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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Superior selective adsorption of anionic organic dyes by MIL-101 analogs: Regulation of adsorption driving forces by free amino groups in pore channels

Wei Zhang,Run-Zhi Zhang,Yun Yin,Ji-Min Yang

We herein report that the forces driving the adsorption of dyes onto MIL-101-NH 2 micro/nanoparticles, which are electrostatic , hydrogen bonding , and π-π stacking interactions, pore-volume, and steric hindrance , can be modulated by varying the molar ratio of terephthalic acid and 2-aminoterephthalic acid in the reaction system. The adsorption capacities of MIL-101-NH 2 -1 were determined to be 2967.1 mg g −1 for Congo red (CR), 461.7 mg g −1 for methyl orange (MO), and 259.8 mg g −1 for acid chrome blue K (AC), which were higher by 117.0%, 102.2%, and −19.6%, respectively, compared with those of pristine MIL-101. This adsorption behavior could be rationalized based on the molecular structure of the dye, its zeta potential , BET specific surface area, and the adsorption characteristics of the dye. The study revealed that free –NH 2 groups increase the hydrogen bonding and electrostatic interactions between MIL-101-NH 2 micro/nanoparticles and linear anionic dyes, thereby improving the adsorption performance for linear anionic dyes by overriding the effect of pore-volume. On the other hand, the increased steric hindrance between MIL-101-NH 2 micro/nanoparticles and a nonlinear anionic dye decreased the adsorption performance for the nonlinear dye, overriding the effects of hydrogen bonding, and electrostatic interactions. The adsorption uptakes of MIL-101-NH 2 -1 toward the linear anionic organic dyes (CR and MO) were found to be much higher than those of the other two MIL-101-NH 2 adsorbents investigated herein. However, the adsorption uptake of MIL-101-NH 2 -1 toward the nonlinear anionic organic dye (AC) was the smallest owing to different adsorption mechanisms. The adsorption performance of MIL-101-NH 2 is governed by the synergetic interplay between the hydrogen bonding, electrostatic and π–π stacking interactions, pore-volume, and the steric hindrance of the adsorbent.

CAS / MDL: 7789-02-8 75-59-2
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SENSORS AND ACTUATORS B-CHEMICAL · 2020 · IF 7.1

A novel photoelectrochemical immunosensor for N1-methyladenine detection based on BiVO4/g-C3N4 heterojunction with signal amplification of TiO2@NH2-MIL-125(Ti)

Yunlei Zhou,Yue Wang,Shurong Li,Xi Fang,Huanshun Yin,Po Wang,Shiyun Ai

Photoelectrochemical (PEC) immunosensor was designed to detect N 1 -methyladenosine (m 1 A), where BiVO 4 /g-C 3 N 4 heterojunction was employed as photoactive material, polyamidoamine (PAMAM) and 4-carboxyphenylboronic acid (CPBA) were used as m 1 A antibody immobilization matrix, and Ti-based metal-organic framework encapsulated heterostructure of TiO 2 @NH 2 -MIL-125(Ti) was adopted as signal amplification. Due to the interaction between TiO 2 and phosphate, TiO 2 @NH 2 -MIL-125(Ti) was captured after immunoreaction between m 1 A and its antibody, which can further improve the detection sensitivity with increased PEC response. Under optimal experimental conditions, this method presented wide dynamic range (0.05–35 nM) with the low determination limit (16.7 pM, S/N = 3). This detection strategy showed good detection reproducibility, stability and selectivity. This method was applied to assess the effect of antibiotics on m 1 A content in the leaves, stems and roots of rice seedlings.

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APPLIED CATALYSIS B-ENVIRONMENTAL · 2019 · IF 14.229

Tuning Lewis acidity of MIL-88B-Fe with mix-valence coordinatively unsaturated iron centers on ultrathin Ti3C2 nanosheets for efficient photo-Fenton reaction

Munir Ahmad,Xie Quan,Shuo Chen,Hongtao Yu

Iron containing MOFs have been currently estimated as greater candidates for heterogeneous Fenton catalysts due to their open pores and well dispersed metallic components. However, metals in majority of MOFs are bounded by organic linkers, which reduces Lewis acid sites and make them not available for H 2 O 2 activation. Creating coordinatively unsaturated metal centers (CUCs), acting as Lewis acid sites, is a feasible approach for efficient photo-Fenton activity. Here, we successfully synthesized a photo-Fenton CUCs-MIL-88B-Fe catalyst with mixed-valence (Fe II /Fe III ) on ultrathin Ti 3 C 2 nanosheets. The Lewis acidity was probed by TPD-NH 3 and IR-pyridine analysis and tested for pollutants degradation. The results showed that CUCs-MIL-88B-Fe/Ti 3 C 2 displayed highest photo-Fenton activity under visible light irradiation at pH 3.0 and 10 mM H 2 O 2 . This could be attributed with the CUCs, fast H 2 O 2 activation, high Lewis acidity and carrier separation with Ti 3 C 2 nanosheets due to its high charge mobility. Furthermore, CUCs-MIL-88B-Fe/Ti 3 C 2 exhibited a good stability and reusability.

CAS / MDL: 68-12-2 100-21-0
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Journal of Energy Storage · 2023 · IF 9.4

Myristic acid-tetradecanol-capric acid ternary eutectic/SiO2/MIL-100(Fe) as phase change humidity control material for indoor temperature and humidity control

Min Li,Fan Luo,Xianghui Liang,Shuangfeng Wang,Xuenong Gao,Zhengguo Zhang,Yutang Fang

Building materials with the dual function of temperature and humidity regulation can improve people's living comfort and reduce energy consumption. In this work, a simple and convenient strategy for building a comfortable indoor temperature and humidity environment was proposed. The phase change humidity control material (PCHCM) was prepared by the mixing of form-stable composite phase change material (CPCM) as temperature-control component and hygroscopic MIL-100(Fe) as humidity-control component. In PCHCM, the CPCM was obtained by molten recombination of myristic acid, tetradecanol, and capric acid (MA-TD-CA) as phase change material and hydrophilic fumed silica (SiO 2 ) as porous carrier, and MIL-100(Fe) was synthesized by low-temperature solution method. Thermal analysis indicated that, under the optimized mass ratio of 28.8%MA-61.2%TD-10%CA, the CPCM containing 30 % SiO 2 could effectively prevent the leakage of ternary eutectic , with a suitable phase change temperature and enthalpy (21.74 °C, 96.70 J·g −1 ). The thermal and wet performance evaluation confirmed that the PCHCMs containing 40–50 % CPCM had human body comfortable phase change temperature (26.96–27.26 °C) and high saturation adsorption capacity (0.179–0.205 g/g) at 60 % RH as well as outstanding thermal and wet cycle reliability, indicating the novel MA-TD-CA/SiO 2 /MIL-100(Fe) PCHCM has broad application potential in room temperature and humidity control and building energy conservation .

CAS / MDL: 334-48-5 544-63-8
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Journal of Water Process Engineering · 2023 · IF 7

A direct Z-scheme MoS2/NH2-MIL-68(In)-derived In2S3 photocatalyst for efficient photocatalytic reduction of Cr(VI) under visible-light irradiation

Chumin Yan,Xiaoli Dong,Yu Wang,Nan Zheng,Hongchao Ma,Xiufang Zhang

Inorganic semiconductors prepared from MOFs as sacrificial precursors are promising photocatalytic materials. In this work, the direct Z -scheme MoS 2 /NH 2 -MIL-68(In)-derived In 2 S 3 (MoS 2 /In 2 S 3 ) heterojunction composites have been synthesized by sulfidation treatment of MoS 2 /NH 2 -MIL-68(In) (MoS 2 /NM68) composites. Morphological and crystal structural results confirmed that MoS 2 was uniformly dispersed in In 2 S 3 . According to the reduction for Cr(VI) experimental results, the photocatalytic performance of MoS 2 /In 2 S 3 heterojunction composite under visible light irradiation is significantly better than that of pristine MoS 2 and In 2 S 3 , respectively. In addition, the photocatalytic activities of the MoS 2 /In 2 S 3 (II) at different pH and high concentrations of Cr(VI) were also investigated. This paper presents a novel approach to the construction of heterojunction photocatalytic materials using MOFs as sacrificial precursors.

CAS / MDL: 207398-97-8 1317-33-5
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2023 ·Vol. 170 ·期 12 ·120504 · IF 3.9

Three-Dimensional Porous Structural Polyvinylidene Fluoride-Blending Ethylene Carbonate and MIL-125 (Ti) Composite Membrane-Based Gel Polymer Electrolyte for Lithium Metal Battery

Zhenyu Fu,Yuhan Li,Lirong Huang,Weiya Zhang,Ling Weng

Lithium metal batteries are considered promising contenders for the next generation of high energy density batteries. However, lithium metal anode with inhomogeneous lithium deposition in liquid electrolyte causes the uncontrolled growth of lithium dendrites. Owing to the high dielectric constant, thermal stability and electromechanical stability of polyvinylidene fluoride, we design a novel gel polymer electrolyte consisting of porous polyvinylidene fluoride polymer matrix, liquid electrolyte, ethylene carbonate and MIL-125 (Ti) (Ti8O8(OH)4(BDC)6, BDC = 1,4-benzene dicarboxylate) for facilitating Li+ transfer and alleviating the growth of lithium dendrites. The high dielectric constant environment facilitates the dissociation of Li+, and the porous polymer matrix structure accommodates more Li+ for fast transfer. Ethylene carbonate reduces the crystallinity of the polymer matrix and improves the ionic conductivity. MIL-125 (Ti) nanoparticles with surface area and uniform micropores improve toughness for enhancing mechanical property, and synergistically promote the Li+ transfer for building stable interfacial phase to alleviate the growth of Li dendrites. Therefore, the gel polymer electrolyte has high ionic conductivity of ∼1.50 × 10−3 S cm−1 at 25 °C, and quasi-solid-state Li/LiFePO4 battery has high discharge capacity of 153.5 mAh g−1 after 250 cycles at 25 °C and 0.3 C.

CAS / MDL: 90076-65-6
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Journal of Water Process Engineering · 2023 · IF 7

Green water-etching synthesized La-MIL-101(Fe)-NH2@SiO2 yolk-shell nanocomposites with superior pH stability for efficient and selective phosphorus recovery

Shuangli Li,Yu Zhang,Sen Qiao,Jiti Zhou

Although MIL-101(Fe) has a homogeneous distribution of active metal sites, the relatively low stability of its coordination bonds limits its potential for application, especially in harsh environments. Here, a novel lanthanum-doped MIL-101(Fe)-NH 2 @mesoporous SiO 2 yolk-shell (LMFN-YS) material, synthesized by green water-etching, has effectively improved the adsorption capacity and stability of MIL-101(Fe)-NH 2 . Compared to traditional acid-base etching methods, water etching offered a more co-friendly and cost-effective approach to producing yolk-shell structures. Due to the mesoporous protective shell of mesoporous SiO 2 and more exposed active sites, the yolk-shell materials showed a faster adsorption rate (30 min) and a larger uptake capacity (240.0 mg P/g) than those of MIL-101. The material also exhibited broad range of pH stability from 2 to 10 and displayed good cyclic regeneration ability, with a removal efficiency of 75.9 % after three cycles. Additionally, it demonstrated excellent selectivity towards various coexisting anions such as Cl − , NO 3 − , SO 4 2− , CO 3 2− and HCO 3 − at diverse ionic strengths ranging from 0.001 to 1 M. The superior performance of L 1 MFN-YS (yolk-shell materials of La: Fe = 1:1) was attributed to a combination of factors, including ligand exchange between La(Fe)-OH and phosphates, Lewis acid-base interaction and electrostatic attraction. Additionally, high phosphate removal performance was observed in the real petrochemical wastewater (initial concentrations of 5.48 mg P/g) with a residual effluent concentration of 0.05 mg P/L, which was below the A-level standard of phosphate effluent in China (0.5 mg/L). This work provides a green method for preparing yolk-shell materials with improved ability to treat phosphate wastewater.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Tightly contacted heterojunction of ZnS/ZIS/In2S3: In situ construction from ZIF-8@MIL-68(In) and visible-light induced photocatalytic hydrogen generation

Boyi Yan,Zhongqiao Sun,Yide Han,Hao Meng,Xia Zhang

The construction of a tightly contacted heterojunction consisting of multi-components is proven to be one of the effective strategies to promote the photogenerated charges separation and to develop high-efficient photocatalysts in hydrogen evolution . Herein, a ternary hollow heterostructure of ZnS/ZIS/In 2 S 3 has been fabricated by using a binary MOF@MOF (ZIF-8@MIL-68(In)) as the precursor, and an in-situ sulfurization of ZIF-8@MIL-68(In) is controlled to optimize the photocatalytic performances. The resulting samples are signed as Z@M- t , where the t is pointed to the sulfurization time being varied from 4 h to 48 h. It’s shown that the hierarchical and hollow architecture is formed for Z@M- t , and with the reinforced light harvest ability in both UV and visible light regions. In the subsequent visible-light-induced photocatalytic hydrogen generation, the optimized Z@M-24 manifests significantly improved hydrogen evolution rate of 607.34 μmol g -1 h −1 , which values are evidently higher than that by the single MOF and binary ZIF-8@MIL-68(In) heterostructure. The electrochemical analyses and the electron paramagnetic resonance (EPR) spectrum were analyzed to clarify the charge transfer routes and the enhanced photocatalytic mechanism, in which the contribution of each metal sulfide is also discussed. Finally, the good photocatalytic stability and reusability of Z@M-24 heterostructure are also represented, which define the structure superior brought by the effective heterojunction based on the in-situ sulfurization strategy of binary ZIF-8@MIL-68(In), and determine their prospect applications in the efficient H 2 production under visible light irradiation.

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Symmetry-Basel · 2023 ·Vol. 15 ·期 7 ·1334 · IF 2.7

A Symmetry Concept for the Self-Assembly Synthesis of Mn-MIL-100 Using a Capping Agent and Its Adsorption Performance with Methylene Blue

Guolin Song,Chengzhu Shen,David Bassir,Qiulin Li

In this study, a facile strategy of regulated self-assembly synthesis of Mn-MIL-100, using sodium acetate (CH3COONa) as a mono-dentate ligand capping agent (CA), was proposed. The as-prepared product is denoted Mn-MIL-100-CA. The coordination modulation of CH3COONa, led by its interference in the connectivity and symmetry of the metal centers and organic nodes, plays a vital role in the synthesis process. The crystallinity, morphology, topology, and properties of such MOF products were improved, since the self-assembly process of Mn-MIL-100-CA was promoted and regulated effectively. The materials were systematically characterized via XRD, SEM, N2isotherms, XPS, and TGA in terms of crystallization behavior, morphology, topology, chemical composition, and thermal and water stability. The ability of Mn-MIL-100 and Mn-MIL-100-CA to remove methylene blue (MB) from an aqueous solution was investigated using a UV–vis spectrophotometer. The results indicate that with the addition of a molar ratio of 50% CH3COONa, Mn-MIL-100-CA particles developed a regularly symmetrical morphology, i.e., ‘spherical pyramid-like structure’ crystals with a dimension of 2~5 μm. Their specific surface area and pore volume increased by 59.2% and 56.7%, respectively. The increased proportion of Mn3+implies reduced crystal defects and improved crystal structural order and integrity, and therefore an enhanced water stability. Mn-MIL-100-CA exhibited excellent adsorption performance towards MB from aqueous solution. The equilibrium adsorption value was as high as 1079.9 mg/g, which is 44.7% higher than that of Mn-MIL-100 without the addition of CA. The good adsorption capacity and excellent water stability mean that Mn-MIL-100-CA has great potential for the practical removal of MB dye pollutants from water.Keywords:metal organic frameworks;Mn-MIL-100;capping agent;symmetry;self-assembly;methylene blue adsorption

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SEPARATION AND PURIFICATION TECHNOLOGY · 2019 · IF 5.107

A new MOFs/polymer hybrid membrane: MIL-68(Al)/PVDF, fabrication and application in high-efficient removal of p-nitrophenol and methylene blue

Yuanming Tan,Zhongqiao Sun,Hao Meng,Yide Han,Junbiao Wu,Junli Xu,Yan Xu,Xia Zhang

MOFs/polymer hybrid membranes combine the special surface activity of MOFs and the excellent carries nature of porous polymer and thus exhibit unexpected adsorption/separation performances in the solid-phase extraction. In this paper, a new kind of MOFs/polymer composite membrane , MIL-68(Al)/PVDF have been fabricated for the first time through blending the MIL-68(Al) nanoparticles and polyvinylidene fluoride (PVDF) casting solution and following the lyotropic phase transition. Some means such as SEM, XRD and FT-IR are used to character the structure of these hybrid membranes. The membrane performances including the hydrophilic/hydrophobic properties, membrane porosity and membrane water flux are also measured. The effects of doping amount of MIL-68(Al) on the structure and performances of MIL-68(Al)/PVDF hybrid membranes are discussed. Two persistent organic pollutants : p -nitrophenol (PNP) and methylene blue (MB) are chosen as main adsorption objects to evaluate the adsorption activity of MIL-68(Al)/PVDF hybrid membranes. The influences of various conditions on the adsorption activities are investigated in detail and the optimum adsorption conditions are determined. All the MIL-68(Al)/PVDF hybrid membranes exhibit enhanced adsorption capacity compared to pristine PVDF, and the adsorption activities of hybrid membranes are promoted continually with the increasing doping contents of MIL-68(Al). The adsorption thermodynamics analysis indicates that the adsorption process is mainly characterized by Langmuir monolayer adsorption and chemical adsorption . The coordination bonding formed between NO 2 of PNP and Al(III) of MIL-68(Al), and the acid-base interaction between the sulfur of MB and Al(III) of MIL-68(Al) may be responsible to the highest removal efficiency of PNP and MB. The good dynamics adsorption and regeneration performances indicate the prospect applications of these MOFs/PVDF hybrid membranes in the separation of organic contaminants from industrial waste water.

CAS / MDL: 100-21-0
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MICROCHEMICAL JOURNAL · 2018 · IF 2.746

Hydrogen-bonding-induced efficient dispersive solid phase extraction of bisphenols and their derivatives in environmental waters using surface amino-functionalized MIL-101(Fe)

Man Gao,Wei Liu,Xuran Wang,Yanyan Li,Peipei Zhou,Liwan Shi,Buxing Ye,Randy A. Dahlgren,Xuedong Wang

Herein, we investigated in detail the relationship between surface properties and extraction performance of virgin and amino-functionalized MIL-101s(Fe) for the extraction of 10 bisphenols (BPs) and their derivatives. These BPs were used as model contaminants due to their different hydroxyl groups and contrasting polarities. The differential sorption efficiencies for relatively polar BPs (BPF, BPE, BPA , BPB , BPZ, BPAP and BPP) lies in the formation of hydrogen-bonding between OH of target analytes and NH 2 of two MIL-101s(Fe). However, the surface properties of MIL-101(Fe) and NH 2 -MIL-101s(Fe), such as S BET and pore structure , determined the extraction recoveries for BPs derivatives (BADGE, BADGE·2H 2 O and BFDGE·2H 2 O) due to lack of OH in their molecular structures. NH 2 -MIL-101s(Fe) nanosorbent was successfully applied to the preconcentration/extraction of trace BPs and their derivatives by dispersive solid-phase extraction (DSPE) method. Following optimization of the main factors, recoveries for BPs ranged from 90.8 to 117.8% and their LODs were 0.016–0.131 μg L −1 in environmental waters. Experimental precisions based on relative standard deviations were 0.9–4.9% for intra-day and 1.3–7.6% for inter-day analyses, respectively. These findings provide important information on how to design and modify nanosorbents for highly efficient extraction of pollutants having contrasting polarities. Moreover, the newly developed NH 2 -MIL-101s(Fe)-based DSPE method has a good application prospect in pretreatment of trace pollutants in real-world waters.

CAS / MDL: 68-12-2
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2019 · IF 6.361

Surface-defect-rich mesoporous NH2-MIL-125 (Ti)@Bi2MoO6 core-shell heterojunction with improved charge separation and enhanced visible-light-driven photocatalytic performance

Shiyu Zhang,Meng Du,Junyan Kuang,Zipeng Xing,Zhenzi Li,Kai Pan,Qi Zhu,Wei Zhou

Mesoporous NH 2 -MIL-125(Ti)@Bi 2 MoO 6 core-shell heterojunctions with surface defects were fabricated through a facile solvothermal method . The mesoporous core-shell structure with a large relative surface area of 87.7 m 2  g −1 and narrow pore size of 8.2 nm extends the photoresponse to the range of visible light due to the narrow band gap of ∼1.89 eV. The visible-light-driven photocatalytic degradation efficiency of highly toxic dichlorophen and trichlorophenol were 93.28 and 92.19%, respectively, and the corresponding rate constants were approximately 8 and 17 times higher than the rates achieved by pristine NH 2 -MIL-125(Ti). The photocatalytic oxygen production rate was increased to 171.3 µmol g −1 . Recycling for several cycles indicates high stability, which is favorable for practical applications. The excellent photocatalytic performance can be ascribed to the formation of the core-shell heterojunctions and to the surface defects that favor charge separation and visible light absorption; the mesoporous structure offers an adequate number of surface active sites and mass transfer. This novel mesoporous core-shell photocatalyst will have potential applications in the environment, and this strategy offers a new insight into fabrication of other high-performance core-shell structure photocatalysts.

CAS / MDL: 10312-55-7
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