ANALYTICAL CHEMISTRY
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2011
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IF 5.874
Cheng-Xiong Yang,Xiu-Ping Yan
The diverse structures and pore topologies, accessible cages and tunnels, and high surface areas make metal–organic frameworks attractive as novel media in separation sciences. Here we report the slurry-packed MIL-101(Cr) column for high-performance liquid chromatographic separation of substituted aromatics. The MIL-101(Cr) packed column (5 cm long × 4.6 mm i.d.) offered high-resolution separation of ethylbenzene (EB) and xylene, dichlorobenzene and chlorotoluene isomers, and EB and styrene. The typical impurities of toluene and o-xylene in EB and styrene mixtures were also efficiently separated on the MIL-101(Cr) packed column. The column efficiencies for EB, m-dichlorobenzene, and m-chlorotoluene are 20000, 13000, and 10000 plates m–1, respectively. The relative standard deviation for five replicate separations of the substituted aromatics was 0.2–0.7%, 0.9–2.9%, 0.5–2.1%, and 0.6–2.7% for the retention time, peak area, peak height, and half peak width, respectively. The MIL-101(Cr) offered high affinity for the ortho-isomer, allowing fast and selective separation of the ortho-isomer from the other isomers within 3 min using dichloromethane as the mobile phase. The effects of the mobile phase composition, injected sample mass, and temperature were investigated. The separation of xylene, dichlorobenzene, and chlorotoluene on MIL-101(Cr) was controlled by entropy change, while the separation of EB and styrene on MIL-101(Cr) was governed by enthalpy change.
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CRYSTENGCOMM
·
2025
·Vol. 27
·期 5
·678-686
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IF 2.6
Dongling Xie,Jianan Wang,Bo Huang,Yiyi Yang,Dunmin Lin,Chenggang Xu,Fengyu Xie
Rational design of viable routes to develop affordable and efficient oxygen evolution reaction (OER) catalysts is essential for advancing electrochemical water splitting, yet significant challenges remain, particularly in seawater. Here, we propose a ligand defect engineering strategy to modify the electronic structure of NH2-MIL-88B(Fe) using a monodentate ligand (acetic acid, AcOH), inducing ligand vacancies in NH2-MIL-88B(Fe) for oxygen evolution in an alkaline seawater electrolyte, thereby improving the performance of the electrocatalysts. The resulting defective MOFs (denoted as NH2-MIL-88B(Fe)-x) exhibited exceptionally high catalytic activity for OER, requiring low overpotentials of 313 and 329 mV at a current density of 100 mA cm−2 in 1 M KOH and simulated seawater (1 M KOH + 0.5 M NaCl) solutions, respectively. Experimental analyses revealed that the introduction of AcOH can modulate the d-band center of active sites in NH2-MIL-88B(Fe)-x and play a critical role in alleviating chloride ion (Cl−) corrosion, thereby enhancing catalytic stability in seawater. When directly used as an OER catalyst in an alkaline electrolyte, wind and solar power were harnessed to operate the NH2-MIL-88B(Fe)-x || Pt/C configuration to drive the electrolytic water reaction. Thus, the ligand defect strategy can be employed to design and prepare high-performance OER electrocatalysts, particularly for generating H2 through water electrolysis powered by renewable energy sources.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Yumeng Zhao,Guoshu Gao,Peng Zhu,Cun Liu,Xiongfu Zhang,Feichao Wu,Guohui Yang
Metal-organic framework (MOF) membranes hold great potential for acetic acid dehydration by pervaporation. However, it remains challenging to develop stable MOF membranes suitable for this application due to the corrosion of membranes by acetic acid. Herein, we report a robust aluminum (Al)-based MIL-96 membrane on porous ceramic tubes for acetic acid pervaporation dehydration. It is prepared by an induction strategy with Al-Sol@MIL-96-C layer, obtained by calcining an Al-based sol layer containing small MIL-96 seeds. The induced layer possesses a sponge-like structure and high reactivity, favoring the uniform growth of MIL-96 crystals and establishing a strong connection between the membrane layer and the support. The achieved MIL-96 membrane, with a thickness of ∼2 μm, exhibits excellent performance in separating 90 wt% acetic acid/water mixtures by pervaporation, showing a high separation factor of ∼3000 with a permeation flux of 1.54 kg/(m 2 ·h). Notably, due to the connectivity of the Al-Sol@MIL-96-C layer, these membranes show long-term operational stability for over 200 h, as well as great tolerance to ultrasonic treatment, highlighting the enormous potential for applications. This work provides a feasible approach to fabricate robust MOF membranes for pervaporation separation of acetic acid/water mixtures.
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Materials
·
2025
·Vol. 18
·期 6
·1343
·
IF 3.2
Hangmin Xu,Hao Song,Xiaozhi Wang,Xingwang Zhu
The substantial release of industrial carbon dioxide has been identified as a key factor in the development of various environmental issues. In addressing these concerns, the utilization of photocatalytic technology for carbon reduction has garnered significant attention. The disadvantage of CO2photoreduction is the problem of product yield and selectivity. It is known that MIL-125(Ti) with a high specific surface area (SBET) possesses more active sites using Ti as a node. The calcination of MIL-125(Ti) in a reducing atmosphere has been shown to introduce oxygen vacancies (OV), thereby enhancing the material’s surface and internal pores. This process has been demonstrated to result in a significant increase in the SBETand an enhancement of the Ti3+/Ti4+ratio. The increased Ti3+centers have been found to improve the material’s reducing properties. The results demonstrate that the OV-rich MIL-125-2H material exhibits the high-performance and highly selective photoreduction in CO2.
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JOURNAL OF CATALYSIS
·
2017
·
IF 6.844
Cong Gao,Shuo Chen,Xie Quan,Hongtao Yu,Yaobin Zhang
The Fenton reaction is an efficient technology for degrading refractory organic pollutants in water. Heterogeneous Fenton-like catalysts have been demonstrated to be promising alternatives to homogeneous catalysts because of their reusability and lack of sludge production. These catalysts, however, generally show low activity for generating OH due to their limited exposed active sites and difficulty in the reduction of Fe(III) to Fe(II). Here, enhanced catalytic performance was achieved by using an iron-based metal organic framework (MIL-88B-Fe) as a heterogeneous Fenton-like catalyst over a wide pH range (4–6). The catalytic activity of MIL-88B-Fe was about 1–3 orders of magnitude higher than that of three other conventional catalysts (Fe 2 O 3 , α-FeOOH, and Fe 3 O 4 ) and two other iron-based MOFs (MIL-53-Fe and MIL-101-Fe). The superior activity of MIL-88B-Fe could originate from the abundance of active sites, the flexible structure, and facilitated reduction of Fe(III) to Fe(II). Hydroxyl radicals generated from reaction between MIL-88B-Fe and H 2 O 2 were the main reactive oxidative species for phenol degradation.
研究领域:
环境科学
·
催化化学
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2026
·Vol. 37
·期 19
·1512
·
IF 3.2
Jiang Chaojin,Zhang Yuanyuan,Guan Erbu,Jiang Yuqin,Li Shuaishuai,Xin Yanmei
The development of efficient and economical photocatalysts is the focus of achieving sustainable remediation of water pollution. However, slow photogenerated carrier transfer and insufficient catalytic sites are the main reasons affecting photocatalytic applications. Herein, we developed flake-octahedral BiOBr/MIL-101(Fe) heterojunction catalysts through a facile solvothermal strategy for the degradation of pollutants under visible light irradiation. Scanning electron microscope, X-ray photoelectron spectrometer, Fourier infrared spectrometer, and X-ray diffraction analysis characterizations proved the successful synthesis of flake-octahedral BiOBr/MIL-101(Fe) heterojunction. Absorption spectra and Brunauer–Emmett–Teller analyses showed that the BiOBr/MIL-101(Fe) composites with an atomic percentage of Fe of 9.1 (denoted as BiOBr/MIL III ) had the optimal light absorption and the largest specific surface area. The BiOBr/MIL III achieved a remarkable Rhodamine B (Rh B) degradation efficiency of 94.5% within 60 min, with an apparent rate constant ( k ) of 0.03540 min −1 , demonstrating excellent visible light-driven photocatalytic activity. Photocatalytic mechanistic studies showed that the solvothermal-induced flake-octahedral BiOBr/MIL-101(Fe) III heterojunction promotes the formation of Z-scheme, which significantly enhances the carrier separation efficiency and accelerates the rapid generation of reactive radicals · O 2 − and h + . This work provides a feasible strategy for the construction of flake-octahedral inorganic-MIL photocatalysts with excellent photocatalytic performance.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Yuqi Zhu,Rongbo Li,Zemin Li,Yawei Gu,Rujing Hou,Yichang Pan
Eight silane coupling agents are grafted onto MIL-100(In) membranes for TOL/MCH pervaporation. • Cyclohexyl-configured silane with amine group enables superior TOL/MCH recognition. • Configurational effects maximize binding energy difference, boosting separation factor by 175%. • Two-stage process achieves flux of 402 g·m −2 ·h −1 and separation factor of 8.1. Hydrogen is recognized as a promising green energy carrier, yet its large-scale transportation remains a critical challenge. Toluene/methylcyclohexane (TOL/MCH) serves as a safe and cost-effective liquid organic hydrogen carrier (LOHC), but practical deployment is constrained by inefficient post-dehydrogenation separation. Membrane-based separation offers a potential solution; however, most existing membranes lack sufficient molecular discrimination capability for these two analogues. In this work, MIL-100(In), a metal-organic framework with intrinsic adsorption selectivity toward TOL and MCH, was selected as the membrane substrate. A series of silane coupling agents with and without amino functionality and varying molecular configurations were grafted onto the membrane surface. Remarkably, the three-dimensional saturated cyclohexyl configuration outperforms the planar phenyl group in molecular discrimination among the amino-bearing silanes, overturning the conventional preference for aromatic functionalities. As a result, the separation factor of the MIL-100(In) membrane is enhanced by 175% upon surface modification. Complementary molecular simulations reveal that the spatial configuration of the grafted silane governs the recognition behavior toward aromatic and cycloalkane molecules, as corroborated by binding energy analysis and the minimum intermolecular contact distances obtained from energy-minimized conformations. These findings provide a mechanistic basis for tailoring membrane surface chemistry toward efficient LOHC separation Download: Download high-res image (333KB) Download: Download full-size image
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Food and Bioprocess Technology
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2026
·Vol. 19
·期 6
·299
·
IF 5.6
Li Huina,Wang Guangxian,Wang Songlei,Xia Hongqiang,Lu Yuzhe,Tian Tian,Luo Yulong,Zheng Hao-Bo
This study describes the development of a biodegradable colorimetric membrane by co-pigmenting Lycium ruthenicum anthocyanins (LRA) with catechins, and loading the stabilised complex onto MIL-88B(Fe) dispersed in a chitosan/polyvinyl alcohol (PVA) matrix. Molecular docking simulations revealed favorable non-covalent interactions, primarily hydrogen bonding and π-π stacking, between the anthocyanin and the MIL-88B framework, particularly in proximity to its iron-based coordination nodes. The LRA complex exhibited the highest binding affinity and conformational stability. Density functional theory (DFT) calculations revealed interfacial electron transfer between the LRA and Fe centers, Bader charge analysis indicated electron transfer, with the Fe center losing ~ 0.927 e upon adsorption, providing a possible electronic-level explanation for the enhanced photothermal stability observed in thermogravimetric analysis (TGA) and color retention tests. The optimized film (containing LRA 3% + MIL-88B) exhibits enhanced tensile strength, increased water contact angle to 89.9°, indicating reduced surface hydrophilicity, and significant antioxidant activity, with ABTS radical scavenging rates exceeding 80%. The films exhibited rapid (< 5 min) pH responsiveness over a wide pH range (pH 2–13), demonstrating the potential to reflect the spoilage of beef, lamb, and shrimp through visible colour changes. Soil burial experiments confirmed that the film degraded by approximately 70% within 30 days. This MOF-assisted strategy significantly improved the inherent instability of anthocyanins and provides a sustainable functionalisation solution for smart food packaging systems.
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FOOD RESEARCH INTERNATIONAL
·
2026
·
IF 8.8
Yuhan Li,Lingmei Dai,Dehua Liu,Wei Du
Metal-organic frameworks (MOFs) with tunable porosity are promising carriers for enzyme immobilization, but their practical application is limited by structural instability and difficult recovery. We previously developed an oxidation-reduction (O-R) pyrolysis strategy for mesoporous MIL-88 A, yielding a magnetic carrier (O-R-Meso) with excellent lipase immobilization and recyclable catalysis. Herein, we verify the applicability of this O-R pathway for Fe-based MIL-88 A with tailored pore structures (micro-, meso-, macroporous) by extending it to microporous C-MIL-88 A and macroporous SOM-MIL-88 A. The O-R derivatives (O-R C, O-R-Meso and O-R-SOM) retained the original morphology and pore channel integrity, with improved specific surface area and sufficient magnetization (13–23 emu/g) for magnetic separation. Notably, after O-R pyrolysis, MIL-88 A with various pore sizes essentially maintained or even enhanced the specific activity of immobilized lipase ( Candida antarctica lipase B, CalB), successfully deriving into magnetic carriers with enhanced catalytic efficiency and recyclability. This superiority originates from the preserved pore structure and biocompatible γ-Fe 2 O 3 surface of the O-R derivatives, which effectively retain the native conformation of CalB. Besides, this work systematically compares the secondary structure of free and immobilized CalB on MOF-derived carriers with distinct pore architectures, providing direct structural evidence for the superior enzyme-carrier compatibility of mesoporous materials. In the transesterification synthesis of phosphatidyl EPA/DHA, CalB@O-R-Meso showed the highest EPA/DHA total incorporation, prominent sn -1 positional selectivity, and optimal reusability, outperforming CalB@O-R-C and CalB@O-R-SOM. Furthermore, kinetic studies on the CalB@O-R-Meso-catalyzed system confirmed a Ping-Pong Bi Bi mechanism and revealed competitive product inhibition by phosphatidyl EPA/DHA ( K i = 29.8 mM) with negligible internal mass transfer resistance (η ≈ 1). This work establishes a O-R pyrolysis strategy for tunable porosity Fe-MOFs, clarifies pore size-dependent enzyme -carrier compatibility, and provides a fundamental kinetic basis for phosphatidyl EPA/DHA synthesis.
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ANALYTICA CHIMICA ACTA
·
2026
·
IF 6.1
Peng Zhao,Kai Liu,Yueyan Li,Xiaofang Ban,Yuheng Wu,Jiaqi Liu,Xiaohong Wu,Ziyi Cheng,Fan Wang,Shuo Li,Feng Lin,Huifang Tang,Qingnan Zhao
The excessive activation of sympathetic nerve is closely related to cardiovascular diseases (CVDs). In this study, we developed a novel MIL-100(Fe)@Ag surface-enhanced Raman scattering (SERS) substrate for the simultaneous and effective detection of plasma norepinephrine (NE) and adenosine—two pivotal sympathetic hormones. The microscopic morphology and crystal structure of the substrate were characterized using techniques such as transmission electron microscope (TEM) and X-ray diffraction (XRD). Mechanistically, the HOMO-LUMO energy levels of the detection molecules were calculated using Gaussian. The substrate realized a dual SERS enhancement mechanism through the synergistic effect of localized surface plasmon resonance and interfacial charge transfer. Consequently, the MIL-100(Fe)@Ag platform exhibited high-sensitivity quantitative detection capabilities for NE and adenosine: the detection limit for NE is 0.596 nmol/L; the detection limit for adenosine is 0.24 nmol/L. Crucially, when applied to patients with pheochromocytoma—a neuroendocrine tumor characterized by plasma catecholamine surges, this method achieved robust and stable detection of plasma NE. It offered comparable diagnostic accuracy to conventional mass spectrometry while significantly reducing analysis complexity. Therefore, this innovative strategy may hold great promise for the long-term, decentralized monitoring of sympathetic nerve activity in populations at risk for CVDs or related clinical disorders.
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Nature Communications
·
2026
·
IF 18.1
Lv Guoliang,Zhang Linjuan,Luo Yuanyuan,Zhu Jianqiu,Wu Jilong,Qin Li,Zhang Yanlin,Zhang Zheng,Tan Pengwei,Duan Guotao
Simultaneously achieving chemiresistive gas sensors with high selectivity, sensitivity, and stability remains a significant challenge. In this study, inspired by the H 2 S-specific catalytic enzymes in biological systems, we construct an amorphous unsaturated-ligand MIL-68(Fe) 3D MOF via in situ thermal induction. Without the introduction of extrinsic catalytic or conductive components, this MOF modification strategy creates unsaturated Fe atoms within the framework itself. These atoms function dually as catalytic and conductive sites, thereby overcoming the inherent low conductivity of conventional 3D MOFs and enabling the direct construction of chemiresistive sensor for room-temperature molecular olfactory sensing. The targeted water-adsorption-coordinated catalytic mechanism bypasses the limitations of traditional oxygen adsorption processes to achieve unprecedented comprehensive performance, including fingerprint-level selectivity (against 29 interfering gases), superior sensitivity coefficient (~83/ppm), ultra-low measured lower limit (1 ppb), rapid gas sensing response/recovery characteristics (~30 s/73 s), and excellent long-term stability at room temperature.
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MICROCHEMICAL JOURNAL
·
2026
·
IF 5.2
Li Zhang,Minjie Liang,Chao Li,Jia Jiao,Fengbo Li,Jianjiao Xin,Jing Pan,Ruyan Xie,Haijun Pang,Shaobin Li
A novel PA-MIL-88A composite was designed for detection of phytic acid. • Structural optimization through controllable etching provides a new paradigm for the functionalization of MOF materials. • MIL-88A is water-degradable, and PA is natural plant extract. This strategy follows green analytical chemistry guidelines. • The sensor exhibits low LOD and a wide linear range. • The sensor exhibits excellent practical applicability in fruit juice. Ascorbic acid (AA) may cause adverse reactions when consumed in excess, posing conceivable wellness threats to humans. Consequently, accurate detection of AA content in food is crucial for ensuring food safety and safeguarding human health. This work successfully developed an electrochemical sensor based on phytic acid-etched modified MIL-88A (PA-MIL-88A) for detecting AA in juices. The electrochemical performance of the PA-MIL-88A composite was evaluated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Experimental results indicate that the PA-MIL-88A composite exhibits excellent linearity for AA detection, with a linear range of 10 μM–2640 μM and the limit of detection as low as 2.68 μM. Furthermore, the sensor demonstrated excellent reproducibility, repeatability, and long-term stability. When detecting juice samples, it exhibited significant advantages in recovery rates and relative standard deviation (RSD) values. This work broadens the application of MIL-88A in electrochemical sensing and provides new insights for food detection. Download: Download high-res image (89KB) Download: Download full-size image
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