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ANALYTICAL LETTERS · 2020 · IF 1.467

Fluorescent Determination of Mercury (II) and Glutathione Using Amino-MIL-53(Al) Nanosheets

Meijuan Ren,Huan Wang,Yuanyuan Liu,Qin Ma,Wenjing Jia,Mingzhu Liu,Huiju Wang,Yongchang Lu

Amino-MIL-53(Al) nanosheets were synthesized by a hydrothermal reaction and were employed as a fluorescent probe because of their high quantum yield and excellent stability. The amino-MIL-53(Al) nanosheets have a maximum fluorescence emission peak at 435 nm using an excitation wavelength of 335 nm. The fluorescent intensity of luminophor at 435 nm was linearly quenched when mercury (II) (Hg2+) was added, which occurred due to the adsorption of Hg2+ onto the luminophor surface. Under these conditions, the fluorescent signal of the system is in the “turn-off” state. Following the addition of glutathione (GSH) into the system, the quenched fluorescence intensity may be partially restored based on the reaction between glutathione and Hg2+. In this condition, the fluorescent signal of the amino-MIL-53(Al)-Hg2+ system is in the “turn-on” state. Therefore, the amino-MIL-53(Al) nanosheets were successfully used as a “turn-off-on” fluorescent sensing system to determine the concentrations of Hg2+ in Tibetan medicine and glutathione in rabbit serum. A good correlation coefficient was obtained between the quenching of the fluorescence intensity of luminophor and the concentration of Hg2+ using the optimized conditions. A linear range was acquired from 1.96 nM to 38.27 μM with a detection limit of 0.23 nM of Hg2+ based upon a signal-to-noise ratio of three. For glutathione, the linear dynamic range was from 210 nM to 15.25 μM with a detection limit equal to 8.11 nM based upon a signal-to-noise ratio of three. This developed sensor system has the advantages of high selectivity, favorable sensitivity and simple operation for the determination of Hg2+ and glutathione in real samples.

研究领域: 分析化学 · 生物化学
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RSC Advances · 2022 ·Vol. 12 ·期 38 ·24670-24680 · IF 4.036

Postsynthetic of MIL-101-NH2 MOFs supported on PVDF membrane for REEs recovery from waste phosphor

Wei Qin,Along Yu,Xue Han,Junwei Wang,Jiayin Sun,Jianli Zhang,Yaqing Weng

With the increasing demand for rare earth elements (REEs) due to their wide application in high technology, their recovery and separation from waste sources has gradually come onto the agenda. Herein, a new kind of MIL-101-NH2 (M1N) MOF functionalized with diethanol anhydride (DGA) incorporated into a polyvinylidene fluoride (PVDF) membrane (DGA-M1N@PVDF) has been fabricated for the sorption of REEs from a simulated acid leaching solution of waste phosphor, which contains a large amount of REEs. FTIR, TGA, XRD, fluorescence spectra and XPS analysis were used to characterize the synthesized composite membrane. Batch tests were employed to determine the optimal sorption conditions for Y and Eu adsorbed on DGA-M1N@PVDF adsorbent, such as pH (1–5), content of M1N MOFs (0–40 wt%), contact time (10–180 min) and ion concentration (0–20 mg L−1). Maximum adsorption capacities for Y and Eu on DGA-M1N@PVDF reached 991.7 μg g−1 and 98.76 μg g−1 for trace REE solution, respectively. Moreover, a pseudo-second-order kinetic model accurately described the sorption process, and the plotted isothermal data indicated that the Langmuir model was more suitable than the Freundlich model for Y and Eu sorption with monolayer and chemical adsorption. Meanwhile, FTIR and XPS analyses revealed that the Y and Eu adsorption on the DGA-M1N@PVDF composite membrane was mainly caused by the N and O atoms of the –CONH or –COOH groups coordinated with metal ions. Furthermore, after five cycles, the recovery efficiency by DGA-M1N@PVDF for REEs remains above 82% and the XRD patterns were consistent with the original sample, which implied that the DGA-M1N@PVDF membrane has preferable stability, recyclability and good efficiency in REE separation from waste phosphor solutions.

研究领域: 材料科学 · 环境工程
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DALTON TRANSACTIONS · 2025 ·Vol. 54 ·期 8 ·3467-3477 · IF 3.3

TiO2/CoOx heterostructure decorated MIL-100(Fe) by atomic layer deposition for enhanced photocatalytic oxygen production

Wenhui Hu,Zhongxin Song,Lingna Sun,Lei Zhang,Qianling Zhang,Xiangzhong Ren,Yongliang Li

Efficient separation of photogenerated charge carriers is essential for maximizing the photocatalytic efficiency of semiconductor materials in oxygen evolution reactions (OER). This study presents a novel trimetallic photocatalyst, MIL-100(Fe)/TiO2/CoOx, synthesized through a facile microwave-assisted hydrothermal method followed by atomic layer deposition (ALD). The porous MIL-100(Fe) serves as a support for the sequential deposition of TiO2 and CoOx layers via ALD, which enhances electron–hole pair separation and minimizes their recombination. Characterization using transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) confirms the uniform deposition of TiO2 and CoOx layers on the MIL-100(Fe) surface. The optimized photocatalyst, processed with 20 deposition cycles of Co, exhibits exceptional photocatalytic OER performance, with an oxygen evolution rate of 558.3 μmol g−1 h−1. This enhancement in activity is attributed to the synergistic interaction between the spatially separated TiO2 and CoOx cocatalysts, which facilitates efficient charge transfer and increases the number of active sites. These findings highlight the potential of ALD-fabricated heterostructures in the development of advanced photocatalysts for sustainable energy production.

CAS / MDL: 7439-89-6
研究领域: 材料科学 · 能源化学
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Catalysts · 2020 ·Vol. 11 ·期 1 ·24 · IF 3.52

The Research on the Construction and the Photocatalytic Performance of BiOI/NH2-MIL-125(Ti) Composite

Juan Du,Jiaxin Zhang,Tingyu Yang,Renming Liu,Zhiyi Li,Dandan Wang,Tong Zhou,Yucun Liu,Chunbo Liu,Guangbo Che

The BiOI/NH2-MIL-125(Ti) composite photocatalyst with excellent photocatalytic performance was prepared by the solvothermal method. For the BiOI/NH2-MIL-125(Ti) (BNMT) system, the contents of NH2-MIL-125(Ti) in BNMT-4, BNMT-5, BNMT-7, BNMT-9, and BNMT-10 were 4 wt %, 5 wt %, 7 wt %, 9 wt %, and 10 wt %, respectively. XRD, XPS, SEM, and TEM characterizations indicated that BiOI/NH2-MIL-125(Ti) was successfully prepared. Brunauer, Emmett, and Teller (BET) and UV–vis diffuse reflectance spectra photoelectrochemical analysis indicated that BNMT-9 can make the specific surface area and photo absorption region larger than BiOI. In addition, the separation efficiency of photogenerated carriers was improved, and the recombination efficiency was reduced. The degradation percentages of Rhodamine B (RhB) and p-chlorophenol (P-CP) reached 99% and 90% over BNMT-9 under visible light irradiation. Additionally, the catalysts had high stability. The results of the active spices trapping experiments test indicated that h+was the main active species. The possible degradation mechanism was proposed.Keywords:photocatalysis;BiOI;NH2-MIL-125(Ti);organic pollutants

研究领域: 材料科学 · 环境科学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2020 · IF 3.99

Anatase TiO2@MIL-101(Cr) nanocomposite for photocatalytic degradation of bisphenol A

Yuan Tang,Xiaohong Yin,Manman Mu,Yue Jiang,Xiaoli Li,Hao Zhang,Tianwei Ouyang

A series of anatase TiO 2 @MIL-101(Cr) was synthesized using the solvothermal method for photocatalytic degradation of bisphenol A (BPA). The characterization of the composites showed that they had an octahedral shape that was similar to that of MIL-101(Cr), but the particle size was reduced to about 300–500 nm. The amount and surface area of the TiO 2 in the composites jointly influenced the photocatalytic degradation; in optimal conditions, 59 % TiO 2 @MIL-101(Cr) could achieve 99.4 % BPA degradation in 240 min under UV irradiation. This superior photocatalytic performance was the result of the effective separation of electron-hole pairs and a narrow band gap. Moreover, the optimal composite exhibited excellent stability, indicating its suitability for reuse. Reasonable pathways of BPA degradation were proposed based on the detected intermediates during the degradation, where the oxidative radical O 2 − played a dominant role.

CAS / MDL: 7727-43-7 7789-02-8
研究领域: 环境科学 · 材料科学
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Journal of Pharmaceutical Analysis · 2021 · IF 4.769

MIL-53-based homochiral metal-organic framework as a stationary phase for open-tubular capillary electrochromatography

Xiaodong Sun,Bing Niu,Qi Zhang,Qin Chen

Homochiral metal-organic frameworks (MOFs) have attracted considerable attention in many fields of research, such as chiral catalysis and chiral chromatography. However, only few homochiral MOFs can be effectively used in capillary electrochromatography (CEC) and their performances are far from adequate. In this study, we successfully synthesized achiral nanocrystalline MIL-53. A facile post-synthetic modification strategy was then implemented to functionalize the product, yielding a homochiral MOF: l -His-NH-MIL-53. This MOF was then employed as a chiral coating in open-tubular CEC mode (OT-CEC), and, as such, it exhibited high enantioselectivities for several racemic drugs. The homochiral MOF and the fabricated capillary coating were systematically characterized using transmission electron microscopy, scanning electron microscopy (with energy-dispersive X-ray spectrometry), Fourier-transform infrared spectroscopy, X-ray diffractometry, thermogravimetric analysis, circular dichroism spectroscopy, Brunauer-Emmett-Teller surface area measurements, and X-ray photoelectron spectroscopy. This study is expected to provide a new strategy for the design and establishment of MOF-based chiral OT-CEC systems.

研究领域: 分析化学 · 材料科学 · 色谱学 · 纳米技术
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JOURNAL OF SOLID STATE CHEMISTRY · 2025 · IF 3.5

Study of LiCl/MIL-101(Cr)@GO composites for water adsorption

Mengyao Li,Ping Wu,Xiaoli Han,Shanshan Shi,Shiping Zhang,Li Wang,Min Xu,Xiulan Huai

Adsorption-based thermal energy conversion systems offer a sustainable solution for space heating and cooling applications. However, due to the limited performance of solid adsorbents, the large-scale application of this technology still requires further research. To address this challenge, we developed a composite adsorbent by integrating a graphene oxide (GO)-modified metal-organic framework (MIL-101(Cr)) with LiCl. The material was characterized using a variety of techniques to assess its improvement in three areas: water adsorption performance, heat propagation rate and stability. The synthesized material was systematically characterized to evaluate three key performance parameters: water adsorption capacity, thermal conductivity, and cyclic stability. The optimized composite LMG-3 (90 wt% LiCl) exhibits a tenfold increase in water absorption capacity compared to MIL-101(Cr)@GO at P/P 0 = 0.3. The introduction of GO significantly increases the heat diffusion coefficient, and the material exhibits excellent cyclic stability and inhibits salt deliquescence, demonstrating its potential for adsorptive thermal storage applications.

CAS / MDL: 7447-41-8
研究领域: 材料科学 · 能源工程
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Molecular Catalysis · 2024 · IF 3.9

Photocatalytic selective oxidation of HMF to DFF based on hollow CdS QDs/MIL-101 composites under visible light

Yuwei Liang,Chunling Hu,Peng Chen,Qi Li,Jianning Wu,Zhiyong Liu,Jichang Liu,Yanlong Tai

5-hydroxymethylfurfural (HMF) can catalyte into 2,5-diformylfuran (DFF) which had received much attention as a potential biomass resource. Here, we used a simple and effective method to construct hollow CdS quantum dot (CdS QDs)/MIL-101 heterostructures with high contact area and multiple active sites. The structure of heterostructures could improve photocatalytic activity by charge transfer, photogenerated carrier separation and the multiple refractions of light supported within the hollow-structured CdS QDs. The detailed catalytic mechanism was illustrated by trap agent experiments and electron paramagnetic resonance (EPR) spectroscopy, in which superoxide radicals (·O 2 - ) play a decisive role in the catalytic oxidation of HMF to DFF. Furthermore, the large specific surface area of MIL-101 adsorbs O 2 from the reaction system thereby accelerating the ·O 2 - formation process. Under environmental conditions, 70 % CdS QDs/MIL-101 exhibited optimal catalytic performance. Comparing with pure CdS QDs, the photocurrent enhances 1.8 times, HMF conversion is 1.5 times and DFF selectivity is 1.2 times. This work provide a useful way to improve the conversion of biomass by Z-heterostructures under ambient conditions.

研究领域: 化学工程 · 材料科学 · 环境科学
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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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Scientific Reports · 2019 ·Vol. 9 ·期 1 ·1-11 · IF 4.011

WO3 in suit embed into MIL-101 for enhancement charge carrier separation of photocatalyst

Wang Linjuan,Zan Ling

Compositing nanoparticles photo-catalyst with enormous surface areas metal–organic framework (MOF) will greatly improve photocatalytic performances. Herein, WO 3 nanoparticles are partly embedded into pores of MIL-101 or only supported on the outside of representative MIL-101, which were defined as embedded structure WO 3 @MIL-101@WO 3 and coating structure WO 3 &MIL-101 respectively. Different pH, concentration and loading percentage were researched. XRD, TEM and BET were carried to analyze the composites. Compared with the pristine WO 3 , all WO 3 loaded MOF nanocomposites exhibited remarkable enhancing for the efficiency of photocatalytic degradation methylene blue under visible light. Their activity of the same loading percentage WO 3 in embedded structure and coating structure have increased for 9 and 3 times respectively compared with pure WO 3 . The WO 3 @MIL-101@WO 3 has 3 times higher efficiency than WO 3 &MIL-101, because the shorter electron-transport distance can make a contribution to electron–hole separation. The further mechanism involved has been investigated by radical quantify experiment, XPS and photoluminescence spectroscopy.

研究领域: 材料科学 · 环境科学
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Journal of the Taiwan Institute of Chemical Engineers · 2021 · IF 5.876

Manipulated adsorption of C8 aromatics in MIL-53(Cr) through pre-adsorbing water molecules

Anqi Sun,Ying Wu,Zhenjiang He,Peng Bai,Jiafei Lyu,Xianghai Guo

The flexible metal-organic framework MIL-53(Cr) has been demonstrated to be an efficient adsorbent for liquid phase adsorption and separation, while the effect of this attractive “breathing effect” on its performance remains uncertain. In this research, by increasing the amount of introduced water, MIL-53(Cr) first shrank into a narrow pore form through bound water and then reopened due to the introduction of free water. Using MIL-53(Cr) with diverse amounts of water as an adsorbent, the liquid-phase adsorption and separation of C8 aromatics, including o -xylene (OX), p -xylene (PX), m -xylene (MX) and ethylbenzene (EB), was manipulated by the pre-adsorbed water in MIL-53(Cr). Pre-adsorbing water in MIL-53(Cr) induced a preference reversal between MX and PX, where dry samples preferentially adsorbed MX, while high-water-addition samples preferred PX instead. In addition, the reopened MIL-53(Cr) with high water addition hardly adsorbed EB, thereby increasing the selectivity of xylene isomers to EB. A longer equilibrium time was observed on MIL-53(Cr) with high water addition, during which the adsorption preference shifted from OX to MX to PX. Further molecular simulation provided a microscopic explanation that water molecules in the pores tended to package around MX and EB, hindering their interaction with frameworks or other adsorbates.

CAS / MDL: 7789-02-8 100-21-0
研究领域: 化学工程 · 材料科学
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Chemistry-An Asian Journal · 2020 ·Vol. 16 ·期 1 ·64-71 · IF 4.056

Preparation of a Dual-MOF Heterostructure (ZIF@MIL) for Enhanced Oxygen Evolution Reaction Activity

Tao Zhao,Dong Wang,Chen Cheng,Dazhong Zhong,Genyan Hao,Guang Liu,Jinping Li,Qiang Zhao

Graphical A ZIF@MIL heterostructure was successfully prepared by an in situ solvothermal method. Compared to pure ZIF-67 and MIL-100, the heterostructure possesses a larger electrochemical surface area and exhibits a remarkable catalytic performance with a low overpotential of 232 mV and a small Tafel slope of 57 mV dec −1 at 10 mA cm −2 . Although metal-organic frameworks have proven to be excellent electrocatalytic materials, their application as electrode materials remains limited. The preparation of heterostructures is considered an effective method to improve catalytic activity. Herein, we describe the design and assembly of a dual-MOF heterostructure (CoNi−ZIF-67@Fe−MIL-100, denoted ZIF@MIL). Specifically, we grew a layer of MIL-100 in situ on a bimetallic ZIF-67 surface using a solvothermal method. We demonstrate that the ZIF@MIL has remarkable OER electrocatalytic performance, requiring a low overpotential and showing a small Tafel slope, compared to pure ZIF-67 and MIL-100 in 1.0 m KOH. More importantly, it has excellent operational durability for 50 h at 100 mA cm −2 . The high catalytic activity of ZIF@MIL can be attributed to the heterostructure that can expose more active sites, the synergistic effect between ZIF-67 and MIL-100, and improvement of electron transfer ability. Our work provides a new way to design and prepare dual-MOF crystals with different structures as electrocatalysts.

研究领域: 材料科学 · 电化学
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