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UIO-66
JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2018 · IF 5.091

Trichloroacetic acid-modulated synthesis of polyoxometalate@UiO-66 for selective adsorption of cationic dyes

Liang Zeng,Ling Xiao,Yangke Long,Xiaowen Shi

In this study, POM@UiO-66 nanoparticles were fabricated by encapsulation of POM (K 6 P 2 W 18 O 62 polyoxometalate) into mesoporous UiO-66 metal organic framework through a solvothermal method with trichloroacetic acid as a modulator to promote the defects formation of UiO-66. The as-prepared samples were characterized by TEM , SEM, PXRD , TG, XPS , and EDX elemental mapping, and the successful combination of POM and UiO-66 was confirmed. Two cationic dyes, rhodamine B and malachite green , and one anionic dye orange G were employed to investigate the adsorption performance of POM@UiO-66. The adsorption data showed that the removal process of cationic dyes by POM@UiO-66 matched well with the pseudo-second-order model and Langmuir isothermal model. The resulting POM@UiO-66 nanoparticles exhibited high adsorption to cationic dyes but low adsorption to anionic dyes, and the adsorption capacities of rhodamine B, malachite green, and anionic dye orange G were 222.6, 190.6 and 40 mg g −1 , respectively. Furthermore, the cationic dyes could be selectively removed from a cationic-anionic dye binary system. These results suggested that the novel polyoxometalate-based UiO-66 material is a promising candidate for the adsorption of cationic dyes from effluent.

CAS / MDL: 10026-11-6 10213-10-2
研究领域: 材料科学 · 环境科学
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ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE · 2024 · IF 1.1

Construction of [P4442]2[IDA]/Zirconium Metal-Organic Framework (UiO-66) for Curing with Epoxy Resin

Zhiwei Zhang,Yilin Ma,Encheng Liu,Junjie Cheng,Fengfeng Chen,Bin Ling,Ningyu Di,Junkuo Gao

Curing agents for epoxy resin (EP) are one of the most important branches in the polymer materials field due to their enormous potential in many fields, but constructing them in a well-controlled curing temperature remains challenging. Herein, a novel curing agent is constructed by the zirconium metal-organic framework (UiO-66) and [P 4442 ] 2 [IDA] through an impregnation method. [P 4442 ] 2 [IDA]@UiO-66 is utilized as a functional nanofiller and curing agent to construct the [P 4442 ] 2 [IDA]@UiO-66/EP nanocomposites. The chemical structures of [P 4442 ] 2 [IDA]@UiO-66 were investigated by XRD, SEM, DSC, and TG characterizations. The various [P 4442 ] 2 [IDA]@UiO-66 with different loading amounts of [P 4442 ] 2 [IDA] were used to investigate the curing behaviors of the EP-51. The DSC results confirm that the curing temperature of the [P 4442 ] 2 [IDA]@UiO-66/EP is higher than that of [P 4442 ] 2 [IDA]/EP. In addition, the kinetic parameters and the activation energy of the curing reaction were acquired according to the fitting of Kissinger equation and Ozawa equation. The drying time of [P 4442 ] 2 [IDA]@UiO-66/EP system at 40 °C was enhanced 17 times compare to that of [P 4442 ] 2 [IDA]/EP system. This study opens new avenues for the rational design of EP nanocomposites by employing ionic liquids@MOFs composite materials as curing agent for wide engineering applications.

CAS / MDL: 67-56-1
研究领域: 材料科学 · 化学工程
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ANALYST · 2022 ·Vol. 147 ·期 24 ·5655-5662 · IF 5.227

A novel electrochemical sensor based on AuPd/UiO-66-NH2/GN composites for sensitive dopamine detection

Ying Zhou,Ruichun Li,Guomei Zhang,Yan Zhang,Caihong Zhang,Shaomin Shuang

Metal–organic frameworks (MOFs) have emerged as interesting nanomaterials owing to their large surface area, high porosity, tunable pore architecture and easy functionalization. However, an inferior electrical conductivity hinders their application in electrochemical sensing. In this paper, gold–palladium alloy/UiO-66-NH2/graphene (AuPd/UiO-66-NH2/GN) composites were synthesized by loading alloys on the surfaces of MOFs and then attaching them to the graphene surface. The addition of metal nanoparticles and graphene enhanced the electron transfer ability of MOFs. Then, composites were used to modify a glassy carbon electrode (GCE) to construct a sensitive dopamine (DA) electrochemical sensor. The developed sensor manifested two linear relationships in lower concentration ranges and in higher concentration ranges with a 0.21 × 10−6 mol L−1 low detection limit (3σ/k) under optimal conditions. The results certified that the constructed sensor had high selectivity, excellent reproducibility and good stability, and had been used successfully for DA detection in actual human serum samples.

研究领域: 材料科学 · 分析化学 · 生物医学
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

The metal organic framework of UiO-66-NH2 reinforced nanofiltration membrane for highly efficient ion sieving

Yongtong Lei,Lijing Zhu,Jilong Xu,Shuan Liu,Zhixiang Zeng,Xiaocheng Li,Gang Wang

Metal organic framework (MOF) with fine pore structures, ultra-high porosity and large specific surface area can provide more water transport channels while achieving precise sieving of different sizes of ions, which is a promising material for high efficiency desalination. However, particle agglomeration, interface incompatibilities and interface defects severely restrict the performance of MOF-based membranes. It is still a challenge to construct MOF-based desalination membranes with both high water permeability and high ion sieving. Herein, the UiO-66-NH 2 based nanofiltration membrane was fabricated by in-situ growth of UiO-66-NH 2 on Nylon membrane and composed with polyamide (PA) layer by interfacial polymerization (IP). With 12 h solvothermal reaction, the UiO-66-NH 2 nanoparticles are found uniformly loaded on the Nylon substrate. Therefore, the water molecule transport channels provided by UiO-66-NH 2 nanoparticles reduce the transport resistance, which can improve the water permeability. More importantly, UiO-66-NH 2 nanoparticles are found to be involved in the IP process, which can reduce the interfacial defects and thus enhance the bonding force between the PA layer and base film. The synergistic effect of the UiO-66-NH 2 and PA layer improves the nanofiltration performance of the membrane with rejection rate of 92.97% for Na 2 SO 4 and the pure water permeance (PWP) of 11.55 L m −2 h −1 bar −1 . The N-UN12 @PA membrane also has excellent antifouling performance (flux recovery ratio (FRR) of 95.86%, reversible fouling ratio (Rr) of 33.93%, irreversible fouling ratio (Rir) of 4.14%). Unlike the mixed-matrix membrane (MMM) and polycrystalline MOF membrane, this strategy provides a promising method to prepare high-performance nanofiltration membrane for desalination.

研究领域: 材料科学 · 环境工程
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Carboxymethyl chitosan–modified UiO-66 for the rapid detection of fenpropathrin in grains

Xiaoyao Wang,Haizhi Huang,Siyao Zhong,Xuping Shentu,Zihong Ye,Xiaoping Yu

Fenpropathrin residues in grain are potentially harmful to humans. Therefore, a fluorimetric lateral flow immunoassay using a zirconium-based organic skeleton (UiO-66) as a signal marker was developed for detecting fenpropathrin. Herein, carboxymethyl chitosan (CMCS) was used to modify UiO-66 and improve its water solubility to facilitate stable binding with sodium fluorescein (NaFL). This resulted in formation of a new fluorescent probe that is more suitable for lateral flow immunoassay (LFIA). The materials were characterized via electron microscopy , Fourier-transform infrared spectroscopy, and powder X-ray diffraction. CMCS and NaFL were successfully bound to UiO-66. Under optimized conditions, the constructed NaFL/UiO-66@CMCS-LFIA exhibited a good linear relationship within the range of 0.98–62.5 μg/L, with a detection limit of 3.91 μg/L. This probe was fourfold more sensitive than traditional colloidal gold nanoparticle-based LFIA. Finally, NaFL/UiO-66@CMCS-LFIA was successfully applied to detect fenpropathrin in wheat and maize samples. The detection limit was 1.56 μg/kg and recoveries ranged from 96.58 % to 118.56 %. This study provides a sensitive, stable, and convenient method for the rapid detection of pesticide residues .

研究领域: 分析化学 · 食品安全 · 生物技术
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RSC Advances · 2019 ·Vol. 9 ·期 19 ·10702-10714 · IF 3.049

Self-assembled membrane manufactured by metal–organic framework (UiO-66) coated γ-Al2O3 for cleaning oily seawater

Cunlong Li,Yuqing Zhang,Ming Yong,Wei Liu,Jiaqi Wang

In order to effectively clean oily seawater with anionic polyacrylamide (APAM), UiO-66 coated γ-Al2O3 (UA) composites were firstly synthesized using γ-Al2O3 as a template to induce the growth of high hydrophilic UiO-66 on its surface to form a uniform UA self-assembled membrane. The UA composites and self-assembled membrane were characterized and analyzed. Also, the membrane performance was investigated. The results show that the hydrophilicity of particles is enhanced with the water contact angle decreasing from 39.8° (γ-Al2O3 particles) to 26.2° (UA composites) by introducing the UiO-66 coating. Moreover, the UA self-assembled membrane performs attractive water yield and separation performance. The oil concentration in the permeate treated by the first class of UA self-assembled membrane declines apparently from 91.22 to 18.90 mg L−1, while the water yield is as high as 657.89 L m−2 h−1. The reclaimed separation experiments show that the membrane materials could be recycled by calcination at 200 °C and hydraulic cleaning, which gives the material potential application in cleaning oily seawater.

CAS / MDL: 68-12-2 10026-11-6
研究领域: 材料科学 · 环境工程
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CATALYSIS LETTERS · 2022 ·Vol. 153 ·期 3 ·836-849 · IF 2.936

Acid Regulation of Defective Sulfonic-Acid-Functionalized UiO-66 in the Esterification of Cyclohexene with Formic Acid

Jiang Haoran,Xue Changhao,Sun Weijie,Gong Zhaoxiang,Yuan Xia

The esterification of cyclohexene with formic acid is the first step in synthesizing cyclohexanol via the indirect hydration of cyclohexene. In this work, we improved the efficiency of the esterification reaction by constructing a sulfonic-acid-functionalized UiO-66 solid-acid catalyst containing defect sites. By using acetic acid as the modulator, ZrCl 4 as the zirconium source, and 2-sulfoterephthalic acid monosodium salt as the ligand, a sulfonic-acid-functionalized UiO-66-SO 3 H with defect sites was prepared using a solvothermal synthesis method. Additionally, we also prepared UiO-66 with defect sites for comparison. We then investigated the regulation effects of acetic acid addition amount on the defect structures and acidity of the as-prepared materials. The results showed that the addition of acetic acid caused lattice defects in the as-prepared materials with a missing linker, and the specific surface area, pore volume, pore size, and particle size of the material changed significantly. The number of defect sites was determined by thermogravimetric analysis. Additionally, pyridine infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis indicated that the ratio of Lewis acid to Brønsted acid sites, and the total acid content in the defect materials, greatly increased compared to pure UiO-66 and UiO-66-SO 3 H, which greatly enhanced the acid catalytic performance of the material. Among these, UiO-66-SO 3 H(20), which was prepared by adding 20 mL of acetic acid, exhibited the best catalytic activity. The conversion rate of cyclohexene reached 83.4%, the selectivity toward cyclohexyl formate was 99.8%, and the catalyst could be reused three times. Graphical Abstract The purpose of this work was to improve the efficiency of the esterification reaction of cyclohexene with formic acid by constructing a sulfonic acid-functionalized UiO-66 solid acid catalyst containing defective sites. The regulation effect due to the amount of acetic acid added on the defect structure and acidity of the as-prepared materials was investigated.

CAS / MDL: 110-83-8
研究领域: 化学 · 催化材料
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Enhanced removal of lead ions and methyl orange from wastewater using polyethyleneimine grafted UiO-66-NH2 nanoparticles

Shao-zhong Hu,Ting Huang,Nan Zhang,Yan-zhou Lei,Yong Wang

The discharge of wastewater rich in heavy metals and organic substances has led to the deterioration of the ecosystem, resulting in serious environmental and food pollution, and there is an urgent need to treat the pollutants in the wastewater. Metal organic frameworks (MOFs) have the advantages of large specific surface area and pore volume, as well as the designability of their structures, and are extremely promising materials for wastewater treatment. In this work, a novel adsorbent was synthesized by grafting polyethyleneimine (PEI) onto the UiO-66-NH 2 metal framework (PEI@UiO-66-NH 2 ) via glutaraldehyde-assisted reaction. This new type of adsorbent not only exhibits improved chemical stability in water but also shows greatly increased adsorption sites in comparison with the common UiO-66-NH 2 . The various factors that possibly affect the adsorption behaviors of the PEI@UiO-66-NH 2 were systematically studied. The results show that the PEI@UiO-66-NH 2 can nearly reach the adsorption equilibrium of Pb(II) and methyl orange (MO) within 5 min. The theoretical adsorption capacities toward Pb(II) and MO achieve 692.80 mg/g and 497.51 mg/g, respectively. Specifically, the dynamic theoretical adsorption models were established through the study of the dynamic adsorption of pollutants, providing the theoretical guidance for the scale-up experiments of wastewater treatment with this adsorbent. PEI@UiO-66-NH 2 also shows excellent recycling performance for removing Pb(II) and MO. All these results suggest that PEI@UiO-66-NH 2 has a good application prospect for the removal of wastewater containing Pb(II) and MO.

研究领域: 环境科学 · 材料科学
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2023 · IF 6.1

A novel UiO-66-NH2/graphene oxide composite thin membrane for retarding membrane wetting in membrane distillation

Fangqing Li,Lin Chen,Yufei Wei,Zhiwei Yin,Keying Que

Membrane distillation (MD) is considered an emerging desalination technology. However, the presence of surfactants allows liquid to penetrate the membrane, resulting in membrane wetting, which hinders the commercialization of MD. In this study, we use very few modified materials to prepare novel Janus thin membranes that immobilize modified materials (graphene oxide (GO) and UiO-66-NH 2 ) on polytetrafluoroethylene (PTFE) hydrophobic base membranes via crosslinkers. The composite thin membrane properties with eight different ratios and contents of GO and UiO-66-NH 2 were fabricated and tested by a feed solution of sodium chloride containing a high concentration of sodium dodecyl sulfate. An optimal ratio of Janus membrane with high flux without affecting the effluent water quality was obtained. The Janus membrane exhibited excellent anti-wetting properties compared to the original PTFE membrane. A desalination rate of up to 99.9% was still available even under 48 h of long-term operating conditions by maintaining a flux of approximately 21.2 L/(m 2 ·h). The anti-wetting mechanism of this membrane was further confirmed by the modified XDLVO model. It suggested that the novel Janus membrane could be a highly promising substitute to the MD process for the resource-based treatment of surfactant-containing wastewater, which played an important role in promoting its application.

研究领域: 环境科学 · 材料科学
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ACS Applied Materials & Interfaces · 2021 · IF 9.229

NH2-UiO-66 Coated with Two-Dimensional Covalent Organic Frameworks: High Stability and Photocatalytic Activity

Yongchao Wang,Qing Yang,Fangli Yi,Ruowei Lu,Yanxia Chen,Cheng Liu,Xinyu Li,Cuijuan Wang,Hongjian Yan

The poor stability and low catalytic activity of NH2-UiO-66 in basic solutions require the reactions to be conducted in acidic solutions, which seriously hinders its potential photocatalytic application. Herein, we report that NH2-UiO-66 coated with two-dimensional covalent organic frameworks (COFs) via imine bond connection presents not only high photocatalytic activity but also high stability and adaptability to the solution environment. The NH2-UiO-66/COF hybrid material was fabricated through the Schiff base reaction of NH2-UiO-66 with 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)trianiline (TAPT) and 2,4,6-triformylphloroglucinol (TP). The hybrid material showed high stability in an alkaline environment, with only 4.7% of NH2-UiO-66 decomposed after the photocatalytic reaction. The optimum photocatalytic H2 evolution rate was 8.44 mmol·h–1·g–1 when triethanolamine was used as an electron-donating agent. The results presented here illustrate the possibility for effectively improving both the photocatalytic performance and stability of NH2-UiO-66 by coupling with COFs.

研究领域: 材料科学 · 光催化领域
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SENSORS AND ACTUATORS B-CHEMICAL · 2021 · IF 7.46

RhB/UiO-66-N3 MOF-based ratiometric fluorescent detection and intracellular imaging of hydrogen sulfide

Xia Gao,Guangming Sun,Xinke Wang,Xiaodong Lin,Shuo Wang,Yaqing Liu

As a vital signaling molecules, hydrogen sulfide (H 2 S) with abnormal concentrations is correlated with many diseases. Therefore, development of novel assays for quantitative and selective detection of H 2 S is important. Herein, we synthesized a host-guest metal-organic framework (MOF), i.e., RhB/UiO-66-N 3 (here, RhB means rhodamine B) by a mildly and simply way, as reaction-based ratiometric fluorescent nanosensor for selective detection and intracellular imaging of H 2 S. In the presence of H 2 S, the RhB/UiO-66-N 3 exhibits dual emissions at 425 nm and 575 nm under irradiation of single excitation wavelength. The blue fluorescence at 425 nm (F 425 ) is attributed to the H 2 S-mediated biorthogonal reduction of azide to amine, and the red fluorescence at 575 nm (F 575 ) originating from RhB is served as an internal reference. With increasing concentrations of H 2 S, the intensity of blue fluorescence increases while the intensity of red fluorescence has no obvious change. With F 425 /F 575 as readout, turn-on and ratiometric fluorescence detection of H 2 S was achieved with good selectivity and sensitivity. Interestingly, RhB/UiO-66-N 3 can be tuned from microscale to nanoscale sizes, and endows high stability under physiological conditions. The exogenous and endogenous H 2 S in live cells has been further targeted and imaged, demonstrating its considerable potential for extensive applications.

研究领域: 生物化学 · 医学 · 材料科学
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POLYMER BULLETIN · 2025 · IF 4

Preparation of M2070-UiO-66-OH@[BMim][PF6]/Pebax mixed matrix membranes and CO2 separation

Zhang Chengpeng,Bei Pengzhi,Liu Hongjing,Zhao Xu,Shi Meiling,Jing Xiaochun,Li Zhao,Yao Hui

A novel porous liquid, M2070-UiO-66-OH@[BMim][PF 6 ], has been synthesized using zirconium-based metal–organic framework (UiO-66-OH), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMim][PF 6 ]) and polyetheramine M2070. To enhance the CO 2 separation performance, M2070-UiO-66-OH@[BMim][PF 6 ] was incorporated as a filler into a mixed matrix membrane (MMM) using polyether block amide (Pebax-1657) as the membrane matrix. The properties of the synthesized M2070-UiO-66-OH@[BMim][PF 6 ] and the resulting MMMs have been characterized through FTIR, TGA, DSC, and SEM analyses. The results of porous liquid stability revealed that grafting polyetheramine M2070 onto the surface of UiO-66-OH@[BMim][PF 6 ] significantly increased the steric hindrance, thereby preventing agglomeration within the membrane. Additionally, the functional groups (amino and ether) present in M2070-UiO-66-OH@[BMim][PF 6 ] contributed to an increased number of active sites for CO 2 adsorption, facilitating enhanced CO 2 transport through the membrane. Compared to the Pebax membrane, the MMM containing 3% M2070-UiO-66-OH@[BMim][PF 6 ] exhibited significantly improved CO 2 permeability of 104.07 Barrer (an increase of 73.22%) and CO 2 /N 2 selectivity of 92.37 (an increase of 148.95%) at 30 °C and 0.3 MPa, surpassing the 2008 Robeson upper bound. These findings suggest that M2070-UiO-66-OH@[BMim][PF 6 ] is a highly promising additive for the fabrication of mixed matrix membranes with superior CO 2 separation performance. Graphical abstract A porous liquid, (M2070-UiO-66-OH@[BMim][PF 6 ]) has been prepared using UiO-66-OH@[BMim][PF 6 ] as the core and polyetheramine M2070 as the canopy. Afterwards, M2070-UiO-66-OH@[BMim][PF 6 ] has been added to the Pebax matrix to prepare M2070-UiO-66-OH@[BMim][PF 6 ]/Pebax mixed matrix membranes, which have been subjected to gas separation studies.

研究领域: 材料科学 · 环境科学
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