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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2026 · IF 4.4

Fabrication of NH2-MIL-101(Fe)/few-layer Ti3C2 Schottky heterojunctions to boost charge separation for enhanced photocatalytic Cr(VI) elimination

Bingkun Liu,Juncheng Guo,Ziyang Liang,Yuhan Yang,Beibei Liu,Bing Han,Yonghui Zhang

NH 2 -MIL-101(Fe)/few-layer Ti 3 C 2 Schottky heterojunctions are constructed. • NH 2 -MIL-101(Fe)/Ti 3 C 2 composite shows higher photocatalytic activity for Cr(VI) removal. • The Schottky heterojunctions boost the separation of photogenerated charges. • The photogenerated electrons and •O 2 − dominate the Cr(VI) reduction process. The limited charge transfer efficiency of single-component semiconductor photocatalysts remains a critical bottleneck restricting the photocatalytic elimination of harmful pollutants. Here, NH 2 -MIL-101(Fe) nanoparticles are anchored onto few-layer Ti 3 C 2 nanosheets via electrostatic self-assembly to construct NH₂-MIL-101(Fe)/Ti 3 C 2 heterostructure. The few-layered 2D Ti 3 C 2 supplies abundant adsorption and catalytic active sites. Furthermore, benefiting from the Schottky junction and the superior conductive feature of Ti 3 C 2 MXene, the separation and transport of photoinduced carriers are remarkably promoted in the NH 2 -MIL-101(Fe)/Ti 3 C 2 . Accordingly, the optimized NH 2 -MIL-101(Fe)/Ti 3 C 2 –10% sample can remove 95.7% of Cr(VI) after 150 min of visible-light irradiation and still exhibits favorable reusability after three cycles. The electrons and •O 2 − are confirmed as the primary active species driving Cr(VI) reduction. Combined with comprehensive characterizations, a plausible photocatalytic mechanism of Cr(VI) reduction is put forward. This work offers fundamental guidance for developing MXene-based Schottky heterostructures toward improved photocatalytic activity.

CAS / MDL: 10025-77-1 140-22-7
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Results in Chemistry · 2025 · IF 4.2

TiO2 material loaded on LDH/MIL-101(Fe) is doped with La and Fe to effectively remove pyridine: “Performance and mechanism”

Wei Zhang,Ku Yu,Wang Aihe

In this study, pyridine-a representative nitrogen-containing heterrocylic contaminant in coal chemical wastewater-was targeted for photocatalytic degradation. We developed a novel ternary composite photocatalyst through the in-situ integration of layered double hydroxide (LDH) and iron-based metal-organic framework (MIL-101(Fe)) with lanthanum‑iron co-doped TiO 2 via hydrothermal synthesis. These contaminants are characterized by high environmental persistence, low biodegradability, and potential teratogenic/carcinogenic risks. The synthesized LDH/MIL-101(Fe)/La-Fe-TiO 2 composite was systematically characterized using scanning electron microscopy (SEM), UV–Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) analysis. Key findings revealed that: (1) The composite architecture achieves an exceptional specific surface area of 168.96 m 2 /g through synergistic LDH/MIL-101(Fe) integration; (2) La–Fe co-doping effectively extends the photoresponse threshold of TiO 2 to the visible-light region. Under optimized conditions (25 °C, 300 rpm agitation, 400 W irradiation), the system achieved 96.1 % pyridine degradation (initial concentration: 100 mg/L) within 4 h, following pseudo-first-order kinetics (R 2  = 0.99). Remarkably, the catalyst maintained 94.5 % efficiency after five consecutive cycles, demonstrating superior stability. Mechanistic investigations combining GC–MS analysis, electron paramagnetic resonance (EPR) detection, and radical quenching tests identified the reactive species activity sequence as ∙ h + > ∙ OH > O 2 − , ultimately elucidating the complete pyridine mineralization pathway.

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ACS Sustainable Chemistry & Engineering · 2026 · IF 7.6

Elucidating the Role of –NH2 in a NH2-MIL-53-Derived Ni/Al2O3 Catalyst for Long-Term Dry Reforming of Methane

Jiaxin Wang,Shenghua Liu,Xiaoqian Feng,Lijiao Chen,Huan Wang,Yonghua Zhao,Qijian Zhang,Haiyan Wang,Xinwen Guo

Dry reforming of methane (DRM) is a promising route for the simultaneous conversion of CO2 and CH4; despite the effectiveness of C–H bond activation ability of Ni-based catalysts, they face serious challenges due to coking. Herein, two metal–organic frameworks (MOFs), NH2-MIL-53 and MIL-53 were loaded with Ni via impregnation and calcined at different temperatures to prepare Ni/Al2O3 catalysts. The results reveal that the Ni-based catalyst derived from NH2-MIL-53 possesses a higher specific surface area (SSA) due to the presence of –NH2 groups, which remarkably improved the dispersion of Ni. Additionally, the calcination temperatures are found to play an important role. Low-temperature calcination leads to weaker metal–support interaction (MSI) while high-temperature calcination results in lower specific surface area (SSA) and agglomeration of the active component Ni. The Ni/Al2O3 catalyst calcined at 850 °C exhibits moderate MSI and high SSA, leading to excellent catalytic activity (CH4 conversion ∼68%, CO2 conversion ∼80%) and stability (>50 h with coking ≈0.022 mmol C·gcat–1·h–1) at 750 °C with a GHSV of 96,000 mL/(gcat·h). The derived porous alumina restricts Ni sintering. In situ DRIFT results show that such a catalyst benefits the formation of key intermediate b-HCOO* due to high Ni dispersion. This work provides new insights and directions for optimizing the performance of MOF-derived catalysts.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2026 · IF 5.4

Enhanced photodegradation performance and mechanism of MIL-101(Fe)@AgI@TPA/TPB photocatalyst with double Z-scheme heterojunction for oxytetracycline hydrochloride

Bolong Liang,Hongbin He,Xi Zhu,Shu-Xuan Liang

The residue of oxytetracycline hydrochloride (OTC) has emerged as a significant concern impacting both human health and the ecological environment. Photocatalysis has a good application prospect in the treatment of antibiotic pollution due to its advantages of lost cost, high efficiency and environmental friendliness, and the development of photocatalyst has become crucial for achieving effective photocatalytic degradation. The preparation of Z-scheme heterojunction is regarded as an effective strategy to enhance photocatalytic activity. Herein, double Z-scheme MIL-101(Fe)@AgI@TPA/TPB heterojunction materials were innovatively designed and successfully prepared. MIL-101(Fe)@AgI@TPA/TPB could achieve 95.09 % OTC removal efficiency under visible light irradiation in 70 min. The investigation of photoelectric properties and mechanisms revealed that MIL-101(Fe)@AgI@TPA/TPB had a broader range and enhanced ability for light absorption, along with a narrower band gap. It was determined that ·O 2 - and ·OH were the primary active species involved in the photocatalysis process. The mechanism of double Z-scheme heterojunction capable of facilitating efficient photocatalytic degradation was proposed, and the intermediate products and decomposition pathways of OTC in the photocatalytic degradation process were analyzed. This study provides innovative insights into practical application through the prepared double Z-scheme heterojunction photocatalyst aimed at remediating OTC contamination in water environments.

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APPLIED CATALYSIS B-ENVIRONMENTAL · 2026 · IF 19.7

Regulating nitrogen activation and proton supply to boost photocatalytic nitrogen fixation via Co-ZnO/ MIL-125(SH)2 S-scheme heterojunction

Qi Chen,Zefeng Yang,Yueling Chen,Jionghua Wu,Jimmy C. Yu,Ling Wu

More efficient N 2 activation and carrier dynamics are needed for effective solar-driven ammonia synthesis. Herein, a heterojunction photocatalyst (Co-ZnO/MIL-125(SH) 2 ) was constructed by using MIL-125(Ti) with sulfhydryl functionalization and Co-doped ZnO for photocatalytic nitrogen fixation. A series of characterization reveal that the formation of S-scheme charge transfer greatly enhances interfacial charge separation for more available carriers. The presence of Ti 3 + sites in MIL-125(SH) 2 also facilitates the adsorption and activation of N 2 , effectively leveraging the photogenerated electrons for N 2 conversion. Moreover, the introduction of Co-ZnO increases the hydrophilicity of the catalytic surface. This allows more water molecules to be oxidized by photogenerated holes to release H + for the N 2 hydrogeneration process. As a result, a high photocatalytic ammonia production rate of 50.8 μmol•g −1 •h −1 is achieved under visible light irradiation. This study presents an insight into engineering S-scheme heterojunction composite by coupling molecular coordinate activation and improved protons supply for efficient photocatalytic nitrogen fixation.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2026 · IF 9.1

Electronic effect-guided ligand functionalization of MIL-101 (Fe): Unlocking a new perspective for regulating ROS generation in Fenton-like systems

Jing Li,Jinquan Wan,Yan Wang

In peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs), the precise regulation of reactive oxygen species (ROS) generation pathways is a core challenge for achieving selective degradation of target pollutants. In this study, we propose an electronic effect-guided ligand functionalization strategy by systematically introducing electron-donating (-OH, -NH 2 ) and electron-withdrawing (-NO 2 ) groups into the MIL-101 (Fe) framework, thereby establishing a quantitative structure-activity relationship between the electronic structure, coordination environment of Fe centers and ROS generation. The results demonstrate that electron-donating groups (-OH, -NH 2 ) significantly promote the non-radical pathway dominated by singlet oxygen ( 1 O 2 ), achieving efficient degradation of the electron-rich pollutant sulfamethoxazole (SMX) with removal efficiencies of 93.0% and 91.2%, respectively. Notably, the 1 O 2 contribution rate in the MIL-101(Fe)-OH system reached 95.07%. Correlation analysis reveals a significant positive correlation between C O content and 1 O 2 contribution. Combined experimental characterization and DFT calculations indicate that the selective generation of ROS results from the synergistic effects of multiple factors, including electronic structure, adsorption energy, and charge transfer. Electron-donating groups enhance the electron density at the Fe center, elongate the Fe O bond length, and optimize PMS adsorption energy, thereby promoting the self-disproportionation of the key SO 5 •- intermediate to generate 1 O 2 . This work highlights the promotional role of functional group electronic effects on the non-radical pathway, elucidates the core mechanism governing ROS generation, and provides a mechanistic framework for the design of highly selective Fenton-like catalysts. Environmental implication This study employs an electron-effect-guided ligand functionalization strategy to systematically reveal the structure–activity relationship between the electronic structure and coordination environment of metal nodes in Fe-MOFs and the ROS generation. The electronic effects of functional groups enable the precise regulation of ROS, and electron-donating groups significantly promote nonradical pathways, thereby achieving efficient degradation of the electron-rich contaminant sulfamethoxazole. This work highlights the promotion of nonradical pathways by the electronic effects of functional groups, clarifies the core mechanism governing ROS generation, and provides new insights for the design of highly efficient and selective catalysts.

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JOURNAL OF CHROMATOGRAPHY A · 2026 · IF 4

Metal-organic framework MIL-101(Cr) functionalized β-cyclodextrin-modified magnetic multi-walled carbon nanotubes for efficient extraction of amphenicol antibiotics

Lin Lv,Hongmei Liu,Tao Song,Yan Zhao

Given the extensive use of amphenicol antibiotics and their potential adverse effects on human health, the development of simple and highly sensitive detection methods is essential to ensure food safety. In this work, a novel and highly efficient magnetic sorbent based on β-cyclodextrin-modified magnetic multi-walled carbon nanotubes functionalized with MIL-101(Cr) (Fe 3 O 4 @β-CD@MWCNTs@MIL-101(Cr)) was developed and combined with ultra-high-performance liquid chromatography-mass spectrometry (UHPLC-MS/MS) to achieve highly sensitive detection of three amphenicol antibiotics (chloramphenicol, thiamphenicol, and florfenicol) in honey samples. The key factors influencing extraction efficiency in the magnetic solid-phase extraction process were identified using the Plackett-Burman experimental design, whereas the optimal experimental conditions were determined through Box-Behnken design-based response surface methodology optimization. Under these optimized conditions, favorable linear relationships for amphenicol antibiotics were observed within the concentration range of 0.5–250 ng mL − 1 (R 2 ≥ 0.9951). The method exhibited detection limits of 0.04–0.07 μg kg − 1 . Recovery rates ranged from 83.2% to 97.9%, with intra-day and inter-day precisions both below 7.2%. This method provides an efficient tool for monitoring amphenicol antibiotics in complex matrices.

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TALANTA · 2023 · IF 6.1

Determination of trace bisphenols in milk based on Fe3O4@NH2-MIL-88(Fe)@TpPa magnetic solid-phase extraction coupled with HPLC

Qingying Wang,Lianfang Chen,Xiaoyan Cui,Jie Zhang,Yaohui Wang,Xiupei Yang

Herein, a covalent organic framework (COF) was grown on a magnetic metal-organic framework (MOF) by a solvothermal method for the efficient extraction of bisphenols (BPs). The magnetic solid-phase extraction (MSPE) of four bisphenols (bisphenol A, bisphenol B , bisphenol AF and bisphenol C) was carried out without adjusting the pH and salt concentration. When 30 mg Fe 3 O 4 @NH 2 -MIL-88(Fe)@TpPa was used to adsorb for 25 min, 6 mL methanol was used to elute for 20 min, and the extract was detected by high-performance liquid chromatography (HPLC). The proposed method has a low detection limit of 0.011–0.036 ng mL −1 , a wide linear range of 0.05–100 ng mL −1 , and a correlation coefficient (R 2 ) of 0.9980–0.9998. The intra-day and inter-day precisions are 0.74–2.54% and 1.68–3.72%, respectively. Bisphenol A was determined by applying the proposed method to the determination of actual milk samples. The standard addition experiment showed that the relative recovery of the four bisphenols was 85.70–119.7%. Pseudosecond-order, first-order, Langmuir and Freundlich models were applied to explore the adsorption characteristics of Fe 3 O 4 @NH 2 -MIL-88(Fe)@TpPa. In general, the established Fe 3 O 4 @NH 2 -MIL-88(Fe)@TpPa-MSPE-HPLC-UV method exhibits attractive sensitivity, simple manipulation, and excellent reusability, and it has excellent prospects for the detection of trace BPs in complex milk matrices.

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CHEMOSPHERE · 2023 · IF 8.8

Visible light enhanced persulfate activation for degradation of tetracycline via boosting adsorption of persulfate by ligand-deficient MIL-101(Fe) icosahedron

Gangya Cheng,Chen Yuan,Wansheng Ruan,Ben Ma,Xinyu Zhang,Xinjing Yuan,Zhihui Li,Dan Wang,Fei Teng

In this work, Fe-based metal-organic frameworks (Fe-MOFs) are prepared by a simple solvothermal method, in which acetic acid/N, N-dimethylformamide (HAc/DMF) mixture solvents are employed to regulate the particle morphology, exposed facets and ligand defects. At HAc/DMF = 0/50, 5/45 and 8/42 (volume ratio), the irregular particles (MIL-53(Fe)), elongated icosahedrons (5H-MIL-101(Fe)) and icosahedrons (8H-MIL-101(Fe)) are obtained, respectively. Under visible light irradiation (λ > 420 nm) and the addition of sodium persulfate (PS), 5H-MIL-101(Fe) shows the highest degradation activity for tetracycline (TC). Specifically, 80% of TC has been removed by 5H-MIL-101(Fe) within 25 min, and the degradation kinetics rate is 3.03 times higher than that over MIL-53(Fe). The improvement of catalytic activity is mainly attributed to the active facets exposed and ligand defects of 5H-MIL-101(Fe). Density functional theory (DFT) calculation further confirms that the active facets exposed and ligand defects of 5H-MIL-101(Fe) favor the adsorption and activation of PS, benefiting the generation of •SO 4 − . Besides, a probable degradation pathway of TC is proposed based on trapping experiments and liquid chromatography-mass spectrometry (LC-MS) test. Furthermore, the toxicities of intermediates are predicted by the quantitative structure-activity relationship (QSAR) mathematical model. This work demonstrates that visible light enhanced PS activation (Vis-PSA) can more effectively degrade organic pollutants, and this work also provides a simple strategy to precisely regulate ligand defects and actively exposed facets of Fe-MOFs to enhance the adsorption and activation of PS.

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

Magnetic Fe3O4/MIL-101 composite as a robust adsorbent for removal of p-arsanilic acid and roxarsenic in the aqueous solution

Xiao-Ying Li,Wen-Qing Ding,Pan Liu,Lei Xu,Ming-Lai Fu,Baoling Yuan

The p -arsanilic acid ( p -ASA) and roxarsenic (ROX) are typical organic arsenic compounds (OACs), which can be evolved into highly poisonous inorganic arsenic species in the aqueous solution. Herein, a magnetic MOFs-based composite of Fe 3 O 4 /MIL-101 was successfully obtained by a stepwise solvothermal method and further used in the adsorption of p -ASA and ROX. The structural and physicochemical characteristics of Fe 3 O 4 /MIL-101 were firstly investigated in detail. It was found that Fe 3 O 4 microspheres were evenly embedded on the polyhedral MIL-101 surface after the solvothermal process and exhibited a strong superparamagnetic property. After adsorption, a simple external magnetic field can be used to quickly separate the composite from the aqueous solution. The adsorption experiments indicated that the composite is an excellent adsorbent with maximum adsorption capacities of 683.44 and 946.57 mg·g −1 for p -ASA and ROX, respectively. In addition, the effects of composite dosage, initial pH and co-existing anions on the adsorption efficiency were investigated. The main adsorption mechanism consists of the existence of hydrogen bonding , π-π stacking and As-O-Fe coordination between Fe 3 O 4 /MIL-101 composite and OACs. We believe that this study would be very meaningful to promote the application of magnetic MOFs based composites for effective adsorption for OACs in the environmental remediation.

CAS / MDL: 121-19-7
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JOURNAL OF NANOBIOTECHNOLOGY · 2022 ·Vol. 20 ·期 1 ·1-12 · IF 9.429

A UCMPs@MIL-100 based thermo-sensitive molecularly imprinted fluorescence sensor for effective detection of β-lactoglobulin allergen in milk products

Hong Liping,Pan Mingfei,Yang Xiao,Xie Xiaoqian,Liu Kaixin,Yang Jingying,Wang Shan,Wang Shuo

In this study, a thermo-sensitive molecularly imprinted fluorescence sensor was developed for the specific detection of β-Lactoglobulin (β-LG) allergen in milk products. The metal–organic frameworks (MIL-100) with a high specific surface area was coated on the surface of upconversion micro-particles (UCMPs). As the core, an imprinted polymer layer allowing for swelling and shrinking with response to temperature was prepared, which exhibited high adsorption and mass transfer capabilities for β-LG allergen. The fluorescence intensity of UCMPs@MIL-100@MIP decreased linearly with the concentration of β-LG in the range of 0.1–0.8 mg mL−1, and the limit of detection was 0.043 mg mL−1. The imprinting factor reached 3.415, which indicated that excellent specificity of the UCMPs@MIL-100@MIP for β-LG allergen. In the analysis of β-LG allergen in actual milk samples, the proposed UCMPs@MIL-100@MIP fluorescence sensor produced reliable and accurate results (recovery: 86.0–98.4%, RSD: 2.8–6.8%), closely related to the results of standard HPLC method (correlation coefficient: 0.9949), indicating that its feasibility in the detection of β-LG allergen.Graphical Abstract

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POLYHEDRON · 2022 · IF 2.975

Green synthesis of Hesperitin dihydrochalcone glucoside by immobilized α-l-rhamnosidase biocatalysis based on Fe3O4/MIL-101(Cr) metal-organic framework

Chunqing Wang,Na Xia,Siming Zhu,Lin Chen,Liang Chen,Zhendong Wang

In this study, α- l -rhamnosidase was immobilized on magnetic Fe 3 O 4 /MIL-101 (Cr) nanoparticles using MIL-101(Cr) as precursor by crosslinking method. The crosslinking agent concentration ratio and crosslinking time were EDC/NHS 1:1 and 2 h, respectively. The immobilized materials were characterized by FT-IR, XRD, SEM and VSM. The saturation magnetization of the prepared magnetic nanoparticles was 46.2 emu/g. The optimum pH and temperature of immobilized enzyme were 6 and 60 °C. The application of immobilized enzyme in the preparation of hesperidin dihydrochalcone glucoside (HMGDC) by hydrolysis of hesperidin dihydrochalcone (HSDDC) was studied. The results showed that immobilized enzyme had better temperature resistance, repeatability and stability than free enzyme. The immobilized enzyme activity was 293.55 U/g, and the recovery was 116.03%. After treatment at 60 °C for 4 days, the enzyme activity remained at 24.6%. The conversion rate of HSDDC reached 93.1%.

CAS / MDL: 6066-82-6
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