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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2023 · IF 5.2

Bimetal-organic framework MIL-53(Fe,Ni) stimulates peroxydisulfate to degrade rhodamine B: Properties and degradation mechanism

Shiyu Zhang,Mengru Li,Jingwen Wang,Ruonan Zhang,Xiaoyu Ma,Haisheng Tao

Metal-organic frameworks with high porosity have received much attention in environmental pollutant treatment. This study presented a simple single-pot solvent thermal method for the preparation of a bimetal-organic framework MIL-53(Fe,Ni), further used for activated peroxydisulfate to degrade rhodamine B (RhB). The morphology and structure of the sample were characterized by scanning electron microscopy, transmission electron microscopy , x-ray diffraction, photoelectron spectroscopy , fourier transform infrared spectroscopy , and thermogravimetric analysis . The results showed that MIL-53(Fe,Ni) was successfully synthesized by the simple reaction, with high thermal stability and high specific surface area. The effects of pH value, co-existing ions, temperature, humic acid and different real water samples on RhB degradation were systematically investigated. Under optimized conditions, 93.9% of RhB was degraded within 180 min, together with excellent reusability. Quenching experiments and electron paramagnetic resonance showed that both free radicals (∙OH, SO 4 ∙- and O 2 ∙- ) and non-free radicals ( 1 O 2 and direct charge transfer) were responsible for the RhB degradation. In addition, the identification of intermediates by high-resolution mass spectrometer and reaction site prediction calculations (electrostatic potential, Fukui function and molecular orbit analysis), proposing a possible degradation pathway of RhB. The work highlights the broad applications of bimetal-organic frameworks in advanced oxidation processes .

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JOURNAL OF NANOBIOTECHNOLOGY · 2023 ·Vol. 21 ·期 1 ·1-17 · IF 10.2

Cascade reaction triggering and photothermal AuNPs@MIL MOFs doped intraocular lens for enhanced posterior capsular opacification prevention

Hong Yueze,Fang Qiuna,Bai Ting,Zhao Peiyi,Han Yuemei,Lin Quankui

Posterior capsular opacification (PCO) is the most common complication after cataract surgery. Present strategies can’t meet the clinical needs of long-term prevention. This research reports a novel intraocular lens (IOL) bulk material with high biocompatibility and synergistic therapy. Gold nanoparticles (AuNPs) doped MIL-101-NH 2 metal–organic frameworks (MOFs) (AuNPs@MIL) was firstly fabricated via in situ reductions. Then the functionalized MOFs were uniformly mixed with glycidyl methacrylate (GMA) and 2-(2-ethoxyethoxy) ethyl acrylate (EA) to form the nanoparticle doped polymer (AuNPs@MIL-PGE), and which was used to fabricate IOL bulk materials. The materials’ optical and mechanical properties with different mass contents of nanoparticles are investigated. Such bulk functionalized IOL material could efficiently remove residual human lens epithelial cells (HLECs) in the capsular bag in the short term, and can prevent PCO on demand in the long run by near-infrared illumination (NIR) action. In vivo and in vitro experiments demonstrate the biosafety of the material. The AuNPs@MIL-PGE exhibits excellent photothermal effects, which could inhibit cell proliferation under NIR and doesn’t cause pathological effects on the surrounding tissues. Such functionalized IOL can not only avoid the side effects of the antiproliferative drugs but also realize the enhanced PCO prevention in clinical practice.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Covalently connected core–shell NH2-MIL-125@COFs-OH hybrid materials for visible-light-driven CO2 reduction

Jiajia Wang,Lizhi Wang,Du Zhang,You Wang,Jiawei Li,Fa Zhou,Jianhan Huang,You-Nian Liu

Herein, the covalently connected core–shell metal–organic frameworks (MOFs)@covalent-organic frameworks (COFs) hybrid materials were successfully constructed by coating the stable COF-OH shell on the NH 2 -MIL-125 core. The introduction of the NH 2 -MIL-125 core endowed the hybrid materials with high Brunauer–Emmett–Teller (BET) surface area ( S BET ) and abundant unsaturated metal sites. And the coating of COF-OH shell endowed the hybrid materials outstanding physicochemical stability and visible-light response, and suitable band gaps. Moreover, the thickness of the COF-OH shell was carefully adjusted according to the feeding amount of NH 2 -MIL-125. Impressively, the electron transfer pathway in the formed heterostructure was clarified and it was proven that a type-II heterojunction was generated between the MOFs and the COFs. The formed stable C N covalent bonds in the interfacial layer was beneficial to the photogenerated electron transfer and the electron-hole pairs separation, which greatly enhanced the CO 2 photocatalytic reduction. The product NH 2 -MIL-125@COF-3 exhibited the highest CO yield of 22.93 μmol·g −1 ·h −1 , about 2 times higher than NH 2 -MIL-125 (11.82 μmol·g −1 ·h −1 ) and 3 times greater than COF-OH (7.26 μmol·g −1 ·h −1 ). This work can provide helpful ideas for the careful design of the novel MOFs@COFs hybrid materials as well as useful exploration for the CO 2 photocatalytic reduction.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

Preparation of N and Ce Co-doped MIL-101(Fe) Heterogeneous Catalysts for Efficient Electro-Fenton Oxidation

Jiakang Wan,Ling Wang,Wentao Xu,Zehai Xu,Junsheng Yuan,Guoliang Zhang

Design and synthesis of high-efficiency and stable heterogeneous catalysts for the electro-Fenton process remain challenging. In this study, a co-doped Ce and N metal–organic framework MIL-101(Fe) heterogeneous catalyst (Ce/N-MIL-101(Fe) was synthesized by a facile one-step solvothermal method. Polyvinyl pyrrolidone played dual roles during the fabrication process, which not only acted as a nitrogen source for doping but also prevented MIL-101(Fe) molecules from aggregating and reinforcing the formation crystal with a complete polyhedral crystal shape. The introduction of Ce significantly enhanced the density of active sites and promoted the Fe3+/Fe2+ cycle of the reaction system. Owing to the specific structure and properties, the rate of electron transfer in the catalytic process was significantly promoted. The synthesized Ce/N-MIL-101(Fe) catalyst exhibited a high degradation rate for dyes (>98%) with competitive stability and reusability. Moreover, compared with common electro-Fenton catalysts usually operated in a limited pH range of 3.0–6.0, the working pH range of Ce/N-MIL-101(Fe) was widened up to 10.0. The design concept for producing abundant active sites with co-doping into frameworks can be extended to more heterogeneous electro-Fenton catalysts constituted by other porous materials.

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Molecular Catalysis · 2022 · IF 5.089

Scalable synthesis of MIL-88A(Fe) for efficient aerobic oxidation of cyclohexene to 2-cyclohexene-1-ol

Nan Li,Changping Jian,Yaping Song,Li Wang,Ata Ur Rehman,Yanghe Fu,Fumin Zhang,De-Li Chen,Weidong Zhu

Herein, we reported a facile and scalable approach for the synthesis of Fe-based MOF MIL-88A(Fe) via a simple liquid-phase route at atmosphere pressure, and its application as a heterogeneous catalyst for the efficient aerobic oxidation of cyclohexene to value-added 2-cyclohexene-1-ol. Over 130 g of spindle-shaped MIL-88A(Fe) nanocrystals with high crystallinity, monodispersed particle size, and large specific surface area were easily synthesized per batch according to our method. The resultant MIL-88A(Fe) exhibited a high catalytic activity (conversion: 81%) with 70% selectivity for 2-cyclohexene-1-ol in the aerobic oxidation of cyclohexene with O 2 as the sole oxidant under mild reaction conditions (0.5 MPa of O 2 , 353 K for 8 h), outperforming the analogues reported in the literatures. The combined experimental and theoretical approach support the reaction mechanism of the oxidation of cyclohexene via both the free radical reaction pathway and Fe-mediated reaction pathway, resulting in the selective formation of 2-cyclohexene-1-ol.

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JOURNAL OF MOLECULAR STRUCTURE · 2023 · IF 3.8

SERS imprinted sensor based on Ta2O5/Ag@MIL-101 (Fe) composite for selective detection of 2,6-dichlorophenol

Xiyue Wang,Shang Gao,Junfu Wang,Xinying Fan,Chi Song,Chuanwei Zhou,Shuyun Shi,Dandan Wang,Hongji Li

In this work, a novel sensor for selective detection of 2,6-dichlorophenol (2,6-DCP) is developed by combining the selectivity of molecular imprinting technology (MIPs) with the sensitivity of SERS technology. In order to enhance SERS activity of the substrate, Ag nanoparticles are loaded on Ta 2 O 5 particles by means of photodeposition. The synthesized Ta 2 O 5 @Ag is combined with MIL-101 (Fe) to enrich more target molecules and reduce the limit of detection. Finally, Ta 2 O 5 /Ag/MIL-101(Fe)@MIPs (TAM@MIPs) is synthesized by precipitation polymerization for selective detection of 2,6-DCP. When the concentration of 2,6-DCP changes between the range of 10 −2 ∼ 10 −9 M, the Raman intensity and concentration present a good linear relationship. The correlation coefficient (R 2 ) is 0.9969 and the limit of detection (LOD) of 2,6-DCP is 10 −9 M. Furthermore, Under UV-irradiation, the TAM@MIPs also presents photocatalytic performance, which can effectively degrade the organic interfering molecule adsorbed on its surface and present high-efficiency reproducibility. This method broadens the application field of SERS detection and provides a new procedure for the phenolic pollutant detection.

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Materials Advances · 2023 ·Vol. 4 ·期 3 ·940-947 · IF 5

Construction of a La-ZnIn2S4/MIL-125(Ti) heterojunction for highly efficient photocatalytic degradation of aflatoxin B1

Xiaobing Yang,Junjie Pan,Bingcong Xing,Wenjie Lei,Yingchun Fu,Kejun Cheng

Nowadays, aflatoxin B1 (AFB1) contamination is considered as one of the most common food safety issues for humans and animals. As one of the most advanced oxidation techniques, photocatalytic degradation can break down organic contaminants into nontoxic and harmless materials efficiently. In this paper, we explored the degradation efficiency of AFB1 by ZnIn2S4. To promote the photocatalytic degradation efficiency of AFB1, ZnIn2S4 was coupled with MIL-125(Ti) and then doped with La [this hybrid is denoted as La-ZnIn2S4/MIL-125(Ti)] to effectively convert it via photocatalytic generation of superoxide radicals (˙O2− and ˙OH) and achieve much enhanced photocatalytic performance, which is demonstrated by degrading 97.6% of AFB1. According to the transient photocurrent responses, the doping of La and coupling with MIL-125(Ti) can highly improve the efficient separation of the photoinduced electron–hole pairs on ZnIn2S4, leading to the effective conversion of OH− and O2 into ˙O2− and ˙OH, respectively, during the photodegradation process. This strategy of coupling with MOFs and doping with rare earth elements provides a facile and efficient method for degrading food pollutants produced by aflatoxins.

CAS / MDL: 62-55-5 1162-65-8
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JOURNAL OF SOLID STATE CHEMISTRY · 2022 · IF 3.656

Synergistic removal of organic pollutants by Co-doped MIL-53(Al) composite through the integrated adsorption/photocatalysis

Chunfu Liu,Chenyu Zhu,Han Wang,Shenao Xie,Junyang Zhou,Hongjun Fang

Co-doped metal organic frameworks (MOFs) were fabricated by a facile route and applied to remove (tetracycline, congo red, methylene blue and rhodamine B) through integrated adsorption and photocatalysis . The assembled MOFs composite exhibited larger S BET (889 ​m 2 /g), broad light adsorption, and accelerated carrier kinetics, which helped to enhance adsorption and photocatalysis performance. Specifically, nearly 100% TC (40 ​mg/L) could be removed by the Co-MIL-10 within 12 ​min solar-light irradiation, significantly faster than that of solo MIL-53(Al) (82%) and CoAl-LDH (54%), separately. Furthermore the obtained rate constant (0.2064 min −1 ) was 4.8 times and 9.7 times greater than that of MIL-53(Al) and CoAl-LDH, respectively. The quenching/EPR characterization suggested that photo-generated h + / • O 2 − / • OH species were responsible for TC oxidation , of which h + showed the great impact. Cycling experiments verified the robust stability of the MOFs catalyst. As well, an underlying photocatalytic mechanism of the current system was investigated in detail.

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ENVIRONMENTAL RESEARCH · 2022 · IF 8.431

Facile synthesis of CoFe2O4@MIL–53(Al) nanocomposite for fast dye removal: Adsorption models, optimization and recyclability

Luan Minh Nguyen,Ngoan Thi Thao Nguyen,Thuy Thi Thanh Nguyen,Dai Hai Nguyen,Duyen Thi Cam Nguyen,Thuan Van Tran

The global occurrence of textile dyes pollution has recently emerged, posing a serious threat to ecological systems. To abate dye contamination, we here developed a novel magnetic porous CoFe 2 O 4 @MIL–53(Al) nanocomposite by incorporating magnetic CoFe 2 O 4 nanoparticles with MIL–53(Al) metal–organic framework. This nanocomposite possessed a surface area of 197.144 m 2  g −1 and a pore volume of 0.413 cm 3  g −1 . The effect of contact time (5–120 min), concentration (5–50 mg L −1 ), dosage (0.1–1.0 g L −1 ), and pH (2–10) on Congo red adsorption was clarified. CoFe 2 O 4 @MIL–53(Al) could remove 95.85% of Cong red dye from water with an accelerated kinetic rate of 0.6544 min −1 within 10 min. The kinetic and isotherm models showed the predominance of Bangham and Temkin. According to Langmuir, the maximum uptake capacities of CoFe 2 O 4 @MIL–53(Al), CoFe 2 O 4 , and MIL–53(Al) adsorbents were 43.768, 17.982, and 15.295 mg g −1 , respectively. CoFe 2 O 4 @MIL–53(Al) was selected to optimize Cong red treatment using Box–Behnken experimental design. The outcomes showed that CoFe 2 O 4 @MIL–53(Al) achieved the highest experimental uptake capacity of 35.919 mg g −1 at concentration (29.966 mg L −1 ), time (14.926 min), and dosage (0.486 g L −1 ). CoFe 2 O 4 @MIL–53(Al) could treat dye mixture (methylene blue, methyl orange, Congo red, malachite green, and crystal violet) with an outstanding removal efficiency of 81.24% for 30 min, and could be reused up to five cycles. Therefore, novel recyclable and stable CoFe 2 O 4 @MIL–53(Al) is recommended to integrate well with real dye treatments systems.

CAS / MDL: 121-44-8
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DALTON TRANSACTIONS · 2022 ·Vol. 51 ·期 48 ·18473-18479 · IF 4.569

MIL-47(V)-derived carbon-doped vanadium oxide for selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran

Yan Zhou,Shanshan Lv,Han Li,Qikang Wu,Taiyu Chen,Shaohuan Liu,Wanying Li,Wenjuan Yang,Zheng Chen

The development and transformation of biomass-derived platform compounds is a sustainable way to deal with the fossil fuel crisis. 5-Hydroxymethylfurfural (HMF) can be reduced or oxidized to produce many high-value compounds; however, it is challenging to effectively produce 2,5-diformylfuran (DFF) due to overoxidation. In this work, a carbon-doped V2O5 (C–V2O5) material was obtained through pyrolysis of MIL-47(V) nanorods, a typical metal–organic framework material. The X-ray diffraction patterns and X-ray photoelectron spectra showed that the graphitized carbon species were incorporated in C–V2O5. High-efficiency HMF oxidation, high specific selectivity for DFF and excellent recycling could be achieved with the C–V2O5 catalyst. Fourier-transform infrared spectroscopy combined with density functional theory (DFT) calculation revealed that graphitized carbon weakens the VO bond and promotes the formation of oxygen vacancies in C–V2O5, thus improving the catalytic activity in the oxidation of furfuryl alcohols. The V4+ induced by oxygen vacancies will be oxidized by O2 to form V5+, so that the cycle can be realized. It exhibits remarkable selectivity in the oxidation of different alcohols produced from biomass based on the relatively constant active sites in C–V2O5.

CAS / MDL: 7718-98-1
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Food Analytical Methods · 2022 ·Vol. 15 ·期 10 ·2830-2839 · IF 3.498

N-Doped TiO2–Carbon Composites Derived from NH2-MIL-125(Ti) for Electrochemical Determination of tert-Butylhydroquinone

Tang Jing,Li Jie,Liu Tianna,Tang Wenjing,Li Nali,Zheng Shengbiao,Guo Jiahao,Song Changchun

Electrochemical determination of tert-butylhydroquinone (TBHQ) is vital to food safety due to negative health effects; however, bare electrode of traditional electrochemical sensors generally has a narrow linear range and low sensitivity, limiting their practical application. Accordingly, the nano-architecture fabricated with N-doped TiO 2 –carbon nano-composites (TiO 2 /NC) is prepared by the thermolysis of NH 2 functionalized MIL-125(Ti) metal–organic frameworks (NH 2 -MIL-125(Ti)). TiO 2 /NC composites are firstly developed as the electrochemical material for electrochemical determination of TBHQ. The TiO 2 /NC composites with a highly porous structure, excellent conductivity and electron transportation, and large surface area show remarkable electrochemical oxidation ability for TBHQ. Under optimal conditions, TiO 2 /NC composite-modified electrode presents a broader linear response to TBHQ concentration of 0.05–100 μM with the detection limit as low as 4 nM (S/N = 3). Finally, the sensor platform is implemented directly to determine TBHQ in edible oil for evaluation of its practical application. TiO 2 /NC composites sensor fabricated perform larger linear range with high sensitivity and anti-interference properties, which can be used as a potential for electrochemical determination of TBHQ.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2022 · IF 5.518

Exposed carboxyl functionalized MIL-101 derivatives for rapid and efficient extraction of heavy metals from aqueous solution

Tuckyun Cheang,Wenbin Huang,Weiping Li,Siyu Ren,Haihui Wen,Ting Zhou,Yongcheng Zhang,Weihao Lin

Exploring efficient adsorbent for heavy metals remediation from wastewater and contaminated soil is a pursuing issue. Robust functionalized metal-organic frameworks (MOFs) represent one of burgeoning scavengers because of their tunable structural topology , designable functionalities and extraordinary affinity for heavy metal ions . In this present work, we report a facile and versatile strategy to synthesize a series of carboxyl-functionalized MIL-101(Fe) derivatives by microwaving a solution of organic ligands with varying carboxyl number and Fe 3+ ions. The resulting MIL-101(Fe) derivatives were characterized using various techniques including scanning electron microscope (SEM), powder X-ray diffraction, Fourier transformed infrared, Brunauer–Emmett–Teller specific surface area and X-ray photoelectron spectroscopy. The intrinsically carboxyl-rich characteristic and large surface area of MIL-101-(COOH) 2 afford fast adsorption kinetics (< 15 min) and high saturation capacity (467.6 mg/g) for Pb(II). Strikingly, it can efficiently capture Pb(II) possessing impressive adsorption efficiencies (> 90%) over a wide pH range of 4.5–11.0. Moreover, the resulting MIL-101-(COOH) 2 simultaneously exhibited high affinity toward different types of heavy metal ions, including borderline Lewis acid (Pb(II), Cu(II) and Ni(II)), soft Lewis acid (Cd(II) and Hg(II)) and hard Lewis acid (Eu(III) and Cr(III)). Such impressive treatment for Pb(II)-contaminated lead-acid battery industrial wastewater (more than 96.7%) can be attributed to the coordination arising from abundant carboxyl groups in the pores of MIL architecture with target heavy metal ions. Significantly, these findings validate the exceptional potential of carboxyl-functionalized MIL-101(Fe) derivatives in the application of heavy metal ions remediation.

CAS / MDL: 89-05-4 528-44-9
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