CHEMICAL ENGINEERING COMMUNICATIONS
·
2025
·
IF 2
Fan Pan,Lijiang Tian,Fulong Chen,Jie Zhang
The photocatalytic efficiency of titanium dioxide(TiO2) is easy to restrict by rapid recombination of carriers, narrow spectrum response range, and low specific surface area. Constructing heterojunctions has been widely acknowledged as a viable strategy to enhance the photocatalytic performance of TiO2. Here, TiO2@MIL-101(Cr) heterojunction was synthesized via the in-situ method and applied to adsorbing and photocatalytic degrading of gaseous benzene. The findings demonstrate 40TM exhibited the best adsorption(1157.03 μgC6H6/(g·h)) and photocatalytic(817.80 μgC6H6/(g·h)) performance, which were 2.05 and 5.21 times of TiO2, respectively. The enhancement of adsorption performance probably resulted from the higher specific surface area(637.33 m2/g) and the micro-mesoporous structure. The excellent photocatalytic performance might stem from the extended wavelength response range(400–700 nm) and the Z-scheme heterojunction formation. The possible mechanism is that electrons in MIL-101(Cr) and holes in TiO2 could participate in redox reactions to generate radicals, with superoxide radicals(∙O2−) and hydroxyl radicals(∙OH) being identified as the primary active species for benzene degradation. Overall, this investigation offers a valuable reference for the application of heterojunction catalysts in the field of adsorption-photocatalytic degradation of volatile organic compounds (VOCs).
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Yongxiang Jiang,Yang Liu,Jia Bao,Xin Wang,Xiaomin Hu
Emerging Contaminants (ECs) in water bodies pose significant environmental concerns. Adsorption technology, known for its low cost, high efficiency, and ease of use, is a promising solution for ECs removal. This study investigated the adsorption performance of MIL-101(Fe), an iron-based metal-organic framework (MOF), for ECs with different molecular sizes. Sodium p-perfluorous nonenoxybenzenesulfonate (OBS), diclofenac sodium (DCF), and tetracycline hydrochloride (TCH) were selected as representative ECs, covering PFAS substitutes, NSAIDs, and antibiotics. MIL-101(Fe) exhibited specific surface area, excellent mesoporous structure and abundant surface active sites, enabling efficient adsorption. Under optimized conditions (pH = 5.8, 6, and adsorbent dosages 9, 40, 20, and 20 mg), removal efficiencies for OBS, DCF, and TCH reached 95.9 %, 97.5 %, and 86.4 %, respectively. Cyclic tests showed stable performance after five adsorption-desorption cycles. Kinetic studies indicated that OBS followed a pseudo-first-order model, while DCF and TCH adhered to a pseudo-second-order model. The maximum adsorption capacities for OBS, DCF, and TCH were 945.1, 1595.9, and 439.5 mg·g −1 , respectively. Adsorption mechanisms revealed that smaller molecules like OBS and DCF easily entered the mesopores, while larger TCH molecules faced diffusion restrictions. The molecular interactions among OBS, DCF, and TCH involved electrostatic attraction toward -SO₃ − groups and pore filling in OBS, diffusion into the pore interior followed by hydrogen bonding with -NH₂ and π-π stacking in DCF, and surface-confined hydrogen bonding with -OH/-NH₂ and π-π interactions in TCH. This study provided a theoretical basis for efficient treatment of ECs with various molecule structures by Fe-MOFs adsorption materials.
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Catalysis Science & Technology
·
2019
·Vol. 10
·期 1
·138-146
·
IF 5.726
Ting Wang,Xueqin Tao,Yi Xiao,Ganhua Qiu,Yun Yang,Benxia Li
While heterogeneous photocatalysis is regarded as a sustainable strategy to achieve organic reactions for the production of high-value-added organics, photocatalytic efficiency is generally limited by poor charge separation, dull surface catalytic activity and the consequently caused insufficient generation of active species. Herein, the hybrid structures of metal–organic frameworks (MOFs) incorporated with Pd ultrasmall nanocrystals are synthesized, and their photocatalytic performance is evaluated by the oxidative coupling of benzylamine as a model reaction. The photocatalytic activity of the Pd/MIL-125-NH2 hybrid material with an optimal Pd loading is greatly superior to that of the pristine MIL-125-NH2, achieving a high benzylamine conversion rate of 3136 μmol h−1 gcat−1 at 94.08% conversion. The enhanced charge transfer and separation in Pd/MIL-125-NH2 are verified by photoluminescence spectroscopy and photoelectrochemical experiments. Photogenerated reactive oxygen species are probed by 3,3′,5,5′-tetramethylbenzidine (TMB) as an indicator and the reactive intermediates in the photocatalytic systems are identified by in situ ESR detection. The results confirm that the optimized Pd/MIL-125-NH2 hybrid catalyst possesses higher ability for molecule activation and that both superoxide radical (˙O2−) and singlet oxygen (1O2) are the dominant oxidative species in the present photocatalytic system. Therefore, the dual advantages of Pd/MIL-125-NH2 hybrid structures for promoting the photogenerated charge transfer/separation and providing highly catalytic sites for molecule activation contribute to higher photocatalytic activity.
研究领域:
材料科学
·
化学工程
·
环境科学
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TALANTA
·
2025
·
IF 6.1
Luyang Zhao,Yang Song,Guoyang Xie,Hengyi Xu
A colorimetric assay based on the Fe/Al bimetallic organic framework NH 2 -MIL-53(Fe, Al) was developed for the sensitive detection of Escherichia coli O157:H7 ( E. coli O157:H7), a critical pathogen threatening food safety. The framework’s high specific surface area facilitated efficient antibody immobilization, whereas the incorporation of Al 3+ enhanced electron transfer between Fe 2+ /Fe 3+ , thereby significantly boosting peroxidase activity. The optimized NH 2 -MIL-53(Fe, Al) exhibited 1.4-fold and 4.9-fold higher relative absorbance than NH 2 -MIL-53(Fe) and NH 2 -MIL-53(Al), respectively. And it demonstrated 40-fold and 2-fold greater affinity for TMB and H 2 O 2 , respectively, compared to the natural enzyme. By integrating a dual-recognition system based on antibody and aptamer, the method enabled rapid detection with a limit of detection of 10 1 CFU/mL in colorimetric mode. Its successful application in complex matrices, including lettuce, juice, pool water, and chocolate milk, had yielded satisfactory recovery and precision, confirming its promising potential for food safety monitoring.
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ACS Omega
·
2019
·
IF 2.584
Xiaofang Liu,Hu Pan,Heng Zhang,Hu Li,Song Yang
Enlarging the dispersed micropores of metal-organic frameworks to the well-ordered mesostructure can enhance the accessibility of acidic sites for reactants resulting in the improvement of selectivity. With the regulation of cetyltrimethylammonium bromide/Cr3+ and ClSO3H sulfonation, a series of mesoporous MIL-101(Cr)-SO3H (MMSs) with multiple pore sizes and acidic properties were synthesized and explored to further facilitate the furfuryl alcohol (FA) ethanolization to ethyl levulinate (EL) for the first time. The optimal catalytic activity of 83.8% EL yield at full FA conversion demonstrated that the appropriate mesopore size, acidic density, and accessible −SO3H sites contributed to the superior performance of the MMS(0.3)-0.15. The turnover frequency value (14.8 h–1) obtained with MMS(0.3)-0.15 was comparable to the commercial Nafion NR50 (18.3 h–1) and much higher than the classical Amberlyst-15 (1.9 h–1), confirming the predominant catalytic performance. Furthermore, two coexistent reaction paths with 2-ethoxymethylfuran and 4,5,5-triethoxy-pentan-2-one as intermediates indicated the possibility of producing EL from FA.
研究领域:
化学工程
·
材料科学
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MICROPOROUS AND MESOPOROUS MATERIALS
·
2026
·
IF 4.5
Yan Jin,Hui Zhang,Tengfei Li,Shaojie Lei,Meier Jiaerheng,Dezhang Ren,Zhibao Huo
Biodiesel has emerged as a promising alternative to conventional diesel due to its renewability and environmental friendliness. In this study, a MIL-101(Cr) featuring synergistic acid sites was developed through a combined defect engineering and post-sulfonation strategy, enabling efficient esterification of oleic acid under mild conditions. Defects were introduced in the MIL-101(Cr) through a mixed-ligand approach. The existence of abundant oxygen vacancies in the defect-engineered MIL-101(Cr) was confirmed by electron paramagnetic resonance (EPR), which could provide adequate grafting sites for the subsequent sulfonation. The sulfonic acid-functionalized MIL-101(Cr) catalyst (MRBSX) was then synthesized by post-sulfonation with chlorosulfonic acid as the sulfonation agent. The chemical structure and sulfonic acid density of MRBSX were systematically investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), brunauer-emmett-teller (BET), and Fourier-transform infrared spectra (FT-IR), and other characterization techniques. Acid-base titration combined with elemental analysis (EA) demonstrated the successful loading of sulfonic acid groups in MRBSX, highlighting the promotional role of oxygen vacancies in enhancing acid site density and catalytic efficiency. Under optimized reaction conditions (100 °C, 6 wt%, 3 h, and M/O = 8:1), the MRBSX with 10 mol% benzoic acid achieved a high oleic acid conversion of 96.7 % and a corresponding biodiesel yield of 91.5 %. Therefore, the proposed synergistic strategy of defect engineering and post-sulfonation is effective in constructing high-performance solid acid catalysts, demonstrating promising potential in green energy conversion applications.
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KEY ENGINEERING MATERIALS
·
2015
·
IF 0
Xin Liu,Yan Ying Zhao
An N, N-dimethylformamide (DMF)-functionalized metal–organic framework, namely, DMF-MIL-101(Cr), was prepared and then used for the adsorptive removal of methylene blue (MB), a cationic dye, from aqueous solutions. MIL-101(Cr) was synthesized by the hydrothermal method. Next, by dipping the MIL-101(Cr) sample in DMF, DMF-MIL-101(Cr) was synthesized. The results of X-ray diffraction analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis confirmed that DMF and MIL-101 could be combined successfully. More importantly, the MB uptake capacity of DMF-MIL-101(Cr) was significantly higher than that of MIL-101(Cr). Unlike MIL-101(Cr), DMF-MIL-101(Cr) could adsorb the entire MB in a solution with a concentration of 10.92 mg/L, owing to the electrostatic interactions between DMF and the MB molecules. In 100 mL of a 10.92-mg/L MB solution, DMF-MIL-101(Cr) can reach a state of absorbance equilibrium within10 min. After that, the adsorption process exhibited the characteristics of a zero-order reaction. This result indicates that it may be possible to exploit different functionalization methods and improve the rate of adsorption of dyes onto metal–organic frameworks.
研究领域:
环境化学
·
材料科学
·
吸附技术
·
废水处理
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DOI
Journal of Materials Chemistry C
·
2019
·Vol. 7
·期 18
·5451-5460
·
IF 6.641
Wubin Wu,Jingchao Wang,Tianyong Zhang,Shuang Jiang,Xiaoyuan Ma,Guanghui Zhang,Xia Zhang,Xingwei Chen,Bin Li
Different fusiform-shaped MIL-88A materials were successfully prepared by adjusting the mole ratio of the central metal ion and the organic ligand and using different polar solvents. With differently shaped MIL-88A supports, several Ag/AgCl@MIL-88A (ACML) were prepared successfully using the in situ growth method. These ACML composites showed a good photocatalytic activity under the simulated sunlight and visible light. The employment of Cl− ions, anchored on the surface of MIL-88A, could improve the dispersion and stability of the loaded Ag/AgCl nanoparticles. The s-ACML composite showed excellent photocatalytic stability during the cycle tests. The in situ growth strategy provided a facile method to design and synthesize MOF composite photocatalysts for wastewater treatment. In addition, based on the related optical and electrical characterization analysis, a possible mechanism of the ACML composite photocatalytic activity was proposed.
研究领域:
材料科学
·
光催化
·
环境工程
·
纳米复合材料
·
金属有机框架材料（MOFs）
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ENERGY CONVERSION AND MANAGEMENT
·
2018
·
IF 6.377
Hui Li,Fengsheng Liu,Xiaoling Ma,Zhongjie Wu,Yan Li,Linhua Zhang,Shoujun Zhou,Yaxin Helian
Strontium oxide (SrO) is restricted by poor reusability and pore structure in catalyzing transesterification for biodiesel production. To address this problem, metal organic frameworks is employed as a carrier to support strontium carbonate by mechanical mixing method (MM) and in situ titration method (ST), and then calcined under inert atmosphere to obtain the catalyst of MM–SrO and ST–SrO. As a comparison, the reusability of pure SrO is compared and the homogeneous contribution of leached active sites for ST–SrO and MM–SrO are also assessed. The catalysts are characterized by TG, XRD, FTIR, EDS, Hammett indicator titration, nitrogen adsorption–desorption, and VSM. From the catalyst reusability, MM–SrO exhibits the excellent performance, where the maximum conversion of 96.19% is achieved at molar ratio of methanol to oil 12, catalyst addition 8 wt% (refer to oil), reaction temperature 65 °C within 30 min. And the conversion of 82.49% is still obtained at the third cycle, which could be easily separated from the mixture by external magnetic field after each cycle as well. In order to optimize the activation condition and investigate MM–SrO deeply, thermal characteristics of its corresponding precursor are further evaluated, where the TG experiments are conducted at heating rate of 20, 30, and 40 °C/min. and kinetic parameters are calculated through model–free method and Avrami theory, respectively.
研究领域:
化学工程
·
催化材料
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ChemPlusChem
·
2026
·Vol. 91
·期 8
·e70223
·
IF 3.1
Huan V Doan,Huong T T Tran,Duyen T Le,Xuan N Pham
In this study, a novel Ni–MoO 3 @MIL‐101(Cr) composite catalyst was synthesized via a one‐step hydrothermal method for the oxidative desulfurization (ODS) of dibenzothiophene (DBT). The catalyst combines the high specific surface area of MIL‐101(Cr) with the redox properties of Ni–MoO 3 , providing an effective synergy between adsorption and catalytic oxidation. The incorporation of Ni as a promoter significantly enhances catalytic activity, enabling complete sulfur removal (∼100%) under mild conditions (50 °C) within 60 min. Structural characterizations (scanning electron microscopy, X‐ray diffraction, and SAED) reveal that the catalyst retains its nanosheet–nanorod morphology and crystalline MoO 3 phase after repeated use, with only a slight decrease in the crystallinity of the MIL‐101(Cr) framework. Mechanistic analyses using X‐ray photoelectron spectroscopy, Raman, and temperature‐programmed reduction demonstrate that surface oxygen vacancies and Lewis acid sites promote ODS activity, while highly dispersed Ni–MoO 3 species facilitate H 2 O 2 activation and Mo 6+ /Mo 5+ redox cycling, leading to efficient generation of reactive oxygen species. The catalyst also exhibits excellent stability, maintaining 98.7% DBT conversion after five cycles. These results demonstrate that the strong Ni–Mo synergistic effect and efficient oxygen activation make Ni–MoO 3 @MIL‐101(Cr) a robust and highly efficient catalyst for deep fuel desulfurization. This study presents a significant advancement in the field of oxidative desulfurization by developing a synergistic Ni–MoO 3 redox catalytic system confined within the porous MIL‐101(Cr) framework. Unlike conventional catalysts, the designed material effectively enhances H 2 O 2 activation through cooperative interactions between Ni and Mo species, enabling rapid and ultra‐deep removal of refractory sulfur compounds under mild conditions. The integration of redox‐active sites with a high‐surface‐area MOF support not only improves catalytic efficiency but also ensures excellent stability and recyclability. This work provides new insights into the rational design of bimetallic catalysts for green fuel purification and offers a promising strategy for achieving sustainable and energy‐efficient desulfurization processes.
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Chemical Engineering Journal Advances
·
2026
·
IF 6.9
Long Liu,Jie Zou,Zihao Zhou,Yuxuan Yang,Xueqiang Shao,Yangyang Bian,Mingwen Zhang,Jinbei Yang
In this study, functionalized ionic liquids were precisely anchored onto the pores and surfaces of the high-specific-surface-area MIL-101(Fe) metal-organic framework (MOF) carrier through covalent bonding, achieving the ordered arrangement of active sites and the modulation of the local microenvironment. Specifically, carboxyl-functionalized imidazolium ionic liquids bridge Fe³⁺ ions and terephthalic acid ligands to construct the supported acidic ionic liquid MIL-101(Fe)-[(CH₂COOH)₂IM][HSO₄] via solvothermal co-assembly. The obtained catalyst efficiently facilitates the esterification of various free fatty acids with methanol for biodiesel production. The catalyst was characterized by XRD, FT-IR, XPS, SEM, BET-BJH, and TGA. The catalyst demonstrated high acidity (6.31 mmol/g), excellent thermal stability, and efficient catalytic performance. Under the operating conditions optimized by response surface methodology (catalyst dosage of 8.64%, methanol-to-oleic acid molar ratio of 16.9:1, reaction temperature of 67.0 °C, and reaction time of 4.0 h), the oleic acid conversion over MIL-101(Fe)-[(CH₂COOH)₂IM][HSO₄] reached 97.66%, and it still maintained favorable catalytic performance after 7 cycles. In addition, MIL-101(Fe)-[(CH₂COOH)₂IM][HSO₄] also exhibited broad substrate applicability, and could serve as a promising catalyst for biodiesel preparation.
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
·
2026
·Vol. 74
·期 28
·22312-22323
·
IF 6.7
Peng Huajie,Gao Di,Xiao Zhengyue,Yue Zhixiang,Xu Peng,Qiu Ping
Compared with natural-enzyme-based detection strategies,
nanozymes
offer notable advantages in stability, environmental tolerance, and
cost-effectiveness. In this study, we designed and synthesized a Pt@Fe-MIL-88
composite with both oxidase (OXD)-like activity and intrinsic fluorescence.
The material efficiently catalyzes 3,3 ′ ,5,5 ′ -tetramethylbenzidine
(TMB) oxidation, generating a color change while quenching its fluorescence.
Glyphosate (Gly) specifically inhibits the OXD-like activity of Pt@Fe-MIL-88,
reducing oxTMB production and thereby alleviating fluorescence quenching,
enabling dual colorimetric and fluorometric signal readout. The inhibition
mechanism was elucidated through FTIR, XRD, XPS characterization,
molecular dynamics simulations, and DFT calculations. Accordingly,
a natural-enzyme-free, colorimetric-fluorometric dual-mode sensing
platform for Gly was established. The platform exhibits high sensitivity,
excellent selectivity, and strong anti-interference capability, with
accuracy and reliability validated by spike recovery tests in real
samples. This work presents a new strategy for developing stable,
rapid, and low-cost multimodal detection methods for pesticide residues.
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