-101 catalyst, it is valuable to produce 2-HEF by controlling the temperature of 160°C in the EC hydrogenation rection. © 2021 Society of Chemical Industry and John Wiley & Sons, Ltd.

CAS / MDL: 96-49-1 100-21-0
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Nanomaterials · 2020 ·Vol. 10 ·期 9 ·1655 · IF 4.324

Molecularly Imprinting Polymers (MIP) Based on Nitrogen Doped Carbon Dots and MIL-101(Fe) for Doxorubicin Hydrochloride Delivery

Yuqiong Shi,Yuxuan Wang,Jinhua Zhu,Wei Liu,Md. Zaved H. Khan,Xiuhua Liu

MIL-based molecularly imprinted polymer (MIP) nanocomposites were successfully synthesized through a simple and versatile stirring auxiliary encapsulation method. MIP as a carrier has been applied to the highly efficient selective recognition and sustained release of doxorubicin hydrochloride (DOX). The adsorption mechanism and release behavior of[email protected]in vitro were also discussed. Adsorption studies showed that MIP using DOX as template had specific selectivity to DOX, and its optimal drug loading efficiency reached 97.99%. The adsorption isotherm accorded with Freundlich models. The cumulative release curve showed that at the conditions of pH 5.5 and 7.4, the nanomaterials have a slow-release effect on the release of DOX. In addition, the cytotoxicity and bioactivity of MIP nanoparticles on HepG2 and HL-7702 cell lines measured by MTT assay also proved their low toxicity and biological activity. The cell activity of HepG2 and HL-7702 incubated with MIP for 24 h was 69.9% and 76.07%, respectively. These results collectively illustrated that the MIP nano-materials synthesized in this study can be efficiently employed to the drug delivery systems.Keywords:MIP;nanocomposites;drug delivery;DOX;controlled release

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CHEMICAL ENGINEERING JOURNAL · 2020 · IF 10.652

Implanting polyethylene glycol into MIL-101(Cr) as hydrophobic barrier for enhancing toluene adsorption under highly humid environment

Jiaxing Wang,Yaseen Muhammad,Zhu Gao,Syed Jalil Shah,Shuangxi Nie,Lihan Kuang,Zhongxing Zhao,Zhiwei Qiao,Zhenxia Zhao

Adsorption of volatile organic compounds (VOCs) under high humidity is crucial for metal–organic frameworks (MOFs) in practical applications. To enhance competitive adsorption of VOCs under humidity, polyethylene glycol (PEG) with hydrophobic short-chains was implanted as hydrophobic barrier into MIL-101(Cr). Characterization and simulation results showed that the terminal –OH groups of PEG chains were coordinated with the Cr sites in MIL-101(Cr) and formed a hydrophobic pore (11.2 Å) of “cage-in-cage” geometry. PEG chains significantly hindered the diffusion of water into the MOFs while allowed toluene molecules. The new hydrophobic pores of PEG 5 @MIL-101 enhanced adsorption capacity and diffusivity for toluene by 30.8% (4.68 mmol/g at 1 mbar) and 31.5% (1.88 × 10 −2 ), while decreased adsorption capacity and diffusivity for water by 53.7% and 26.8% compared to primary MOF. Breakthrough curve showed 3.3 times of toluene working capacity on PEG 5 @MIL-101 at 80% RH compared to pristine MIL-101(Cr).

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Catalysts · 2020 ·Vol. 10 ·期 4 ·453 · IF 3.52

MIL-101(Cr) for CO2 Conversion into Cyclic Carbonates, Under Solvent and Co-Catalyst Free Mild Reaction Conditions

Emmanuelia Akimana,Jichao Wang,Natalya V. Likhanova,Somboon Chaemchuen,Francis Verpoort

Mild reaction conditions (nearly room temperature and atmospheric CO2pressure) for the cycloaddition of CO2with epoxides to produce cyclic carbonates were investigated applying MIL-101(Cr) as a catalyst. The MIL-101 catalyst contains strong acid sites, which promote the ring-opening of the epoxide substrate. Moreover, the high surface area, enabling the adsorption of more CO2(substrate), combined with a large pore size of the catalyst is essential for the catalytic performance. Additionally, epoxide substrates bearing electron-withdrawing substituents or having a low boiling point demonstrated an excellent conversion towards the cyclic carbonates. MIL-101(Cr) for the cycloaddition of carbon dioxide with epoxides is demonstrated to be a robust and stable catalyst able to be re-used at least five times without loss in activity.Keywords:MIL-101;heterogeneous catalyst;CO2cycloaddition;carbonate;ambient conditions

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DALTON TRANSACTIONS · 2019 ·Vol. 48 ·期 16 ·5384-5396 · IF 4.052

Surface functionalization of MIL-101(Cr) by aminated mesoporous silica and improved adsorption selectivity toward special metal ions

Xueping Quan,Zhongqiao Sun,Hao Meng,Yide Han,Junbiao Wu,Junli Xu,Yan Xu,Xia Zhang

Developing novel solid adsorbents with high efficiency and excellent selectivity is always an important target in the removal of toxic metal ions from waste water. In this study, a composite nano-adsorbent NH2-mSiO2@MIL-101(Cr) has been fabricated and applied in the efficient removal of Pb(II) and Cr(VI) for the first time. The nanocomposites were characterized by using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), fourier-transform infrared (FT-IR) spectroscopy and thermal gravimetry analysis (TG). The results indicate that a typical core@shell structure has been fabricated by fully coating a mesoporous SiO2 shell over the micro/mesoporous MIL-101(Cr). As a result, the surface charge and the zeta potentials change significantly. Two toxic metal ions, namely, Pb(II) and Cr(VI) were chosen as the main adsorption targets to evaluate the surface adsorption activities. The adsorption conditions were optimized, the influences of other coexisting ions were explored, and the adsorption selectivity was investigated. Interestingly, the NH2-mSiO2@MIL-101(Cr) nanocomposites display a prominent adsorption activity compared with the original MIL-101(Cr) and non-aminated mSiO2@MIL-101(Cr) and excellent selectivity toward Pb(II) in the presence of other divalent metal ions. The adsorption kinetics and adsorption thermodynamics were simulated accordingly, and the enhanced adsorption mechanism was also suggested. The good reusability and adsorption selectivity of the NH2-mSiO2@MIL-101(Cr) suggest their potential applications in the selective removal of special metal ions such as Pb(II) from the waste water.

CAS / MDL: 919-30-2
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2019 · IF 2.298

Adsorption Behavior and Mechanism of Sulfonamide Antibiotics in Aqueous Solution on a Novel MIL-101(Cr)@GO Composite

Xiuna Jia,Sijia Li,Yudan Wang,Ting Wang,Xiaohong Hou

The occurrence of numerous antibiotics, such as sulfonamides (SAs), in environmental water has recently heightened concerns in consideration of their potential threat to human health and aquatic ecosystems. The removal of pharmaceuticals by adsorption comprises some of the most promising techniques because of their easy regeneration, low cost, and high efficiency. In this work, MIL-101(Cr)@GO, with a high surface area, was synthesized. Its adsorption properties toward three SAs were examined in batch adsorption experiments to probe the underlying factors of adsorption behavior and the mechanism for the first time. The pronounced factors that influenced the adsorption and removal process were investigated. The adsorption kinetics and isotherms were studied in order to characterize the operation. The adsorption kinetics demonstrated that the adsorption process would match the pseudo-second-order kinetic model. Furthermore, the adsorption was spontaneous, entropy was decreased, and the process was exothermic, and the equilibrium data was more appropriate described by the Freundlich isotherm model. Moreover, the adsorption–desorption of MIL-101(Cr)@GO could be consecutively cycled at least five times. MIL-101(Cr)@GO exhibited remarkable removal efficiency compared to MIL-100(Fe), MIL-101(Cr), and other adsorbents. These results demonstrated that MIL-101(Cr)@GO would be a promising adsorbent for the removal of sulfonamides from water samples and even for environmental protection.

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DALTON TRANSACTIONS · 2018 ·Vol. 48 ·期 3 ·989-996 · IF 4.099

Benzoic acid as a selector–modulator in the synthesis of MIL-88B(Cr) and nano-MIL-101(Cr)

Ling Yang,Tian Zhao,Ishtvan Boldog,Christoph Janiak,Xiao-Yu Yang,Qiang Li,Yan-Jia Zhou,Yong Xia,Deng-Wang Lai,Yue-Jun Liu

The concentration of benzoic acid was found to exercise efficient control over the formation of either MIL-101(Cr) or MIL-88B(Cr) under otherwise similar hydrothermal synthetic conditions. Nanocrystals of MIL-101(Cr) with ∼100 nm average size and excellent SBET = 3467 m2 g−1 are obtained at lower concentrations of benzoic acid, while at higher concentrations the microparticulated MIL-88B(Cr) product is formed. Hereby a new efficient synthetic method towards the elusive MIL-88B(Cr), yet reported only once without synthetic details, is proposed. The obtained MIL-88B(Cr) has an interesting and potentially valuable property of retaining its high-volume form (Vcell ∼ 2000 Å3) after thermal activation. The degassing of MIL-88B(Cr) in a vacuum at 250 °C yields a porous material with a SBET area of 1136 m2 g−1, which is around the theoretical maximum. The transition to the denser ‘closed’ form (Vcell ∼ 1500 Å3) occurs only at 350 °C, when all of the benzoate/benzoic acid, hindering the process, is removed.

CAS / MDL: 7789-02-8 100-21-0
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Journal of the Taiwan Institute of Chemical Engineers · 2015 · IF 3

Facile synthesis of magnetic hybrid Fe3O4/MIL-101 via heterogeneous coprecipitation assembly for efficient adsorption of anionic dyes

Zhongwei Jiang,Yuanfang Li

Integration of other functional materials onto the surface or into the matrixes of metal-organic frameworks (MOFs) is an attractive and effective approach to fabricate multifunctional MOFs. Herein, we report a facile and novel strategy for in situ synthesis of magnetic hybrid Fe 3 O 4 /MIL-101 via heterogeneous coprecipitation assembly. Characterizations showed that the Fe 3 O 4 nanoparticles were uniformly coated on the outer-surface of MIL-101. The as-synthesized Fe 3 O 4 /MIL-101 composite holds larger BET surfaces area, pore volume and higher positive charge than MIL-101. These preferable properties make it to be an excellent candidate for adsorption and removal of anionic dye from aqueous solution. The present work provides a new insight for in situ synthesis of Fe 3 O 4 -functionalized MOFs, offering an alternative way to prepare magnetic hybrid materials for a wide range of applications.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2016 · IF 3.299

Adsorption of three selected pharmaceuticals and personal care products (PPCPs) onto MIL-101(Cr)/natural polymer composite beads

Ning Zhuo,Yaqian Lan,Weiben Yang,Zhen Yang,Xiaomin Li,Xia Zhou,Yang Liu,Jiachun Shen,Xuntong Zhang

Porous metal-organic frameworks (MOFs) have great potential as high-effective adsorbents for water treatment. However, poor separability restricts their practical application. To overcome the drawback, both MIL-101(Cr)/sodium alginate (MIL-101(Cr)/SA) and MIL-101(Cr)/chitosan (MIL-101(Cr)/CS) composite beads were prepared and characterized. Adsorption of three selected pharmaceuticals and personal care products (PPCPs) (benzoic acid (BEN), ibuprofen (IBU) and ketoprofen (KET)) onto the two composite beads was investigated and compared with pristine SA and CS beads. Kinetic plots, pH dependence, isotherm data, and influences of ionic strength were reported. The MIL-101(Cr)/CS beads exhibit much higher adsorption capacity than SA, CS and MIL-101(Cr)/SA, and the adsorption amounts of three PPCPs onto MIL-101(Cr)/CS follow the order of KET   >   IBU   >   BEN. The adsorption amounts of the three PPCPs on the MIL-101(Cr)/CS increased quickly during the first 60   min of contact time and then achieved the adsorption equilibrium after ∼180   min. Not only the protonated amine groups but also the Cr center of the adsorbents exerted electrostatic attraction with the deprotonated carboxyl groups of contaminants, as elucidated by X-ray photoelectron spectroscopy (XPS). Based on the adsorption isotherms and π-energy analysis of three PPCPs, π-π interaction of aromatic groups between adsorbents and contaminants also contributed to the adsorption. The MIL-101(Cr)/CS beads exhibited good regenerability over several repeated adsorption/desorption cycles. Overall, this study is believed to enlarge the application of MOFs on the removal of emerging contaminants from waters.

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Analytical Methods · 2016 ·Vol. 8 ·期 15 ·3263-3269 · IF 1.915

Electrochemical determination of lead based on metal–organic framework MIL-101(Cr) by differential pulse anodic stripping voltammetry

Yangjuan Wang,Kejing Du,Yifu Chen,Yijun Li,Xiwen He

Green octahedral crystals of MIL-101(Cr) were synthesized and used for the determination of Pb2+ at the trace level by differential pulse anodic stripping voltammetry (DPASV) because of their good adsorption capability for Pb2+. The synthesized MIL-101(Cr) was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). Parameters affecting the electrochemical process, such as the pH of the electrolyte solution, the volume of the MIL-101(Cr) suspension, the potential and the time for accumulation, were investigated in detail. Under optimal conditions, the electrochemical sensor had a linear response over the concentration range of 1.0 × 10−9 to 1.0 × 10−6 mol L−1 (R2 = 0.999) with a detection limit of 5.0 × 10−10 mol L−1 (S/N = 3). The method was successfully applied to the determination in real samples and good recoveries are obtained from different spiked samples.

CAS / MDL: 7664-39-3
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MICROCHIMICA ACTA · 2016 ·Vol. 183 ·期 12 ·3151-3157 · IF 4.831

Highly chemiluminescent metal-organic framework of type MIL-101(Cr) for detection of hydrogen peroxide and pyrophosphate ions

Yu Haili,Long Dengying

The authors describe a highly chemiluminescent metal-organic framework (MOF) that was obtained by loading the pores of MIL-101(Cr) with luminol. Immobilization is based on Lewis acid-base interactions between the coordinatively unsaturated metal sites of MIL-101(Cr) and the amino groups of luminol. The luminol-loaded MOF displays strong chemiluminescence (CL) in the presence of hydrogen peroxide (H 2 O 2 ) in alkaline solution. Pyrophosphate (PPi), in turn, acts as a quencher of this CL. These findings have been exploited in the design of a CL based method for the determination of either H 2 O 2 or PPi. The assays for H 2 O 2 works in the 3 to 100 μM concentration range and has a detection limit of 0.5 μM. The quenchometric assay for PPi works in the 5 to 70 μM concentration range and has a 1.2 μM detection limit. Luminol-embedded metal-organic frameworks (MOFs) with high chemiluminescent activity were prepared and used for the sensitive determination of either H 2 O 2 or pyrophosphate ions.

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