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MIL-101 (Cr)
MICROCHEMICAL JOURNAL · 2025 · IF 5.1

A highly sensitive photoelectrochemical aptamer sensor based on MIL-101(Cr)&Bi2S3 for chlorpyrifos detection

Zhaoxiang Zhong,Bochi Pan,Yi Xing,Hanlin Xu,Min Zhang,Lei Ding,Faliang Cheng

The extensive global application of chlorpyrifos (CPF) has led to significant environmental accumulation through aquatic systems, presenting substantial risks to ecological integrity and public health. This urgency necessitates advanced detection methodologies with enhanced sensitivity and operational efficiency to ensure environmental safety. Here, we developed a novel photoelectrochemical aptamer sensor utilizing a MIL-101(Cr)&Bi 2 S 3 heterostructure composite. This architecture synergistically integrates the broad-spectrum photon absorption capability of Bi 2 S 3 with the hierarchical porosity and structural stability of MIL-101(Cr), achieving remarkable enhancement in both electron-hole separation efficiency and interfacial charge transfer. The sensing platform was further optimized through aptamer functionalization, which confers precise molecular recognition capabilities while maintaining optimal charge transfer dynamics at the electrode interface. Systematic evaluation demonstrated exceptional analytical performance: a linear detection range spanning four orders of magnitude (0.05–10 μg/mL), ultralow detection limit of 0.022 ng/mL (S/N = 3). The developed methodology provides a versatile framework for adapting to other organophosphorus pesticide detection requirements through modular aptamer replacement.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2026 · IF 3.9

Mixed Matrix Membrane with Fluorinated MIL-101(Cr) Filler for the Separation of CO2 and CH4

Zequn Li,Luogang Wu,Guangcan Huang,Xuetong Cui,Zilong Chen,Qiang Chen,Jian-Rong Li

Mixed matrix membranes (MMMs) incorporating metal–organic frameworks (MOFs) are attractive for molecular recognition and separations, but precisely engineering the MOF filler structure toward maximizing its inherent nanopore separation capability remains challenging. Here, we report a fluorination strategy to functionalize MIL-101 that synergistically optimizes its pore chemical environment and interfacial compatibility with the polymer matrix. Compared with the MIL-101/6FDA-DAM membrane, the incorporation of strong electron-withdrawing fluorinated ligands enhances both the CO2 adsorption affinity of MIL-101 and its hydrogen-bonding interaction with the 6FDA-DAM matrix. The optimized MIL-101-F/6FDA-DAM (10 wt %) membrane achieves a CO2 permeability of 2200 Barrer, a 150% enhancement over the pure 6FDA-DAM membrane, while maintaining a comparable CO2/CH4 selectivity of 21. The excellent separation performance surpasses the 2008 Robeson upper bound. This work provides a simple and effective approach to advancing the gas separation performance of MMMs.

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JOURNAL OF POROUS MATERIALS · 2022 ·Vol. 30 ·期 1 ·311-325 · IF 2.523

Highly efficient adsorptive removal of tannic acid from aqueous solutions by nitro-functionalized MIL-101(Cr)

Li Zhengjie,Zhang Lu,Li Yunlong,Zhou Lilong,Han Jilong,Xu Hong,Yun Jimmy,Shen Shufeng,Liu Runjing

In the present work, functionalized MIL-101(Cr)-X (X = –Br, –CH 3 , –HSO 3 , –NO 2 ) materials with mesoporous pores were synthesized and used for tannic acid (TA) adsorption from aqueous solutions. In comparison with MIL-101(Cr), NO 2 -substituted MIL-101(Cr) was found to have positive surface charge and only slight reduction in its specific surface area, resulting in higher TA adsorption capacity than the parent MIL-101(Cr) and the others. Effect of operating parameters such as adsorption time, temperature, pH and ionic strength on the adsorption performance of MIL-101(Cr)-NO 2 was investigated. The TA adsorption capacity remarkably increases with increasing ionic strength adjusted by CaCl 2 . MIL-101(Cr)-NO 2 exhibits an adsorption capacity of 1619 mg/g, higher than that of the reported adsorbents, probably due to electrostatic interaction, π–π stacking interaction and Cr–O complexation interaction between MOF framework and TA. Adsorption isotherms and kinetic results are in accordance with Freundlich model and pseudo-second-order model, respectively. Moreover, the thermodynamics of TA adsorption on MIL-101(Cr)-NO 2 suggests an endothermic process.

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Materials · 2022 ·Vol. 15 ·期 16 ·5763 · IF 3.748

Template Method for Synthesizing Hierarchically Porous MIL-101(Cr) for Efficient Removal of Large Molecular Dye

Minmin Zou,Hexin Zhu,Ming Dong,Tian Zhao

As one of the most important prototypical chromium-based MOFs, MIL-101(Cr) is well-studied and widely employed in various scientific fields. However, due to its small capture window sizes and curved internal apertures, its application in large molecular removal is quite limited, and given its high stability and high synthetic temperature (>200 °C), it is difficult to achieve hierarchically porous MIL-101(Cr). In our study, hierarchically porous MIL-101(Cr) involving a high macro-/meso-/micropores ratio was designed and synthesized using acetic acid as an additive and silicon dioxide (SiO2) nanoparticles as a template. The optimal hierarchically porous MIL-101(Cr) (A-4) possessed a high specific surface area (2693 m2g−1) and an abundant macro-/mesoporous structure with the addition of SiO2of 200 mg. Compared with the control sample (A-0) with a less macro-/mesoporous structure, A-4 showed good adsorption properties for both coomassie brilliant blue R-250 (CBB, 82.1 mg g−1) and methylene blue (MB, 34.3 mg g−1) dyes, which were 1.36 times and 9.37 times higher than those of A-0. Moreover, A-4 also had good recyclability, and the removal rate of CBB was still higher than 85% after five cycles of adsorption.Keywords:MIL-101(Cr);SiO2;dye adsorption;template

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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Ferrocene Dicarboxylic Acid Ligand-Exchanged Hollow MIL-101(Cr) Nanospheres for Solar-Driven Atmospheric Water Harvesting

Yue Hu,Zhou Fang,Xinyi Wan,Xu Ma,Yuqi Wang,Mengyang Dong,Zhizhen Ye,Xinsheng Peng

Developing efficient water adsorbents for solar-driven atmospheric water harvesting (AWH) still remains a challenge due to the poor photothermal heating ability and slow sorption kinetics of most adsorbents. Postsynthetic ligand exchange (LE) provides an alternative strategy to prepare metal–organic framework (MOF) materials with varied structures and functions. In this work, multifunctional hollow MIL-101(Cr) with ferrocene dicarboxylic acid (Fc(COOH)2) ligand exchanged (HMF) nanospheres are prepared and utilized for efficient AWH. The resulted HMF nanospheres present great visible light absorption (>80%) and photothermal conversion ability (61.6%) due to the introduced Fc(COOH)2 ligand. The water adsorption and desorption rates of the HMF nanosorbent are 2.3 times and 4.5 times that of MIL-101(Cr). The fast water capture and solar-driven release kinetics of HMF nanosorbents indicate its great potential for actual water harvesting. The outdoor water collection experiment demonstrates that the areal water harvesting capacity of the HMF nanosorbent is 1720 g m–2 per cycle with packed thickness of 8 mm. HMF nanosorbents also demonstrate good antibacterial activity (91.4%), which is beneficial to the collection of healthy and safe water. This work provides a facile and practical method to design multifunctional MOFs from the molecular level by LE and to achieve solar-driven AWH and other fields.

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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.

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SCIENCE OF THE TOTAL ENVIRONMENT · 2021 · IF 7.963

Efficient capture of ReO4− on magnetic amine-functionalized MIL-101(Cr): Revealing from selectivity to mechanism

Yawen Cai,Jinghua Feng,Xiaoli Tan,Xin Wang,Zhimin Lv,Weiwei Chen,Ming Fang,Haining Liu,Xiangke Wang

The efficient decontamination of pertechnetate ( 99 TcO 4 − ) is an essential task for managing radioactive 99 Tc in nuclear wastes . Perrhenate, (ReO 4 − ), as a nonradioactive analog, exhibits almost identical physicochemical properties as 99 TcO 4 − . Herein, a novel magnetic amine-functionalized MIL-101(Cr) (NH 2 -MIL-101(Cr)@Fe 3 O 4 ) was prepared and used to efficiently remove ReO 4 − from solution for the facile magnetic separation. A series of environmental parameters were considered to investigate the adsorption performance of NH 2 -MIL-101(Cr)@Fe 3 O 4 . Experimental results suggested that NH 2 -MIL-101(Cr)@Fe 3 O 4 has reached a satisfied adsorption capacity (~401 mg/g) and a very fast adsorption kinetics at pH 7.0. The selectivity for ReO 4 − was maintained even in the presence of interfering anions with relatively high concentrations. ReO 4 − were mainly captured by N-donor sites of the surface-decorated amine via complexation and were trapped in the cavities of modified MIL-101(Cr). NH 2 -MIL-101(Cr)@Fe 3 O 4 exhibits satisfactory adsorption performance for ReO 4 − and can be conveniently separated from wastewaters after adsorption.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2020 · IF 3.573

Urea-Functionalized MIL-101(Cr)@AC as a New Adsorbent to Remove Sulfacetamide in Wastewater Treatment

Qiqi Zhou,Guijian Liu

The presence of sulfa antibiotics in water is becoming increasingly serious and actions need to be taken to establish an effective wastewater purification process for their removal. MIL-101(Cr)@AC was prepared by incorporating activated carbon into the MIL-101(Cr) framework to reduce unused voids in MIL-101. MIL-101(Cr)@AC has a high specific surface area and was successfully synthesized and activated with urea. In this study, the adsorptive removal of the sulfonamide antibiotic, sulfacetamide (SA), from wastewater was studied using urea-activated MIL-101(Cr)@AC for the first time. High SA adsorption efficiency was observed, and an adsorption equilibrium was reached within approximately 60 min. The adsorption kinetics and isotherm records were best fitted using the Langmuir model and a pseudo-second-order model, respectively. Therefore, according to the result of adsorption, a possible mechanism was proposed. Hydrogen bonding between −NH2 on the grafted urea-MIL-101(Cr)@AC and −SO2 groups in SA resulted in an increase in adsorption efficiency. In addition, urea-MIL-101(Cr)@AC exhibited excellent reusability, which is attractive for potential applications in adsorbing SA from wastewater.

CAS / MDL: 7664-39-3 121-57-3
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Diaminomaleonitrile functionalized double-shelled hollow MIL-101 (Cr) for selective removal of uranium from simulated seawater

Jichi Zhang,Hongsen Zhang,Qi Liu,Dalei Song,Rumin Li,Peili Liu,Jun Wang

Hollow metal-organic frameworks (MOFs) have attracted wide interest because of their unique core-shell structure. As a novel uranium adsorbent, diaminomaleonitrile (DAMN) functionalized double-shelled hollow (DSHM) metal-organic framework of chromium(III) terephthalate was prepared by a post-synthetic method of grafting amino group onto coordinatively unsaturated sites (CUS). TEM, XRD, nitrogen sorption and FT-IR spectrometry were used to characterize the obtained DAMN functionalized hollow MOF. The maximum capacity of uranium adsorption is 601 mg g −1 , which exceeds all known functionalized MIL-101 uranium adsorption materials. The optimal adsorption pH is 8 which is close to the pH of seawater. Furthermore, the high selectivity of uranium and high adsorption rate in simulated seawater provide a promising prospect to introduce DSHM-DAMN for the extraction of uranium from seawater. In this work, we first applied hollow MOF for uranium adsorption, which greatly improves the uranium adsorption performance of MOF materials; we also explored the practical application of hollow MOF materials.

CAS / MDL: 7789-02-8 100-21-0
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Catalysts · 2018 ·Vol. 8 ·期 9 ·394 · IF 3.465

Synthesis of Stable Hierarchical MIL-101(Cr) with Enhanced Catalytic Activity in the Oxidation of Indene

Tian Zhao,Ming Dong,Ling Yang,Yuejun Liu

Nowadays, the controllable synthesis of stable hierarchical metal–organic frameworks (MOFs) is very important for practical applications, especially in catalysis. Herein, a well-known chromium–benzenedicarboxylate metal–organic framework, MIL-101(Cr), with a stable hierarchical structure, was produced by using phenylphosphonic acid (PPOA) as a modulator via the hydrothermal method. The presence of phenylphosphonic acid could create structural defects and generate larger mesopores. The synthesized hierarchical MIL-101(Cr) possesses relatively good porosity, and the larger mesopores had widths of 4–10 nm. The hierarchical MIL-101(Cr) showed significant improvement for catalytic activity in the oxidation of indene. Further, the presence of a hierarchical structure could largely enhance large dye molecule uptake properties by impregnating.Keywords:MIL-101(Cr);phenylphosphonic acid;hierarchical;enhanced catalytic activity;large molecule uptake

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RSC Advances · 2018 ·Vol. 8 ·期 49 ·27623-27630 · IF 2.936

Adsorption characteristics of metal–organic framework MIL-101(Cr) towards sulfamethoxazole and its persulfate oxidation regeneration

Xiaoli Huang,Qi Hu,Lei Gao,Qirui Hao,Peng Wang,Dongli Qin

A metal–organic framework, MIL-101(Cr), was used to adsorb sulfamethoxazole (SMZ) in water and activated persulfate (PS) oxidation was investigated to regenerate SMZ-saturated MIL-101(Cr). Adsorption and oxidation were combined in this study. MIL-101(Cr) was characterized by SEM, BET, XPS and FT-IR analyses. Effects of various operating parameters on adsorption efficiency were studied. The dosages of persulfate for SMZ desorption and oxidation were investigated. The results showed that the recommended pH was 6–8 for SMZ adsorption and optimum MIL-101(Cr) dosage was 0.1 g L−1. SMZ adsorption by MIL-101(Cr) was a spontaneous process and nearly exothermic. Saturation adsorption capacity was achieved in 180 s and the adsorption followed the pseudo-second-order model. The maximum adsorption amount of MIL-101(Cr) to SMZ was 181.82 mg g−1 (Langmuir). MIL-101(Cr) also showed good adsorption capacities for sulfachloropyridazine (SCP), sulfamonomethoxine (SMM), and sulfadimethoxine (SDM). Persulfate was helpful for SMZ desorption from the surface of saturated MIL-101(Cr) and sufficient persulfate could simultaneously oxidize the SMZ. XPS analysis showed that the structure of MIL-101(Cr) was stable after the persulfate oxidation process. Regenerated MIL-101(Cr) had the same level of adsorption capacity as fresh MIL-101(Cr). An adsorption–oxidation combined process may be set up based on the results. This study provides basic data for the deep treatment of organic micropollutants in urban water bodies.

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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
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