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Journal of Water Process Engineering · 2021 · IF 5.485

A novel Fe-based bi-MOFs material for photocatalytic degradation of tetracycline: Performance, mechanism and toxicity assessment

Qiuya Zhang,Jun Xu,Xiaoyan Ma,Jinmei Xu,Zeping Yun,Qiaosheng Zuo,Liping Wang

Metal-organic frameworks (MOFs) are new porous materials that attract wide attention due to their environmentally-friendly photocatalytic characteristics. However, poor charge separation in most MOFs largely limits their photocatalytic activity. In this study, a novel Fe-based bi-MOFs heterojunctions material, namely NH 2 -MIL-88B(Fe)@MIL-100(Fe) was prepared by internal extended growth of MIL-100(Fe) on spindle-like NH 2 -MIL-88B(Fe). Compared with pure NH 2 -MIL-88B(Fe) and MIL-100(Fe), the synthesized Fe-based bi-MOFs structure catalyst displayed excellent photocatalytic degradation of tetracycline (TC), with optimal removal of 99.9% achieved in 90 min under neutral conditions. This result is attributed to the sufficient visible light absorption , and the enhanced separation and transfer of h + and e − by the bi-MOFs structure. In particular, ∙O 2 − , h + and ∙OH showed synergistic effects in the photodegradation process, and Fe-based bi-MOFs displayed high stability after five cycles. The inhibition ratio of luminescent bacteria of the degraded solution was lower than 24%, indicating the high efficiency and safety of this Fe-based bi-MOFs for the treatment of antibiotic-contaminated water.

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Nanomaterials · 2021 ·Vol. 11 ·期 8 ·1917 · IF 5.076

Effective Magnetic MOFs Adsorbent for the Removal of Bisphenol A, Tetracycline, Congo Red and Methylene Blue Pollutions

Guangpu Zhang,Rong Wo,Zhe Sun,Gazi Hao,Guigao Liu,Yanan Zhang,Hu Guo,Wei Jiang

A magnetic metal−organic frameworks adsorbent (Fe3O4@MIL-53(Al)) was prepared by a typical solvothermal method for the removal of bisphenol A (BPA), tetracycline (TC), congo red (CR), and methylene blue (MB). The prepared Fe3O4@MIL-53(Al) composite adsorbent was well characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and fourier transform infrared spectrometer (FTIR). The influence of adsorbent quantity, adsorption time, pH and ionic strength on the adsorption of the mentioned pollutants were also studied by a UV/Vis spectrophotometer. The adsorption capacities were found to be 160.9 mg/g for BPA, 47.8 mg/g for TC, 234.4 mg/g for CR, 70.8 mg/g for MB, respectively, which is superior to the other reported adsorbents. The adsorption of BPA, TC, and CR were well-fitted by the Langmuir adsorption isotherm model, while MB followed the Freundlich model, while the adsorption kinetics data of all pollutants followed the pseudo-second-order kinetic models. The thermodynamic values, including the enthalpy change (ΔH°), the Gibbs free energy change (ΔG°), and entropy change (ΔS°), showed that the adsorption processes were spontaneous and exothermic entropy-reduction process for BPA, but spontaneous and endothermic entropy-increasing processes for the others. The Fe3O4@MIL-53(Al) was also found to be easily separated after external magnetic field, can be a potential candidate for future water treatment.Keywords:magnetic;metal-organic framework;adsorption;water treatment

CAS / MDL: 80-05-7
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MICROPOROUS AND MESOPOROUS MATERIALS · 2020 · IF 4.551

Quantitative analysis of hydrogen isotopes gas mixtures by cryogenic chromatography using low loading MOFs as stationary phase

Min Li,Yongtao An,Xintong Li,Xianglin Wang,Ning Zeng,Kelin Chen,Weizhi Yao,Jiangfeng Song,Changan Chen,Xingwen Feng,Ning Liu

Cryogenic gas chromatography is one of the most extensively used methods for quantitative analysis of hydrogen isotopes gas mixtures. However, limitations such as long retention time or low separation resolution exist in the current chromatographic analysis for hydrogen isotope. Due to chemical affinity quantum sieving effect, MOFs materials with open metal sites show good separation performance for hydrogen isotopes. Herein, low loading composites Ni 2 Cl 2 BBTA@γ-Al 2 O 3 was prepared by hydrothermal synthesis , which has been subsequently employed as a stationary phase for gas chromatographic separations of ternary hydrogen isotope gas mixtures (H 2 -HD-D 2 ). Excellent separation resolution at liquid nitrogen temperature was realized, and baseline separation (R = 1.57) of H 2 /HD can be obtained within 11 min. Finally, quantitative analysis of hydrogen isotopes gas mixtures with the good accuracy and repeatability (RSD around 1%) was achieved. Compared with the traditional gas chromatography stationary phase, a shorter packed column of low loading MOFs modified composite showed high efficiency quantitative analysis for hydrogen isotopes gas mixtures.

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NANO · 2020 · IF 1.566

Deposition of MOFs on Polydopamine-Modified Electrospun Polyvinyl Alcohol/Silica Nanofibers Mats for Chloramphenicol Adsorption in Water

Aowen Li,Meimei Zhou,Pingping Luo,Jiaxin Shang,Pengbo Wang,Luxue Lyu

Nanofiber mats produced by electrospinning, with the advantages of specific surface area, porosity and chemical tenability, are an ideal support material for deposition of metal − − organic framework (MOF) crystals. In this study, four types of MOFs (MIL-53(Al), ZIF-8, UiO-66-NH 2 and NH 2 -MIL-125(Ti)) were deposited on polydopamine (PDA)-modified electrospun polyvinyl alcohol (PVA)/SiO 2 organic − − inorganic hybrid nanofiber mats by bulky synthesis. Because of the formation of Si–O–C–O–Si bridges between PVA chains and silica network, electrospun PVA/SiO 2 organic − − inorganic hybrid nanofiber mats are quite stable in water or organic solvents and at high temperature are suitable as supports for MOFs deposition. The PDA layer, which exhibits a powerful adhesive ability to attach foreign objects, can effectively improve growth of MOFs on the surface of PVA/SiO 2 nanofiber mats. The obtained MOF composites combining the unique properties of electrospun nanofibers mats and MOFs particles become flexible and tailorable, greatly expanding the application range of MOFs materials. The synthesized MOF composites were used to adsorb chloramphenicol (CAP) in water. It was found that the four MOF composites could remove CAP from water effectively and MIL-53(Al) composite had the highest adsorption capacity due to the higher specific surface area.

CAS / MDL: 62-31-7
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CHEMOSPHERE · 2020 · IF 5.778

Facile preparation of iron oxide doped Fe-MOFs-MW as robust peroxydisulfate catalyst for emerging pollutants degradation

Yongjie Wan,Jinquan Wan,Joe R. Zhao,Yan Wang,Ting Luo,Shou Yang,Yaxin Liu

A novel catalyst (Fe-MOFs-MW) was facilely synthesized under microwave-assisted with NaOH as modulator for activating peroxydisulfate (PDS). The accelerated nucleation process was confirmed by Johnson-Mehl-Avrami (JMA) model. There were abundant reactive sites on prepared Fe-MOFs-MW while maintaining high Space-Time-Yield value up to 2300 kg/m 3 ·d. Degradation performance of Fe-MOFs-MW as PDS catalyst on sulfamethoxazole (SMX) removal was evaluated. Results indicated that Fe-MOFs-MW with more Fe element anchored (10%) exhibited excellent catalytic capacity for PDS. Besides, the fantastic stability and reusability were confirmed through recycle experiment. After recycled for 4 times, the removal efficiency of SMX and TOC was 88% and 31.3% compared to 98% and 38% without recycling, respectively. An accurate prediction model on the degradation effect with water matrices coexisted was established by response surface methodology (RSM) method. Moreover, SO 4 ·- , O 2 ·- and ·OH were confirmed as the main reactive species through chemical quenching and EPR tests. The mechanism of Fe-MOFs-MW/PDS process mainly based on electron circulation theory was proposed. As the robust PDS catalyst, facile prepared Fe-MOFs-MW was promising in the treatment of emerging pollutants.

CAS / MDL: 7775-27-1
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2020 · IF 7.489

Construction of lanthanum modified MOFs graphene oxide composite membrane for high selective phosphorus recovery and water purification

Ning Wei,Xudong Zheng,Qiao Li,Chenxia Gong,Hongxiang Ou,Zhongyu Li

Metal organic framework materials (MOFs) are kinds of hybrid materials with intra-molecular pores formed by self-assembly of organic ligands and metal ions through coordination bonds. In the paper, a type of MOFs named as [Zn(μ-L)(μ-1,3-dpp)](mof-1), using Zn 2+ as metal ions, 4,4′-oxybis(benzoic acid) and 1,3-di(4-pyridyl)propane as organic ligands was synthesized. The rare earth element lanthanum , which has specific adsorption for phosphorus, is intercalated into mof-1 by the impregnation method in order to remove phosphorus-containing wastewater. In order to optimize the nano-sized La-mof-1 materials to facilitate separation, we prepared a membrane by blending MOFs materials with graphene oxide (GO) by pressure application. The addition of GO not only facilitates the separation of materials, but also has excellent removal ability for water purification . After a series of structural characterization, the adsorption properties of materials were tested. The experimental results showed that the total phosphorus in the water can get to the maximum adsorption capacity when pH = 4.0. It can be viewed in thermodynamic studies that increasing the temperature favors the adsorption reaction. Increasing the temperature to the 318 K, the equilibrium adsorption capacity of the membrane to total phosphorus in the water reached 139.51 mg/g. The adsorption removal rate of total phosphorus can reach 100% when its concentration is lower than 100 mg/L. This highlights the advantages of intercalating lanthanum into MOFs. The penetration curve was drawn by dynamic adsorption experiments to understand the mass transfer mechanism of La-mof-1GO membrane. Since GO also has a large specific surface area, it is another excellent adsorption material. Experimental data showed that compared with the original water sample, the removal rate of COD in the water reached 73.9%.

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Nanomaterials · 2020 ·Vol. 10 ·期 5 ·983 · IF 4.324

CeO2-Supported Pt Catalysts Derived from MOFs by Two Pyrolysis Strategies to Improve the Oxygen Activation Ability

Xueqing Zhu,Hui He,Yanxia Li,Haoyuan Wu,Mingli Fu,Daiqi Ye,Junliang Wu,Haomin Huang,Yun Hu,Xiaojun Niu

Functional metal organic framework (MOF) derivatives have attracted tremendous attention as promising catalysts for various reactions. The thermal decomposition strategies have a vital effect on the structures and physicochemical properties of functional MOF derivatives. Nevertheless, what effect does the pyrolysis strategy have on MOF derivatives need further study. In this work, one-step (under dry air) and two-step (first under N2and then dry air) pyrolysis are chosen to prepare the functional ceria-based MOF derivatives with novel hierarchical pore structure. In comparison with the derivatives prepared by one-step pyrolysis, the two-step pyrolysis composites exhibit better catalytic activity for toluene oxidation due to the higher contents of surface absorbed oxygen species and surface oxygen vacancies. The reusability and durability test demonstrates perfect stability of such functional MOF derivatives. The in-situ UV Raman reveals that two-step strategy is favorable for enhancing the gaseous oxygen activation ability of the functional MOF derivatives. Those findings may instruct the synthesis of functional MOF derivatives via different pyrolysis strategies as well as afford a further understanding of the crucial role of oxygen vacancies.Keywords:metal organic frameworks;functional derivatives;pyrolysis strategies;toluene oxidation;oxygen activation abilities

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Catalysis Science & Technology · 2019 ·Vol. 10 ·期 2 ·315-322 · IF 5.726

One-pot synthesis of bimetallic metal–organic frameworks (MOFs) as acid–base bifunctional catalysts for tandem reaction

Yanjing Hu,Jian Zhang,Hang Huo,Zhe Wang,Xianzhu Xu,Yulin Yang,Kaifeng Lin,Ruiqing Fan

Designing and preparing effective acid–base tandem catalysts is one of the research hotspots at present because assembling antagonistic active sites in one catalyst is still a challenge. In this work, amine-functionalized bimetallic metal–organic frameworks (MIL-101(Al/Fe)–NH2 (X)) were synthesized through a rapid reflux method and acted as acid–base bifunctional catalysts for tandem reaction (deacetalization–Knoevenagel condensation reaction). The bimetallic MOF catalysts exhibit enhanced catalytic activity when compared with monometallic catalysts either MIL-101(Al)–NH2 or MIL-101(Fe)–NH2. The superior performance of MIL-101(Al/Fe)–NH2 (X) has been attributed to the synergistic effect between Al3+ and Fe3+ ions and the hierarchical pore structure. Moreover, the as-synthesised samples showed robust stability, excellent recyclability, and durable catalytic activity.

CAS / MDL: 68-12-2 6017-21-6
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2022 · IF 7.139

Morphology restructuring: MOFs derived Ni3S2@FeCrMoSx/NF as a highly efficient and stable catalyst for water oxidation

Yekai Zhang,Shuai Wang,Hong Zhong,Xin Ma,Zhanfang Cao

Exploring low-cost and high-efficiency OER catalysts is still a challenge. In this paper, self-supporting catalyst-Ni 3 S 2 @FeCrMoS x /NF was prepared using metal organic frameworks as templates. The morphology of the pre-catalyst has been deeply restructured after the sulfidation reaction, which significantly changes the composition and catalytic performance of the catalyst. The overpotential of Ni 3 S 2 @FeCrMoS x /NF is only 144 mV and 241 mV at a current density of 10 and 50 mA cm −2 respectively, the Tafel slope is as low as 45 mV dec −1 . And it can maintain good electrochemical stability at a high current density of 100 mA cm −2 . The outstanding OER performance of Ni 3 S 2 @FeCrMoS x /NF can be attributed to the increase of electrochemical surface area after sulfidation, the synergistic effect among multi-metals and the synergistic effect of polymetallic sulfides generated by sulfidation.

CAS / MDL: 610-92-4
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ADVANCED FUNCTIONAL MATERIALS · 2023 · IF 19

Synergistic Multilevel Sieving Membranes: Integrating Cellular Graphene Skeleton with Continuous MOFs Nanolayer for Superior Multiphase Water Separation

Shizhuo Zhang,Jun Yuan,Shuai Wang,Yunfan Li,Yuhang Xu,Dingyue Sun,Feng Liu,Gary J. Cheng

The emergence of MOF–based separation membranes has transformed liquid contaminant filtration with impressive sieving properties. However, their use in multiphase water filtration is hindered by a limited sieving range and susceptibility to collapse in solution. To address this challenge, an innovative solution is presented: the Multilevel Cellular Graphene Skeleton (MCGK) induced by femtosecond laser, onto which a continuous MOF nanolayer (CMN), specifically ZIF–8, is grown. This forms a groundbreaking multistage micron/nanocomposite pore membrane. The MCGK/CMN membrane significantly expands the range of filterable contaminants and enhances stability. It utilizes a multilevel, multi–pore size sieving strategy for effective multiphase water filtration, achieving an impressive 90% efficiency in self–driven solar steam generation sieving. Additionally, it excels in removing organic pollutants and over 80% of volatile organic compounds (VOCs), while reducing metal ion concentrations. In liquid pressure–driven filtration, it achieves complete oil adsorption and reduces VOCs and metal ion concentrations. This innovative multistage micron/nanocomposite pore membrane holds great potential for diverse practical applications and provides insights for next–generation nanofiltration membranes, promising more efficient and resilient water purification technologies in the future.

CAS / MDL: 10196-18-6 121-44-8
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Boronate-affinity sol–gel-imprinted membranes with MOFs-functionalized rotary-evaporating layers for high-precision specific recognition

Faguang Ma,Ming Yan,Rongxin Lin,Yilin Wu,Jianming Pan

Compared to traditional separation methods, membrane-based separation can reduce environmental impact while reducing energy consumption. However, traditional adsorbents have issues with low selectivity and adsorption capacity because they enclose the majority of their functional sites in their thick structures. In this research, molecularly imprinted nanocomposite membranes were inventively integrated with boronate-affinity sol–gel imprinting technique (BSIT). It is important to note that in this work, the metal–organic frameworks (MOFs) mixed-matrix membrane (MMMs) served as the initial platform for the polydopamine (PDA)-based imprinting layer. The key to the fabrication of the MOFs MMMs was the employment of the rotary evaporation technique. The prepared boronate-affinity sol–gel molecularly imprinted membranes (BS-MIMs) played an important role in the high selectivity of the specific compound shikimic acid (SA) through covalent (boronate-affinity) and non-covalent (–OH and –NH 2 ) effect. This new approach provides a more precise combination of simultaneously increasing selectivity (greater than 5.0) and adsorption capacity (up to 107.87 mg g −1 ). The efficiency of BSIT makes it extremely competitive for the development of selective separation membranes.

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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Ultrasensitive Fluorescence Platform Based on AgNPs In Situ-Incorporated Zr-MOFs for the Detection of Organophosphorus Pesticides

Li Wang,Yi Pan,Zhengwu Wang,Yuanfeng Wang,Xinlin Wei

Organophosphorus pesticides (OPPs) are extensively used in agricultural production, and the contamination caused by their residues has raised significant concerns regarding potential threats to human health. Herein, a novel fluorescence nanoprobe based on an enzyme-mediated silver nanoparticle-modified metal organic framework (AgNPs@PCN-224) was successfully prepared for the rapid detection of OPPs. Initially, AgNPs@PCN-224 were synthesized by reducing silver nitrate (AgNO3) using sodium borohydride (NaBH4) embedded into luminescent PCN-224. This triggered the inner filter effect, leading to fluorescence quenching. Meanwhile, under the catalysis of acetylcholinesterase (AChE) and choline oxidase (CHO), acetylcholine (ATCh) was decomposed to hydrogen peroxide (H2O2), which could destroy AgNPs to form Ag+ released from PCN-224 for fluorescence recovery. Instead, fenitrothion, an OPP, inhibited AChE activity, allowing the quenched fluorescence to be reactivated. Under the current optimum conditions, the fluorescence intensity had a good correlation (Y = −728.5370X + 2178.4248, R2 = 0.9869) over a dynamic range of fenitrothion concentrations from 0.1 to 500 ng/mL, with an LOD of 0.037 ng/mL. In addition, the anti-interference ability and robustness of the proposed sensor was verified for the monitoring of fenitrothion in tea with recoveries of 87.67–103.72% and the relative standard deviations (RSD) < 5.43%, indicating that the system has excellent prospects for OPP determination in practical applications. Furthermore, this work provides a universal platform for screening other enzyme inhibitors to detect OPPs.

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