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CHEMICAL ENGINEERING JOURNAL · 2016 · IF 5.31

Simple fabrication of flake-like NH2-MIL-53(Cr) and its application as an electrochemical sensor for the detection of Pb2+

Hongxu Guo,Dongfang Wang,Jianhua Chen,Wen Weng,Minqiang Huang,Zishan Zheng

A novel metal-organic framework (MOF) material, flake-like NH 2 -MIL-53(Cr), was prepared by a simple reflux method and then characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The as-prepared MOF was found to be an effective material for the selective electrochemical detection of microgram levels of Pb 2+ in aqueous solution. Detection was performed by square wave anodic stripping voltammetry. The NH 2 -MIL-53(Cr)-modified electrode showed excellent selectivity and stability for Pb 2+ detection. The electrochemical properties and applications of the modified electrode were studied. Operational parameters such as pH, deposition potential, and deposition time, were also optimized to detect trace amounts of metal ions. This method offers a new strategy for heavy metal detection using MOF materials.

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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Fabrication of mixed matrix membranes based on PVDF matrix and ZrT-1-NH2 filler for efficient adsorptive removal of Orange G

Bao-Xu Jiang,Shuang-Bao Li,Ting-Ting Xu,Jian Li,Yu-Teng Zhang

Adsorption membranes have become a hot spot for wastewater treatment in recent years. Due to the lack of active sites in traditional inert materials such as polyvinylidene fluoride (PVDF) membranes, it is difficult to bind pollutants in water with high affinity. Therefore, in this study, ZrT-1-NH 2 /PVDF mixed matrix membranes (MMMs) were prepared by combining an amino-functionalized Zr-based metal–organic cage (ZrT-1-NH 2 ) with a polymer substrate via non-solvent-induced phase separation method for the efficient removal of Orange G (OG) from water. This method has many advantages such as simplicity in operation, high applicability, controllable MOFs loading. The structural characteristics and adsorption properties and of MMMs were also investigated through a series of characterizations and experiments. The result shows that in a 100 mL OG solution with an initial concentration of 50 mg/L and pH=3, M60 exhibited significant adsorption capacity, the removal efficiency reached 97.23 %, with an adsorption capacity of 64.18 mg/g, which is much higher than the pristine PVDF membrane. It is mainly attributed to electrostatic interactions and hydrogen bonding interactions between ZrT-1-NH 2 and OG molecules. This is consistent with the DFT calculations. The introduction of ZrT-1-NH 2 filler improves the performance of PVDF membranes and expands their potential applications.

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Magnetochemistry · 2024 ·Vol. 10 ·期 10 ·74 · IF 2.6

Facile Synthesis of Core-Shell Magnetic Iron Oxide@SiO2-NH2 Nanoparticles and Their Application in Rapid Boron Removal from Aqueous Solutions

Qinqin Hu,Manman Zhang,Jiaoyu Peng,Yaping Dong,Wu Li,Lingzong Meng

In this study, amino-functionalized magnetic particles (iron oxide@SiO2-NH2) with core-shell structures were synthesized and evaluated for rapid boron removal from aqueous solutions. The results showed that the specific surface area of the iron oxide@SiO2-NH2(131.24 m2⋅g−1) increased greatly compared to pure iron oxide (30.98 m2⋅g−1). The adsorption equilibrium was less than 2 h, with an adsorption capacity of 29.76 mg⋅g−1at pH = 6 at 15 °C. The quasi-second-order kinetic model described the boron adsorption process well, and both the Langmuir and Freundlich models were suitable for characterizing the adsorption isotherms. The zeta potential and XPS analysis before and after adsorption revealed that the main adsorption mechanism was the hydrogen bonding formation between the terminal -NH2groups of the adsorbent and the boric acid. In addition, the adsorbent still maintained a high adsorption performance after five adsorption–desorption cycles, which illustrated that the iron oxide@SiO2-NH2may be a potential adsorbent for environmental boron removal treatment.

CAS / MDL: 10025-77-1
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CATALYSIS TODAY · 2024 · IF 5.2

IL/MIL-101-NH2 heterogeneous catalyst prepared by acid-base self-assembly for hydrodeoxygenation of 2,5-tetrahydrofurandicarboxylic acid to adipic acid

Jiali Zheng,Zhihui Li,Dongsheng Zhang,Xinqiang Zhao,Qian Zhao,Yanji Wang

Bio-based route for preparing adipic acid (AA) from 5-hydroxymethylfurfural is the direction for achieving green and sustainable AA production. In light of the challenges, such as corrosion and difficulties in recycling of I - containing homogeneous catalyst, large amount, high cost, and significant mass transfer resistance of ionic liquid (IL) catalyst, encountered in the current hydrodeoxygenation of 2,5-tetrahydrofurandicarboxylic acid (THFDCA) to AA process. Herein, 1-sulfobutyl-3-methylimidazolium iodide IL ([HSO 3 -b-mim]·I) was used to functionalize MIL-101-NH 2 through acid-base self-assembly approach, hence, a heterogeneous catalyst, IL/MIL-101-NH 2 was designed and applied in the hydrodeoxygenation of THFDCA to bio-based AA for the first time. When reacted at 180 °C for 2 h, the THFDCA conversion and AA yield were 100 % and 99.9 %, respectively. Moreover, IL/MIL-101-NH 2 exhibited remarkable stability and could be reused multiple times with minimal loss in activity. XRD, SEM, FT-IR, BET, XPS, and TG results revealed that the functionalization process involved the reaction between HSO 3 in the IL and NH 2 in MIL-101-NH 2 , forming a salt that chemically bonded the IL to MIL-101-NH 2 , thereby enhancing stability. The excellent hydrodeoxygenation activity was attributed to the synergistic effect of the Lewis acid site (Cr 3+ ) and the Lewis base nucleophilic site (I - ) within IL/MIL-101-NH 2 .

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ACS Applied Nano Materials · 2024 · IF 5.3

In Situ NH2-MIL-101(Fe) Nanoparticles Modified Pencil Core Electrodes for Simultaneous Ratiometric Electrochemical Detection of Caffeic Acid and Acetaminophen

Linlin Zheng,Xuechuan Lv,Yanan Chen,Bingyu Wei,Wanqing Hao,Ziyi Zhang,Jingru Yang,Ruiyu Liu,Xu Zhu,Yanli Zhou,Maotian Xu,Xiaohan Gao,Hui Dong

The iron-based metal–organic framework (NH2-MIL-101(Fe)) nanoparticles exhibited excellent conductivity, exceptional catalytic effect, sturdy stability flexible structure, etc. Consequently, it has been exploited in various applications. Herein, NH2-MIL-101(Fe) nanoparticles were successfully synthesized via the hydrothermal method and were grown in situ onto the pencil core electrode (PCE) for simultaneous determination of caffeic acid (CA) and acetaminophen (AP). The PCE decorated by NH2-MIL-101(Fe) as electrode substrate, combined with the dual effects of the excellent electrocatalytic activity of NH2-MIL-101(Fe) and the commendable electrical conductivity of PCE, the constructed sensor exhibits superior electrochemical sensing activity. The electrochemical behavior of CA and AP at the electrodes were investigated mainly by differential pulse voltammetry (DPV) and cyclic voltammetry (CV), exhibiting broad linear responses from 0.1 to 500 μM, and 0.08 to 800 μM for simultaneous detection of CA and AP, with detection limits of 29 nM and 24 nM, respectively. Moreover, the results of CA and AP in drug and human urine using this sensor were satisfactory, which proved that the sensor is feasible to simultaneously detect CA and AP.

CAS / MDL: 107-95-9
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JOURNAL OF SOLID STATE CHEMISTRY · 2024 · IF 3.2

Direct Z-scheme charge transfer Bi2O3/UiO-66-NH2 heterojunctions for boosted photocatalytic degradation of tetracycline hydrochloride in different water systems

Shipeng Liao,Muhammad Arif,Xingyue Qian,Guangyu He

The development of hybrid heterostructure photocatalysts with enhanced visible light absorption capacity holds significant importance in environmental remediation. However, the challenge persists in exploiting strong visible-light responsive photocatalysts with both high efficiency and stability. Herein, we successfully synthesized a hybrid Z-scheme heterojunction of Bi 2 O 3 and UiO-66-NH 2 (Bi 2 O 3 /UiO-66-NH 2 ) through a simple hydrothermal route. The visible light photocatalytic performance of Z-scheme Bi 2 O 3 /UiO-66-NH 2 heterojunction is systematically evaluated for persistent antibiotic tetracycline hydrochloride (TC-HCl) both in the clean and real water matrix. All heterojunction catalysts exhibit superior photodegradation capabilities compared to pristine Bi 2 O 3 and UiO-66-NH 2 . The optimal ratio of the two components heterojunction (BUN-150), in particular, demonstrates the highest removal efficiencies for TC-HCl (95 %) within a 90-min timeframe. This remarkable photocatalytic performance is credited to the Z-scheme charge transfer occurring at the interface of Bi 2 O 3 and UiO-66-NH 2 in Bi 2 O 3 /UiO-66-NH 2 heterojunction. The active species experiments and electron paramagnetic resonance analyses are conducted to identify the active reactive species during the TC-HCl degradation (·OH, h + , and ·O 2 − ), and a precise photocatalytic degradation mechanism is explained. Additionally, the photodegradation intermediates of TC-HCl are detected using the HPLC-MS analysis to explain the degradation pathways of TC-HCl. This research paves the way for the development of novel Z-scheme Bi 2 O 3 -based heterojunction catalysts for outstanding photocatalytic applications.

CAS / MDL: 64-75-5
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JOURNAL OF PHYSICAL CHEMISTRY B · 2024 · IF 2.8

Anchoring of Fe-MIL-101-NH2 to the Polymer Membrane Matrix through the Hinsberg Reaction to Promote Conductivity of SPEEK Membranes

Hong-Jie Zhang,Xue-Bin Shang,Xu-Ran Wang,Chen-Xi Zhang,Qing-Lun Wang

SCPEEK@MOF proton exchange membranes, where SCPEEK is sulfinyl chloride polyether ether ketone and MOF is a metal–organic framework, were prepared by doping Fe-MIL-101-NH2 into polymers. The amino group in the MOF and the -SOCl2 group in thionyl chloride polyether ether ketone cross-link to form a covalent bond through the Hinsberg reaction, and the prepared composite membrane has stronger stability than other electrostatic interactions and simple physical doping composite membranes. The formation of covalent bonds improves the water absorption of the composite membrane, which makes it easy for water molecules to form hydrogen bonds. Moreover, SPEEK as a proton conductive polymer and the synergy of MOFs improve the proton conductivity of composite membranes. The composite membranes were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The swelling rate, water absorption, mechanical stability, ion exchange capacity, and proton conductivity of the pure sulfonated polyether ether ketone (SPEEK) membrane were compared with those of the mechanically doped SPEEK/MOF membrane and the composite membrane SCPEEK@MOF doped with different ratios of Fe-MIL-101-NH2, and all of the SCPEEK@MOF showed superior performance. When the Fe-MIL-101-NH2 loading rate of the composite membrane is 2%, the proton conductivity of the composite membrane can reach 0.202 S cm–1 at 363 K and a 98% relative humidity, which is much higher than that of the SPEEK/MOF membrane obtained by simple physical doping under the same conditions.

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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2024 ·Vol. 171 ·期 4 ·047503 · IF 3.1

Simultaneous Determination of Magnolol and Honokiol Using a Glassy Carbon Electrode Modified by UIO-66-NH2 and Electroreduced Carboxylated Graphene Oxide

Zhengjie Zhang,Yiheng Zhang,Yangchun Li,Yurong Wang

An electrochemical sensor for the simultaneous detection of magnolol (MAG) and honokiol (HON) was constructed based on the metal-organic framework, UIO-66-NH2, and electroreduced carboxylated graphene oxide (ErGO-GOOH). The UIO-66-NH2@ErGO-COOH coating was characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. Cyclic voltammetry was applied to investigate the electrochemical behavior of MAG and HON on UIO-66-NH2@ErGO-COOH/GCE. The electroanalytical method for the simultaneous determination of MAG and HON was established using linear sweep voltammetry. Under optimal experimental conditions, a linear range of 0.05 ∼ 8 μM and limits of detection of 16 and 7.0 nm for MAG and HON, respectively, were obtained. The sensor exhibited good repeatability, reproducibility, stability and anti-interference ability. The sensor was successfully applied to the simultaneous detection of MAG and HON in urine and serum samples with good recovery.

CAS / MDL: 7487-88-9
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RENEWABLE ENERGY · 2025 · IF 9.1

Ni/N co-doped NH2-MIL-88(Fe) derived porous carbon as an efficient electrocatalyst for methanol and water co-electrolysis

Jingchuan Guo,Yan Gao,Xuankai Cao,Linxuan Li,Xin Yu,Shidan Chi,Haoyu Liu,Guohong Tian,Xudong Zhao

The technology of using electricity generated from renewable energy sources such as wind and solar power for water electrolysis to produce hydrogen has achieved high efficiency, high purity, and environmental friendliness. However, its further development is constrained by the high overpotential of the oxygen evolution reaction (OER) and the high cost of precious metal catalysts. The methanol oxidation reaction (MOR) as an alternative to OER can significantly reduce overall energy consumption and accelerate the hydrogen evolution reaction. This study innovatively utilizes the metal-organic framework (MOF) of NH₂-MIL-88(Fe) to introduce Ni doping, preparing a series of Fe x Ni y -MOF and their bimetallic carbon derivatives (Fe x Ni y /C) through solvothermal synthesis and high-temperature carbonization. Results show that FeNi₂/C exhibited excellent performance in OER, with a Tafel slope of 38.69 mV·dec⁻ 1 and an overpotential of 335 mV at 10 mA cm⁻ 2 , comparable to RuO₂. In MOR, the overpotential was 193 mV, reduced by approximately 140 mV compared to OER, with outstanding stability. The catalytic mechanism was analyzed using ion chromatography, revealing the key role of Ni doping in enhancing catalytic activity and stability. This study provides new strategies for improving the electrocatalytic hydrogen production efficiency of renewable energy and reducing the production cost of hydrogen energy.

CAS / MDL: 64-17-5 10312-55-7
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Photocatalytic activation of peroxymonosulfate (PMS) by CNN@NH2-MIL-101(Fe) Z-scheme heterojunction for phthalates degradation under visible light irradiation

Yadan Luo,Chenguang Li,Zhen Liu,Wei Guo,Cuizhu Sun,Shasha Zhao,Qian Wang,Yuanyuan Li,Lingyun Chen,Hao Zheng,Fengmin Li

Phthalates (PAEs) are known to pose a serious threat to the environment and human health duo to their endocrine disrupting effects, thus a great deal of effort has been made to develop destruction technologies for PAEs treatment in the water environment, such as peroxymonosulfate (PMS)-based advanced oxidation technology. Here we prepared an environmentally friendly visible light catalyzer, a heterojunction of carbonitride nanosheets (CNN) doped with NH 2 -iron metal organic frameworks (NH 2 -MIL-101(Fe)), for the activation of PMS to efficaciously remove two representative PAEs—diisobutyl phthalate (DIBP) and diethyl phthalate (DEP)—from the aquatic environment. The CNN@NH 2 -MIL-101(Fe) photocatalyst possesses an excellent visible light harvesting performance with a narrow band gap (1.66 eV), low recombination ratio of photoinduced carriers, and long charge lifetime. The pore volume and surface area of the composite material was increased compared with any single component. The optimum CNN@NH 2 -MIL-101(Fe) catalyst manifested the high performance to activate PMS to degrade DIBP and DEP under visible irradiation with maximum removal of 94.5 ± 2.2 % and 83.4 ± 0.9 %, respectively. Four main active species (•OH, O 2 − •, SO 4 − •, and h + ) were involved in PAEs photodegradation, with h + and SO 4 − • playing a key role in the degradation of DIBP, and h + in the degradation of DEP. The degradation mechanism of DIBP and DEP mainly involved the ester bond cleavage and oxidation   by active species. Additionally, the CNN@NH 2 -MIL-101(Fe) heterojunction exhibited high and stable catalytic performance to activate PMS for PAEs destruction under pH 3 – 9. Therefore, this study provides a new strategy for designing and selecting environment-friendly treatment approach for the effective eradication of PAEs via a PMS-based advanced oxidation process.

CAS / MDL: 299-11-6
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TALANTA · 2024 · IF 5.6

One stone two birds: NH2-UiO-66@MB-based bimodal aptasensor for sensitive and rapid detection of zearalenone in cereal products

Yuting Zhou,Xiang Chen,Xianlu Lei,Meiqi Huang,Miaomiao Ma,Jian Zeng,Fuyan Zhang,Shuang Li,Qi Sun,Tao Le

Zearalenone (ZEN), a prevalent mycotoxin found in cereal crops, poses a significant threat to food safety and human health. To address this issue, there is an urgent need for rapid, sensitive, and cost-effective detection methods. In this study, we developed a novel bimodal aptasensor based on NH 2 -UiO-66@MB composites for ZEN detection. Methylene blue (MB) was encapsulated within NH 2 -UiO-66 nanoparticles to enhance fluorescence intensity, and the ZEN aptamer was attached to NH 2 -UiO-66 via Zr–O–P bonds and Coulombic forces to create a gating effect. In the presence of ZEN, the aptamer bounded to ZEN, triggering a conformational change that released MB, resulting in decreased fluorescence intensity and absorbance. Under optimal conditions, the bimodal aptasensor exhibited wide linear ranges (2.5–300 ng/mL for colorimetry and 0.125–200 ng/mL for fluorescence) and low limits of detection (1.16 ng/mL for colorimetry and 0.03 ng/mL for fluorescence). Furthermore, the aptasensor demonstrated high specificity and reproducibility, with recovery rates ranging from 97.43 % to 103.71 % in spiked cereal products. These findings highlight the potential of the developed bimodal aptasensor as a novel tool for the rapid, accurate, and cost-effective detection of ZEN in cereal products, contributing to improved food safety monitoring.

CAS / MDL: 68-12-2
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RENEWABLE ENERGY · 2024 · IF 9

Transfer hydrogenation of 5-Hydroxymethylfurfural to 2,5-dihydroxymethylfuran by synergistic catalysis with a mixture of ZIF-8 and UiO-66-NH2

Wenli Zhang,Jifei Liu,Hongwei Gu,Cheng Pan,Yifei Long,Qunpeng Cheng,Guozhi Fan

The metal-organic framework materials ZIF-8 and UiO-66-NH 2 , synthesized by hydrothermal methods, were characterized in detail and combined to catalyze the transfer hydrogenation of 5-hydroxymethylfurfural (5-HMF) to 2,5-di(hydroxymethyl)furan (2,5-DHMF) using isopropanol as the hydrogen source. The ZIF-8/UiO-66-NH 2 catalyst mixture exhibited abundant Lewis acid-base sites and a hierarchical multiporous structure with a large specific surface area (564.0 m 2 /g). The conversion of 5-HMF reached 98.2 %, and the selectivity and yield of 2,5-DHMF were 96.2 % and 94.5 %, respectively. The recycling performance of ZIF-8/UiO-66-NH 2 was also investigated, and the conversion of 5-HMF and selectivity of 2,5-DHMF significantly decreased to 78.4 % and 79.1 % in the second run, respectively. The loss of −NH 2 groups was found to be the main reason for the decrease in activity. However, the catalytic activity of the recovered catalyst can be almost completely restored by the addition of a small amount of fresh UiO-66-NH 2 and ZIF-8, and the conversion of 5-HMF and selectivity of 2,5-DHMF were increased to 89.4 % and 95.5 %, respectively. In the proposed reaction mechanism, Lewis acid-base sites play important roles and exhibit a synergistic catalytic effect in the selective conversion of 5-HMF to 2,5-DHMF.

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