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MIL-101
APPLIED ORGANOMETALLIC CHEMISTRY · 2024 ·Vol. 38 ·期 9 ·e7614 · IF 3.7

In-situ construction of Bi2O2CO3/MIL-101(Cr) nanosheet catalyst for enhanced photocatalytic degradation of organic dye molecules from water

Qiuyun Zhang,Feiran Xie,Jialu Wang,Tianqing Wang,Jiao Lei,Weihua Li,Jingsong Cheng,Yutao Zhang

For nearly a century, the excessive discharge of organic contaminants has gradually polluted water and endangered people's health, and photocatalysis has been prominently employed to remove persistent recalcitrant organic. Here, MIL-101(Cr) was firstly employed to introduce thin-layered Bi 2 O 2 CO 3 for the formation of Bi 2 O 2 CO 3 /MIL-101(Cr) nanosheet composite, by a simple and low-temperature in-situ growth approach. The phase, morphology, optical, and surface characteristics of the fabricated composite were characterized through XRD, FTIR, SEM-EDS, N 2 adsorption–desorption, UV–Vis DRS, PL, TG, and XPS techniques, and the ability in the photocatalytic breakdown of rhodamine B (RhB) molecule under visible light was also studied. The results of characterization analysis and optical analysis exhibited that Bi 2 O 2 CO 3 /MIL-101(Cr) has large pore size, good visible light response-ability, and the heterojunction created by intercalating Bi 2 O 2 CO 3 on MIL-101(Cr). Photocatalytic studies revealed that Bi 2 O 2 CO 3 /MIL-101(Cr) had superior RhB degradation activity than pure MIL-101(Cr) and Bi 2 O 2 CO 3 , which achieved 97.1% with visible light irradiation for 20 mg/l RhB. Meanwhile, the Bi 2 O 2 CO 3 /MIL-101(Cr) composite displayed good recyclability after three cycles as revealed by XRD and FTIR analysis proving their excellent stability. This study provides feasible insight into developing novel and efficient MIL-101-based heterojunction catalysts for environmental remediation in the future.

研究领域: 环境科学 · 材料科学
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2021 ·Vol. 22 ·期 19 ·10412 · IF 5.924

Enhanced Fungicidal Efficacy by Co-Delivery of Azoxystrobin and Diniconazole with Cauliflower-Like Metal–Organic Frameworks NH2-Al-MIL-101

Huiping Chen,Yongpan Shan,Lidong Cao,Pengyue Zhao,Chong Cao,Fengmin Li,Qiliang Huang

Long-term use of a single fungicide increases the resistance risk and causes adverse effects on natural ecosystems. Controlled release formulations of dual fungicides with different modes of action can afford a new dimension for addressing the current issues. Based on adjustable aperture and superhigh surface area, metal–organic frameworks (MOFs) are ideal candidates as pesticide release carriers. This study used Al3+as the metal node and 2-aminoterephthalic acid as the organic chain to prepare aluminum-based metal–organic framework material (NH2-Al-MIL-101) with “cauliflower-like” structure and high surface area of 2359.0 m2/g. Fungicides of azoxystrobin (AZOX) and diniconazole (Dini) were simultaneously encapsulated into NH2-Al-MIL-101 with the loading content of 6.71% and 29.72%, respectively. Dual fungicide delivery system of AZOX@Dini@NH2-Al-MIL-101 demonstrated sustained and pH responsive release profiles. When the maximum cumulative release rate of AZOX and Dini both reached about 90%, the release time was 46 and 136 h, respectively. Furthermore, EC50values as well as the percentage of inhibition revealed that AZOX@Dini@NH2-Al-MIL-101 had enhanced germicidal efficacy against rice sheath blight (Rhizoctonia solani), evidenced by the synergistic ratio of 1.83. The present study demonstrates a potential application prospect in sustainable plant protection through co-delivery fungicides with MOFs as a platform.Keywords:NH2-Al-MIL-101;controlled release;dual encapsulation;synergistic effect;rice sheath blight

CAS / MDL: 10312-55-7
研究领域: 植物保护 · 材料科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Hydrogen bond donor functionalized poly(ionic liquids)@MIL-101 for the CO2 capture and improving the catalytic CO2 conversion with epoxide

Yichen Jiang,Dazhi Li,Yifei Zhao,Jianmin Sun

Hydrogen bond donor functionalized poly(ionic liquids) were incorporated into MIL-101 framework for synthesis of composites PIL-R@MIL-101 (R = COOH, OH, NH 2 ). The effect of different hydrogen bond donors on CO 2 -epoxide cycloaddition reaction was discussed through XPS, NH 3 -TPD characterizations. Thereinto, PIL-COOH@MIL-101 showed efficient catalytic performance in the cycloaddition reaction of CO 2 and epichlorohydrin , 92.7% substrate conversion was obtained under 70 °C, 1.0 MPa, cocatalyst- and solvent-free conditions for 2.5 h. The improved activity was benefited from the synergistic effects of Lewis acidic Cr centers, carboxyl group, and nucleophilic Br - , together with the high surface area (1178 m 2 /g), and good CO 2 affinity. In addition, PIL-COOH@MIL-101 also showed facile recovery method by easy centrifugation and good recycling stability. Considering the good CO 2 affinity, excellent catalytic performance in CO 2 cycloaddition reaction, better thermal and recycling stabilities, the facilely prepared functionalized poly(ionic liquid)@MIL-101 composite would exhibit promising application prospect in CO 2 capture and conversion.

研究领域: 材料科学 · 化学工程 · 环境科学
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JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL · 2015 · IF 3.615

Pt nanoparticles entrapped in mesoporous metal–organic frameworks MIL-101 as an efficient catalyst for liquid-phase hydrogenation of benzaldehydes and nitrobenzenes

Huiyan Pan,Xiaohong Li,Yin Yu,Junrui Li,Jun Hu,Yejun Guan,Peng Wu

Metal organic-framework MIL-101 and inorganic mesoporous composites Al 2 O 3 @SBA-15 supported Pt catalysts, Pt/MIL-101 and Pt/Al 2 O 3 @SBA-15 catalysts, were prepared and characterized by means of X-ray diffraction (XRD), N 2 adsorption–desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), CO chemisorption and thermo-gravimetric (TG) analysis. Pt nanoparticles were highly dispersed on both supports. In liquid-phase hydrogenation of nitrobenzene, benzaldehyde and their derivatives, the Pt/MIL-101 catalyst was superior to the Pt/Al 2 O 3 @SBA-15 catalyst in water. For liquid-phase hydrogenation of nitrobenzene with the Pt/MIL-101 catalyst, owing to high solubility of nitrobenzene in ethanol, the reaction in ethanol went much faster than that in water, furnishing a turnover frequency (TOF) in ethanol up to 18,053   h −1 , almost triple of that obtained in water under similar conditions. The highest TOF of 25,438   h −1 was obtained in ethanol for hydrogenation of 3-chloro-nitrobenzene with the Pt/MIL-101 catalyst. As for hydrogenation of benzaldehyde series, 2-fluoro-benzaldehyde and 3-fluoro-benzaldehyde gave the highest TOFs of 5146   h −1 and 3165   h −1 in water with the Pt/MIL-101 and Pt/Al 2 O 3 @SBA-15 catalysts, respectively. We deduce that surface property of MIL-101 with high hydrophobicity is helpful to enrich reactants around the Pt/MIL-101 catalyst in water, where nitrobenzene or benzaldehyde and its derivatives have a limited solubility, so that high catalytic performance was achieved with the Pt/MIL-101 catalyst in water. Of particular note is that the Pt/MIL-101 catalyst can be reused at least four times without loss in activity or selectivity.

CAS / MDL: 98-95-3
研究领域: 材料科学 · 催化化学
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CARBOHYDRATE POLYMERS · 2025 · IF 12.5

pH-responsive starch-based bilayer film functionalized with alliin loaded MIL-101 (Fe) for active food packaging

Sa Liu,Yapeng Chen,XinKuan Li,Yijia Yao,Huashan Wang,Meiyi Wang

Food packaging films containing antimicrobial reagents play a crucial role in preventing bacterial-induced fruit decay. This study proposes a bilayer film consisting of an internal amino-modified starch hydrophilic layer and an external amino-modified polyvinyl alcohol/polylactic acid hydrophobic layer, embedding alliin@MIL-101(Fe) as an antibacterial agent, utilizing the pH reduction of fruit decay sites to achieve pH-responsive release, enhancing antibacterial performance. Fourier transform infrared (FTIR) and scanning electron microscopy (SEM) analyses confirm successful crosslinking between amino and aldehyde groups, resulting in the formation of imine bonds and a mesh-like structure conducive to adsorption. Under acidic conditions, the cumulative release rate of alliin reached 74 % within 36 h. Compared to a simple mixture, the tensile strength of the alliin@MIL/NST-NPVA/PLA film reached 34.771 MPa, and transmittance in the wavelength range of 200–370 nm decreased to 0. The scavenging rate of DPPH free radicals in the film can reach 83 %. In addition, the water vapor permeability and oxygen permeability of the film are approximately 7.62 × 10 −16 [g/ (m 2 ‧24 h‧0.1 mm)] and 6.83 (m 2 ‧24 h‧0.1 MPa), respectively; moisture content and water solubility decreased to 10.99 % and 20.77 %. This composite film extended the shelf life of strawberries from 2 to 7 days, significantly enhancing freshness.

CAS / MDL: 9005-25-8
研究领域: 食品科学 · 材料科学
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npj Clean Water · 2025 ·Vol. 8 ·期 1 ·1-16 · IF 11.4

Preparation of unsaturated MIL-101(Cr) with Lewis acid sites for the extraordinary adsorption of anionic dyes

Keshta Basem E.,Yu Haojie,Wang Li,Yi Hong,Jian Shan,Uddin MD Alim,Ouyang Chenguang,Wang Yu,Yuan Xunchun,Zhang Yanhui,Jin Yang,Basit Abdul,Owais Malik Muhammad,Awan Khan Manqoosh

Anionic dyes contaminate water and severely disrupt aquatic ecosystems, urgently demanding effective treatment solutions for safety. This study explores the synthesis of unsaturated MIL-101(Cr) and its exceptional performance in removing anionic dyes from polluted water systems. The synthesized MIL-101(Cr) exhibits medium Lewis’s acid and strong Brønsted acid sites, a high specific surface area (>3000 m 2 /g), and a Zeta potential of 30 mV, contributing to its strong adsorption capability. Adsorption studies reveal Langmuir isotherm model fitting, with maximum adsorption capacities of 4231, 1266, and 568 mg/g for Acid Blue 92, Congo Red, and Acid Blue 90, respectively. The chemisorption process follows pseudo-second-order kinetics and is spontaneous and exothermic. MIL-101(Cr) demonstrates chemical and water stability, maintaining over 80% removal efficiency after five recycling cycles. This research provides valuable insights into treating anionic dye-contaminated wastewater using MIL-101(Cr) as an efficient adsorbent.

研究领域: 环境科学 · 材料科学
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JOURNAL OF SOLID STATE CHEMISTRY · 2019 · IF 2.291

Synthesis of MIL-101(Fe)/SiO2 composites with improved catalytic activity for reduction of nitroaromatic compounds

Yixuan Huang,Hao Lin,Yanhui Zhang

Carboxylate systems with inert oxide, namely, MIL-101(Fe)/SiO 2 , have been prepared by hydrothermal reactions and characterized. MIL-101(Fe)/SiO 2 exhibits superior catalytic activities for p -nitrophenol reduction with a high conversion of 93.8% in 4 ​min. It is obvious that the catalytic activity for reduction of nitroaromatic compounds is enhanced, however, the proportion of active components on a catalyst is reduced. One hypothesis is that the interfacial effect between SiO 2 and MIL-101(Fe) complexes helps to increase the catalytic activity. The increase of the interface component greatly improved the free energy of the interface of the solid, and the structure-related properties such as the ion valence state and the electron motion transfer of the interface have undergone considerable changes. In addition, the stability of the catalyst under the conditions of different acid-base was also investigated. It is supposed to broaden the application of the interface effect of the complex with SiO 2 .

CAS / MDL: 100-21-0
研究领域: 材料科学 · 催化化学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2022 · IF 5.518

Activation of Na2S2O8 by MIL-101(Fe)/MoS2 composite for the degradation of tetracycline with visible light assistance

Zihao Hu,Beiyang Guo,Huiqi Wu,Fang Zhu,Sridhar Komarneni,Jianfeng Ma

In this paper, MIL-101(Fe) and MoS 2 composites (MIL-101(Fe)/MoS 2 ) were synthesized using a facile solvothermal method . As a new degradation system, the synthesized composites were investigated using persulfate (PS) activation based on visible light (Vis). To establish the superiority of a heterogeneous photochemical catalysis system, the MIL-101(Fe)/MoS 2 was used as the catalyst in the presence of Na 2 S 2 O 8 with visible light irradiation. In the system mentioned, the MIL-101(Fe)/MoS 2 catalyst presented a much better catalytic ability than that of either a single photocatalysis or chemocatalysis system. The better catalytic ability suggests that the MIL-101(Fe)/MoS 2 catalyst was capable of effectively integrating photocatalysis and chemocatalysis leading to the highest degradation efficiency of 85% in 40 min with tetracycline as the target pollutant. The catalytic system MIL-101(Fe)/MoS 2 /PS/Vis degraded TC pollutant by forming species of O 2 ‾, 1 O 2 , hydroxyl radicals (•OH) and sulfate radicals (•SO 4 ‾) to degrade TC. Furthermore, the MIL-101(Fe)/MoS 2 catalyst displayed better catalytic performance compared to those materials that were previously reported, as verified by the good stability (reached 80% after three cycles) and the high TC degradation rate (85%) of the currently developed material. This system may be applicable to the degradation of TC and other challenging organic pollutants .

研究领域: 环境科学 · 材料科学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2023 ·Vol. 140 ·期 25 ·e53978 · IF 3

Anchoring HPW by amino-modified MIL-101(Cr) to improve the properties of SPEEK in proton exchange membranes

Xiaocan Zhang,Huixiao Ma,Tong Pei,Ruochen Zhang,Yiran Liu

Incorporating phosphotungstic acid (HPW) in proton exchange membranes (PEMs) is an effective way to improve proton conductivity, but its leakage remains a problem. It can be solved by immobilizing acid in membranes to enhance the stability of PEMs. Herein, we proposed a novel sulfonated poly(ether ether ketone) (SPEEK) composite membrane (SPEEK/HPW@MIL) that was prepared by blending amino-modified MIL-101(Cr) to anchor HPW. In this work, HPW was anchored through hydrogen bond to minimize its leakage and enhance the overall compatibility. The incorporation of MIL-101(Cr)-NH 2 also helped lower the swelling ratio and improve the dimensional stability. Compared with pristine SPEEK and SPEEK/MIL membrane, the proton conductivity of the SPEEK/HPW@MIL composite membrane increased by 26% and 14%, respectively. The superior performance recommended a promising conception for anchoring HPW in PEMs.

研究领域: 材料科学 · 化学工程
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Advanced Sustainable Systems · 2023 ·Vol. 8 ·期 2 ·2300331 · IF 7.1

Synthesis, Properties of MIL-101(Al)-NH2 Polymers Capable of Absorbing Vapor, Liquid Water Simultaneously

Cailing Yang,Wenxu Zhang,Rongnian Xu,Huaiwu Peng,Zhenshi Zhang,Xiaomei Liu,Li Li,Tingli Li,Jing Li,Pengbo Liu,Xinlu Jin,Yuanyuan Ma,Ziqiang Lei

Modified MIL-101(Al)-NH 2 (MIL-101(Al)-NH 2 -net) is used as a crosslinking agent and acrylic acid (AA) as a monomer, the MIL-101(Al)-NH 2 -net grafted polyacrylic acid (MIL-101(Al)-NH 2 -net-g-PAA (MAP)) composite water-absorbent material is synthesized using the free radical polymerization method to study the application of composite absorbent materials in water collection. The structure and morphology of the composite water-absorbent material are characterized using Fourier transform infrared spectrometry (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), Brunauer Emmett Teller (BET), and thermogravimetric analysis (TG), and the contents of ammonium persulfate (APS), MIL-101(Al)-NH 2 -net, and neutralization degree of AA are optimized. Under optimal conditions, the water absorption ratios of the composite materials in distilled water, tap water, and 0.9% NaCl solution are 744, 169.5, and 85.5 g g −1 . In addition, the properties of collecting water vapor are investigated. At 25 °C, 50% Relative Humidity (RH), 70% RH, and 90% RH, the MAP water vapor adsorption capacity is 0.0312, 0.5760, and 1.6856 g g −1 , respectively. The water vapor adsorption of MIL-101(Al)-NH 2 and MIL-101(Al)-NH 2 self-polymerization products are 0.025 and 0.1278 g g −1 , respectively. The result showed that autopolymerization can improve the water vapor adsorption performance.

研究领域: 材料科学 · 化学工程 · 环境科学
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APPLIED CLAY SCIENCE · 2022 · IF 5.907

Low-cost magnetic clay derivants from palygorskite/MIL-101(Fe) for high-performance adsorption-photocatalysis

Qiushi Jiang,Zhaolian Han,Nan Qu,Lianzhi Sun,Yafeng Yuan,Yating Ren,Zhiqiang Cheng

A low-cost palygorskite (Pal)/MIL-101(Fe) was prepared by solvothermal method and calcined under nitrogen protection to form the magnetic derivant Pal/MIL-101(Fe)-400, the successful combination of which was confirmed. The band gap (1.47 eV) of Pal/MIL-101(Fe)-400 was lower than 2.25 eV of Pal/MIL-101(Fe), indicating a significant improvement in light absorption performance. In addition, Pal/MIL-101(Fe)-400 exhibits stronger photocurrent response and lower impedance due to the formation of Fe 3 O 4 clusters with high electrical conductivity and new active centers by calcination. The prepared Pal/MIL-101(Fe)-400 can achieve 90 mg/g RhB removal completely, which is better than 77.0% adsorption of MIL-101(Fe) and 67.2% adsorption-photocatalytic of Pal/MIL-101(Fe), which also shows superparamagnetism properties and excellent cyclic stability. In addition, Pal/MIL-101(Fe)-400 mainly relies on the action of peroxy radical to oxidize organic pollutants, which is different from Pal/MIL-101(Fe). This work provides a new perspective for the construction of magnetic MOF multifunctional materials for the efficient treatment of pollutants in water.

研究领域: 环境科学 · 材料科学
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TALANTA · 2017 · IF 4.162

Fe3O4 and metal–organic framework MIL-101(Fe) composites catalyze luminol chemiluminescence for sensitively sensing hydrogen peroxide and glucose

Xue Qian Tang,Yi Dan Zhang,Zhong Wei Jiang,Dong Mei Wang,Cheng Zhi Huang,Yuan Fang Li

In this work, Fe 3 O 4 and metal–organic framework MIL-101(Fe) composites (Fe 3 O 4 /MIL-101(Fe)) was demonstrated to possess excellent catalytic property to directly catalyze luminol chemiluminescence without extra oxidants. We utilized Fe 3 O 4 /MIL-101(Fe) to develop a ultra-sensitive quantitative analytical method for H 2 O 2 and glucose. The possible mechanism of the chemiluminescence reaction had been investigated. Under optimal conditions, the relative chemiluminescence intensity was linearly proportional to the logarithm of H 2 O 2 concentration in the range of 5–150   nM with a limit of detection of 3.7   nM (signal-to-noise ratio = 3), and glucose could be linearly detected in the range from 5 to 100   nM and the detection limit was 4.9   nM (signal-to-noise ratio = 3). Furthermore, the present approach was successfully applied to quantitative determination of H 2 O 2 in medical disinfectant and glucose in human serum samples.

研究领域: 分析化学 · 生物医学工程
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