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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Rapid removal of CH3Hg+ by thioctic acid modified NH2-MIL-101 in water

Yingqi Xia,Lijia Liu,Yudan Wang,Chunhong Zhang,Yawen Liu

CH 3 Hg + in water is a neurotoxin that is difficult to eliminate and is readily absorbed by the human body through food chains. In this study, thioctic acid was grafted onto the surface of NH 2 -MIL-101 via an amidation reaction to prepare an adsorption material for the rapid and effective removal of CH 3 Hg + , which is designated as LA-MIL-101.The synthesis of LA-MIL-101 was confirmed through analyses including FT-IR, XRD, SEM, TGA, and XPS. BET results indicate that the specific surface area of LA-MIL-101 is 464.92 m 2 ·g −1 . The ideal conditions for CH 3 Hg + adsorption were explored by varying environmental factors such as pH, contact time, and temperature. Furthermore, the introduction of sulfur significantly enhanced the adsorption capacity for CH 3 Hg + . Batch adsorption experiments demonstrate that LA-MIL-101 exhibits an exceptionally rapid adsorption rate, achieving over 88.3 % of the total removal rate within just one minute. Additionally, LA-MIL-101 shows remarkable adsorption efficacy across a broad pH range. The adsorption behavior of LA-MIL-101 for CH 3 Hg + aligns with the Elovich and Langmuir models, with a maximum adsorption capacity reaching 1391.77 μg·g −1 . LA-MIL-101 also displays a strong anti-interference capability in environments containing humic acid or Na + . Notably, it maintains high removal efficiency under conditions involving coexisting cations, as well as in simulated surface water, simulated groundwater, and natural seawater. Moreover, LA-MIL-101 demonstrates good stability and recyclability, retaining effective adsorption after five adsorption/desorption cycles. XPS results elucidate the adsorption mechanism of CH 3 Hg + , highlighting interactions with sulfur (S) and nitrogen (N) atoms. Overall, LA-MIL-101 exhibits high practicality and significant potential for application in the emergency treatment of CH 3 Hg + in aquatic environments.

研究领域: 环境科学 · 材料科学 · 毒理学
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APPLIED ORGANOMETALLIC CHEMISTRY · 2015 ·Vol. 29 ·期 9 ·618-623 · IF 2.248

Visible-light photocatalytic activity of Ag@MIL-125(Ti) microspheres

Hongxu Guo,Di Guo,Zishan Zheng,Wen Weng,Jianhua Chen

Ag nanoparticle (NP)-decorated MIL-125(Ti) microspheres (Ag@MIL-125(Ti)) were firstly fabricated via a facile hydrothermal and following photo-reduction method. The photocatalysts were characterized using X-ray diffraction, scanning and transmission electron microscopies, X-ray photoelectron spectroscopy and UV–visible diffuse reflectance spectroscopy. The characterization results indicated that Ag NPs were dispersed on the surface of MIL-125(Ti) microspheres, and the Ag NPs had a uniform diameter of about 40 nm. The composites exhibited excellent visible-light absorption, due to the modification with the Ag NPs. The photocatalytic activity for the visible-light-promoted degradation of Rhodamine B was improved through the optimization of the amount of Ag loaded as a co-catalyst, this amount being determined as 3 wt%. Additionally, studies performed using radical scavengers indicated that O 2 − and e − served as the main reactive species. The catalyst can be reused at least five times without significant loss of its catalytic activity. Furthermore, a photocatalytic mechanism for degradation of organics over Ag@MIL-125(Ti) is also proposed. Copyright © 2015 John Wiley & Sons, Ltd.

研究领域: 材料科学 · 环境科学
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RSC Advances · 2020 ·Vol. 10 ·期 4 ·2198-2208 · IF 3.119

Rapid and selective adsorption of a typical aromatic organophosphorus flame retardant on MIL-101-based metal–organic frameworks

Hui Su,Jiaxin Lv,Liansheng Yang,Li Feng,Yongze Liu,Ziwen Du,Liqiu Zhang

The pollution of aromatic organophosphorus flame retardants (aromatic OPFRs) in aquatic environments has drawn great attention over the last few years. Two MIL-101-based metal–organic frameworks (Cr-MIL-101 and Fe-MIL-101-NH2) which possess ordered mesoporous cavities (2.9 and 3.4 nm) and aromatic structures were chosen and prepared to selectively adsorb a typical aromatic OPFR [triphenyl phosphate (TPhP)] from aqueous solution. Pore distribution analysis showed that Cr-MIL-101 and Fe-MIL-101-NH2 had both a mesoporous structure (2–3.5 nm) and microporous structure (1–2 nm), conducive to diffusion and adsorption of TPhP molecules. Compared with Fe-MIL-101-NH2 as well as commercial activated carbon, Cr-MIL-101 showed rapid and efficient adsorption for TPhP, and its initial sorption velocity (v0) calculated from the pseudo-second-order model was up to 568.18 μmol g−1 h−1. The adsorption equilibrium of TPhP on the Cr-MIL-101 was almost achieved within 12 h, while the equilibrium time of other adsorbents required more than 48 h. The study of selective adsorption found that Cr-MIL-101 had a higher sorption amount for aromatic OPFRs than alkyl-OPFRs and other aromatic compounds with different chemical structures. Cr-MIL-101 was able to keep a steady selective adsorption for TPhP in the presence of co-existing aromatic compounds. Based on the analysis of Kow, molecular structure and further density functional theory calculations, hydrophobic interactions may play a dominant role in the selective adsorption process of TPhP, and π–π interactions may be also involved. Cr-MIL-101 exhibits reusability and promising potential to rapidly and selectively remove aromatic OPFR in environmental remediation.

研究领域: 环境科学 · 材料科学
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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Construction of MIL-88(Fe) derived MOF/TiO2 photoanode for efficient photoelectrochemical water splitting

Wenjin Ni,Sicheng Zhang,Lingling Cheng,Tiejun Luo,Hongyun Yang,Tengfei Duan,Dejian Yan

Developing efficient photoanodes for water oxidation is highly promising due to their critical role in producing green H 2 and harnessing solar energy. Herein, a metal-organic framework (MOF)/photoanode was successfully constructed by coating TiO 2 nanorods with MIL-88(Fe) MOF for photoelectrochemical (PEC) water splitting. The results demonstrated that MIL-88(Fe) was uniformly and tightly coated on TiO 2 and functioned as a cocatalyst. The MIL-88(Fe) MOF provides a large surface area and more Fe-O active sites, contributing to high PEC activity by reducing electron/hole recombination and enhancing light response capability. Moreover, the photoanode also exhibited an improved charge conductivity. As a result, the MIL-88(Fe)/TiO 2 photoanode exhibited an excellent photocurrent density of 1.06 mA cm −2 at 1.23 V RHE , which is approximately 2.6 times higher than the pristine TiO 2 . Charge transfer kinetics analyses and electrochemical tests were carried out and revealed that the improved PEC performance was attributed to the introduction of MIL-88(Fe), which promoted charge separation-transfer. This research provided new insights into the design of efficient semiconductor/MOF composite photoanodes for PEC water oxidation.

研究领域: 材料科学 · 能源科学
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CHEMICAL ENGINEERING RESEARCH & DESIGN · 2019 · IF 3.073

CO2 capture and adsorption kinetic study of amine-modified MIL-101 (Cr)

Suresh Mutyala,Madhavi Jonnalagadda,Harisekhar Mitta,Raveendra Gundeboyina

MIL-101 (Cr) was synthesized by a hydrothermal method and used as support to prepare a series of polyethylenimine (PEI) incorporated MIL-101 (Cr) by wet impregnation method. All characterization results revealed that the structure of MIL-101 (Cr) was well-maintained by the incorporation of polyethylenimine and confirmed the presence of PEI within MIL-101 (Cr). The CO 2 adsorption studies were carried out in a fixed bed reactor from 30 to 90 °C, 1 bar. The adsorption of CO 2 has been increased by the incorporation of PEI. It was due to the chemical interaction between the NH 2 and CO 2 groups to form a carbamate. The high CO 2 adsorption capacity 3.81 mmol g −1 was shown by 70 wt% PEI loaded MIL-101 (Cr) at 75 °C, 1 bar, because of more number of NH 2 groups and a high number of CO 2 molecules diffusion. Its adsorption capacity was 4.7 times higher than the adsorption capacity of MIL-101 (Cr) (0.80 mmol g −1 ). Moreover, in moisture condition, CO 2 adsorption capacity was increased to 4.4 mmol g −1 by the formation of ammonium bicarbonate and showed good adsorption stability throughout each adsorption-desorption cycle. The Avrami adsorption kinetic model was well fitted with experimental breakthrough CO 2 adsorption data of MIL-101 (Cr)-PEI-70. It suggested that the adsorption of CO 2 on PEI incorporated material was chemical adsorption.

研究领域: 材料科学 · 环境科学
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International Journal of Nanomedicine · 2025 · IF 6.5

A Multifunctional MIL-101-NH2(Fe) Nanoplatform for Synergistic Melanoma Therapy

Jinlu Shang,Yongjun Chen,Fangliang Wang,Jing Yang,Yi Li,Liuxuan Yang,Xiuqiong Liu,Zhirong Zhong,Chaochi Yue,Meiling Zhou

Background Melanoma is an aggressive form of skin cancer, and single-modality treatments often fail to prevent tumor recurrence and metastasis. Combination therapy has emerged as an effective approach to improve treatment outcomes.Methods In this study, we developed a multifunctional nanoplatform, MIL@DOX@ICG, utilizing MIL-101-NH2(Fe) as a carrier to co-deliver the chemotherapeutic agent doxorubicin (DOX) and the photosensitizer indocyanine green (ICG). MIL-101-NH2(Fe) was synthesized via a hydrothermal method. Drug release was evaluated under different pH conditions, and the photothermal effect was tested under near-infrared (NIR) laser irradiation. Hydroxyl radical and reactive oxygen species generation capacities were quantified. Cellular studies using B16F10 cells assessed cytotoxicity, cellular uptake, migration inhibition, and colony formation suppression. In vivo experiments in melanoma-bearing mice evaluated antitumor efficacy and systemic safety through tumor growth inhibition, histological analyses, and toxicity assessments.Results MIL@DOX@ICG exhibited a uniform octahedral structure with a particle size of approximately 139 nm and high drug loading efficiencies for DOX (33.70%) and ICG (30.59%). The nanoplatform demonstrated pH-responsive drug release and potent photothermal effects. The generation of hydroxyl radicals via the Fenton reaction and reactive oxygen species production under NIR laser irradiation by MIL@DOX@ICG were confirmed. In vitro assessments revealed significant cytotoxicity of MIL@DOX@ICG against B16F10 cells under NIR laser irradiation, with improved efficacy in inhibiting cell proliferation and migration. In vivo studies confirmed the superior antitumor efficacy of MIL@DOX@ICG + NIR treatment, synergistically harnessing chemotherapy, photothermal therapy, photodynamic therapy, and chemodynamic therapy effects while maintaining excellent biocompatibility.Conclusion Our findings underscore the potential of MIL-101-NH2(Fe) nanoparticles as a versatile and effective platform for synergistic melanoma therapy, offering a promising strategy for overcoming the limitations of conventional treatment modalities.

CAS / MDL: 10312-55-7
研究领域: 肿瘤学 · 纳米医学 · 生物材料学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2018 · IF 3.141

Highly Adsorptive Separation of Ethane/Ethylene by An Ethane-Selective MOF MIL-142A

Yongwei Chen,Houxiao Wu,Daofei Lv,Renfeng Shi,Yang Chen,Qibin Xia,Zhong Li

In the petrochemical industry, ethane/ethylene (C2H6/C2H4) separation is one of the most important processes. Herein, we reported an iron-based metal–organic framework MIL-142A for efficiently trapping C2H6 from C2H6/C2H4 mixture, exhibiting preferential adsorption of C2H6 over C2H4. After various characterization techniques to confirm the successful preparation of MIL-142A, the C2H6 and C2H4 adsorptive separation performance was systematically investigated. Results showed that MIL-142A had remarkably higher C2H6 adsorption capacities than that of C2H4 at 298, 288, and 278 K, such as C2H6 and C2H4 adsorption capacities of 3.8 and 2.9 mmol/g at 298 K and 100 kPa, respectively. In addition, the C2H6 and C2H4 adsorption heats were relatively low and in the corresponding ranges 27.3–25.1 and 26.2–23.8 kJ/mol, which is a favorable property for the regeneration of MIL-142A with less energy penalty. Furthermore, it was inferred that the difference between the adsorption heat for C2H6 and C2H4 with the MIL-142A framework governed the selective adsorption of C2H6 over C2H4. The ideal adsorbed solution theory (IAST) selectivity of C2H6/C2H4 was high up to 5.8 in the initial low pressure and then decreased to 1.5 at 298 K and 100 kPa. Besides, breakthrough experiments also corroborated its efficient separation of C2H6/C2H4 mixture. Additionally, MIL-142A had excellent moisture stability, and its framework remained still intact after being exposed to humid conditions (80% RH) for 15 days. These comprehensive properties demonstrated that this unique material MIL-142A, as a high-performance C2H6-selective adsorbent, can be potentially used for highly adsorptive separation of the C2H6/C2H4 mixture.

CAS / MDL: 10025-77-1
研究领域: 材料科学 · 化学工程
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Journal of Chemistry · 2020 · IF 1.79

Hydrothermal Catalytic Conversion of Glucose into Lactic Acid with Acidic MIL-101(Fe)

Xiaofang Liu,Zhigang Liu,Qiuyun Zhang,Hongguo Wu,Rui Wang

MIL-101(Fe) was explored for the first time for the catalytic conversion of glucose into lactic acid (LA). The as-synthesized MIL-101(Fe) was successfully characterized, and its higher specific surface area, porosity, and feasible acid properties were confirmed to determine the remarkable catalytic activity in glucose-to-LA conversion (up to 25.4% yield) compared with other catalysts like MIL-101(Cr, Al) and UiO-66(Zr). The reaction parameters including temperature, reaction time, and substrate species as well as catalyst reusability were discussed.

研究领域: 化学工程 · 材料科学 · 生物化学
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INORGANICA CHIMICA ACTA · 2017 · IF 2.002

Facile synthesis of nano-sized MIL-101(Cr) with the addition of acetic acid

Tian Zhao,Ling Yang,Peiyong Feng,Irina Gruber,Christoph Janiak,Yuejun Liu

MIL-101(Cr), one of the best investigated and widely used metal–organic frameworks, has been easily synthesized with particle diameters in the range from 387(28) nm to 90(10) nm by using acetic acid as a modulator . The particle size of MIL-101(Cr) decreased with increasing acetic acid concentration. The decrease of size in high concentration of acetic acid may be explained with the efficient suppression of the framework extension. In a selected condition, MIL-101(Cr) possessing an average diameter of about 90 nm can be prepared easily and reproducibly in gram-scale, with high BET-surface areas (3200–3500 m 2 /g) and fairly good yield (60–75%).

CAS / MDL: 7789-02-8 100-21-0
研究领域: 材料科学 · 化学工程
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CHINESE JOURNAL OF ANALYTICAL CHEMISTRY · 2022 · IF 1.193

A multiresponsive luminescent hydroxyl-functionalized MIL-53(Al) for detection of F− and water

Linli HOU,Li WANG,Yonghai SONG,Limin LIU

A luminescent hydroxyl-functionalized MIL-53(Al) (OH-MIL-53(Al)) was prepared by one-step solvent thermal method for multiresponsive fluorescence sensor. The OH-MIL-53(Al) exhibited uniform nanospheres with average diameter of 150±20 nm, flexible three-dimensional frameworks, and good dispersion in water. The OH-MIL-53(Al) emitted green fluorescence with a maximum wavelength of 515 nm which showed good fluorescence quenching response for sensing F − and fluorescence enhancement response for water, with good day-to-day stability. The mechanism was based on protonation/deprotonation of hydroxyl group located on OH-MIL-53(Al). Good linear relationship could be found between the luminescence intensity of 515 nm and F − concentrations in the range of 0–60 µM with a determination limit of 70 nM. At the concentrations from 0% to 100%, the fitting curve for water content was in good agreement with the linear equation, and the detection limit was 0.10%. OH-MIL-53(Al) demonstrated excellent fluorescence sensing performance, indicating that it could be used as a multiresponsive sensor to practical application.

研究领域: 材料科学 · 分析化学
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CHEMISTRY AND ECOLOGY · 2024 · IF 1.3

Highly efficient hexavalent chromium removal on polyethylenimine@NH2-MIL-101(Cr) composite

Zhenpeng Li,Dongmei Yan,Jun Li,Ziwei Mai,Fuchuan Huang

Hexavalent chromium (Cr(VI)) is regarded as a water pollutant because of its high toxicity in aquatic environments. In this study, polyethyleneimine-functionalised NH2-MIL-101(Cr) (PEI@NH2-MIL-101(Cr)) was fabricated by a facile wet impregnation method, and its effectiveness at removing Cr(VI) from wastewater was systematically investigated. As suggested by the experimental findings, pH was a significant determinant of Cr(VI) uptake by the fabricated PEI@NH2-MIL-101(Cr). Preferable depiction of adsorption system was achievable with the Langmuir adsorption model and the pseudo-order 2 kinetic model. At 288, 298, and 308 K, the highest adsorbability values were 241.55, 310.56, and 408.16 mg g−1, respectively. Processes like electrostatic attraction, reduction and chelation helped promote the Cr(VI) elimination. SO42− ions had a relatively large impact on the Cr(VI) adsorption compared with other coexisting ions such as NO3−, Cl− and H2PO4−1. Because of its properties of high adsorption capacity and Cr(VI) detoxification, the potential of PEI@NH2-MIL-101(Cr) in the Cr(VI) elimination from wastewater appears to be promising.

研究领域: 环境科学 · 材料科学
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2025 ·Vol. 36 ·期 19 ·1-15 · IF 2.8

NH2-MIL-125/Ti3C2 composite film as a ultrasensitive photoelectrochemical glucose sensor

Li Zi-Yan,Li Ya-Jun,Li Wei,Wang Ze-Hong,Zhao Zhao-Ye,Zhou Ting-Ting,Huang Yi-Rui,Wu Xiang-Feng,Zhang Peng-Liang,Zhen Zi-Yan,Ci Li-Jie

In this study, a photoelectrochemical sensor for the detection of glucose was developed by combining the unique properties of NH 2 -MIL-125 and Ti 3 C 2 film. The relationship between the microstructure of the samples and their performance in glucose detection was investigated. Experimental results demonstrated a linear decrease in the differential pulse voltammetry current of the Ti 3 C 2 /NH 2 -MIL-125-3 photoelectrochemical sensor with increasing glucose concentration. Below 200 μM, the relationship between DPV current and glucose concentration was found to be: I (mA) = − 3.86667 × 10 –8 ·c g (μM) + 3.66 × 10 –4 (c g denoted as the concentration of glucose). Above 200 μM, the relationship was: I (mA) = − 4.03049 × 10 –8 ·c g (μM) + 3.68268 × 10 –4 . Density functional theory calculations were in agreement with the experimental data. The Ti 3 C 2 /NH 2 -MIL-125-3 photoelectrochemical sensor demonstrates exceptional glucose detection capability. This technology has the potential to advance the development of MXenes/MOFs-based photoelectrochemical biosensors.

CAS / MDL: 106-51-4
研究领域: 生物传感 · 材料科学 · 分析化学
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