MICROCHEMICAL JOURNAL
·
2024
·
IF 4.9
Zong-Mu Dong,Yaqing Guo,Liming Qin,Peiyi Zhang,Jian-Feng Wu,Guang-Chao Zhao
A multi-step growing and etching method was used to synthesize metal–organic framework materials (MIL-101) with a hollow structure of distinct shell layers. The resorcinol–formaldehyde organic aerogel (RFOA) was embedded in-situ into the triple-shelled hollow MIL-101 (TSHM) to form a novel RFOA@TSHM spherical multilayer shell composite, which was used as a fiber coating material of solid-phase microextraction for the enrichment and determination of six tetracyclines (TCs) by coupling with HPLC-UV–vis detector in aqueous solutions. Due to the embedding of the RFOA and the multilayer shell structure, the RFOA@TSHM composite is characterized by a stable structure with a larger pore size and specific surface area compared with the TSHM alone. Under optimal conditions, limits of detection of 0.13–1.16 μg L −1 and limits of quantification of 0.43–3.83 μg L −1 were obtained for TCs detection. Moreover, the RFOA@TSHM coating fiber was successfully applied to detect TCs in egg and milk real samples.
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JOURNAL OF HAZARDOUS MATERIALS
·
2025
·
IF 11.3
Renjie Pan,Zongchen Li,Tian-Yang Zhang,Qi Fu,Zheng-Xiong Zheng,Jun Shi,Jian Lu,Chen-Yan Hu,Yu-Lin Tang,Mohamed Gamal El-Din,Bin Xu
Peracetic acid-based advanced oxidation processes (PAA–AOPs), which generate various reactive radicals, have garnered substantial attention for degradation emerging contaminants (ECs). However, nonselective radical-based PAA–AOPs often suffer from interference by water matrix components, causing low contaminants removal efficiency. This study explores the use of amino-(NH 2 )-functionalized metal–organic frameworks (MIL-101(Fe)-NH 2 ) as heterogeneous catalysts for PAA activation, enabling the generation of high-valent iron- (Fe)–oxo species (Fe(IV)) capable of efficiently degrading ECs (80 −100 %, within 30 min). The Fe(II) clusters in MIL-101(Fe)-NH 2 , modulated by electron-donating −NH 2 groups, play a pivotal role in Fe(IV) generation. Scavenger and probe experiments confirmed Fe(IV) as the primary reactive species responsible for ECs degradation. Density functional theory calculations demonstrated that the four-electron transfer to generate Fe(IV) has lower free energy than the two-electron transfer to generate organic radicals (e.g., CH 3 COO • and CH 3 C(O)OO • ). Furthermore, thermodynamically unfavorable CH 3 COO • desorption further promotes Fe(IV) generation. The PAA/MIL-101(Fe)-NH 2 system efficiently degraded SMX ( k app = 121.2 −287.2 M −1 s −1 ) and other ECs ( k app = 40 −432 M −1 s −1 ) with minimal interference from water matrix components and excellent reusability. This study demonstrates that MIL-101(Fe)-NH 2 is a robust catalyst for PAA activation and provides a novel approach for selectively generating Fe(IV) for ECs degradation.
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MICROCHEMICAL JOURNAL
·
2025
·
IF 5.1
Yong Zhang,Jing Wang,Ying Liu,Xuemeng Wu,Lina Gao,Guihua Gao
In this study, a tip foam named as MIL-101(Cr)-NH₂/chitosan (MIL-101(Cr)-NH₂/CS) was prepared by cross-linking chitosan (CS) with MIL-101(Cr)-NH₂ using glutaraldehyde as the cross-linking agent. After freeze-drying, the internal structure of the MIL-101(Cr)-NH₂/CS foam became porous, thereby exposing more MIL-101(Cr)-NH₂, enriching binding sites, ensuring efficient adsorption, and allowing smooth passage of the sample solution. This also facilitates the inhalation and extrusion of the sample solution. Based on the unique advantages of the MIL-101(Cr)-NH₂/CS foam, a method combining pipette tip solid-phase extraction (PT-SPE) with high-performance liquid chromatography equipped with a fluorescence detector (HPLC-FLD) was established for the detection of puerarin and its metabolites (e.g., daidzein and equol) in rat serum. The method exhibited good linearity in the range of 0.5 to 5000 ng/mL, with limits of detection (LOD), lower limits of quantification (LLOQ), and limits of quantification (LOQ) ranging from 0.2 to 15 ng/mL, 0.5 to 50 ng/mL, and 1 to 100 ng/mL, respectively. The relative standard deviations (RSDs) of intra-day and inter-day precision for puerarin, daidzein, and equol were less than 19.8 %, meeting relevant regulatory requirements. The extraction recoveries of puerarin, daidzein, and equol ranged from 80.17 % to 91.70 %, 80.02 % to 87.41 %, and 80.29 % to 85.39 %, with corresponding RSDs of 3.2 % to 10.4 %, 11.2 % to 13.8 %, and 7.9 % to 11.1 %. These results indicate that the developed method meets the methodological requirements for the quantitative analysis of biological samples. The application of MIL-101(Cr)-NH₂/CS foam in PT-SPE further expands the application scope of metal-organic frameworks (MOFs) in solid-phase extraction (SPE) and provides a reference for PT-SPE technology in handling small-volume samples in complex matrices.
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ACS Applied Materials & Interfaces
·
2026
·
IF 7.8
Xiaopeng Zhang,Lin Chen,Longzhu Li,Xiaoming Yan,Junjiang Bao,Ning Zhang,Gaohong He
The introduction of guest metal molecules into metal–organic frameworks (MOFs) is an outstanding method to prepare dual-atom catalysts (DACs) with good oxygen reduction reaction (ORR) activity. However, most of the MOF-derived dual-atom catalysts reported to date exhibit a microporous structure and, therefore, suffer from the underutilization of active sites and poor mass transfer. This study employed NH2-MIL-101 as a precursor to form defect-bearing mesoporous Fe-NC via one-step pyrolysis for adsorbing [Co(en)3]3+, followed by secondary pyrolysis to generate Fe–Co binuclear site catalysts. The mesopores of NH2-MIL-101 are beneficial to [Co(en)3]3+ introduction and can improve the mass transfer of the ORR. Furthermore, the elevated nitrogen content within the [Co(en)3]3+ complex facilitates the co-coordination of Fe and Co with nitrogen, thereby enhancing the formation of Fe–Co diatomic sites. As a result, the obtained FeCo-NC-40 catalyst showed excellent ORR performance with a half-wave potential of 0.915 V (vs RHE). In addition, the liquid-phase Zn–air battery employing FeCo-NC-40 as the cathode catalyst demonstrated a peak power density of 178.13 mW·cm–2 and achieved a discharge specific capacity of 806.13 mAh·g–1 at 10 mA·cm–2, and there was no significant decay in stability for 10 days of continuous cycling.
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MICROCHEMICAL JOURNAL
·
2026
·
IF 5.2
Xu Xu,Yumeng Liu,Jia Lv,Baocheng Ji,Junguang Li,Ke Li,Dianbo Zhao,Yanhong Bai
A modified QuEChERS method was developed in analysis of 52 veterinary drugs. • A novel MIL-101(Cr)–rGO@melamine sponge composite was fabricated. • The fast matrix purification could be achieved within several seconds. • Matrix cleanup was achieved through simple soaking and squeezing. • The method showed low matrix effects, good recoveries, and high precision. Herein, we report the fabrication of an elastic, quick, easy, cheap, effective, rugged, and safe adsorbent using a functionalized melamine sponge (MLS) and used it for the high-throughput analysis of 52 veterinary drugs in beef liver samples via ultraperformance liquid chromatography–tandem mass spectrometry. The as-prepared adsorbent was obtained by successive loading of Matérial Institut Lavoisier-101 (Chromium) [MIL-101(Cr)] and reduced graphene oxide (rGO) on melamine sponge skeletons. Excellent linearity with determination coefficients of ≥0.9942 was obtained across a range of 0.25–200 μg·kg −1 . Relatively low limits of detection (0.1–4.9 μg·kg −1 ) and limit of quantitation (LOQ; 0.3–16.2 μg·kg −1 ) were obtained. When fortified at three levels (1×, 5×, and 10× LOQ), spiked recoveries varied between 63.5% and 115.4%, with the intraday and interday relative standard deviations of ≤12.9%. Through direct infiltration and compression, efficient matrix purification was accomplished within seconds, yielding negligible matrix effects (from −18.4% to +19.1%). Thus, the MIL-101(Cr)–rGO@MLS adsorbent possesses high potential for fast, convenient, and efficient matrix purification in complex sample analysis. Download: Download high-res image (179KB) Download: Download full-size image
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TALANTA
·
2026
·
IF 6.7
Xiao Liang,Haifeng Wei,Xiantao Zeng,Yan Zhang,Cheng Rui,Mingyue Shen,Fan Liu,Lan Guo,Yiqun Wan
Prepared dishes, one of the prominent modern foods, carry the risk of alternaria toxins (ATs) contamination. To address this concern, an efficient dispersed solid-phase extraction (d-SPE) method based on MIL-101(Fe) coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed for the analysis of six ATs in prepared dishes. Characterization results confirmed that the synthesized MIL-101(Fe) possesses a high specific surface area and appropriate pore sizes distribution. Furthermore, computational simulations revealed that ATs could be efficiently absorbed and purified by MIL-101(Fe) via hydrogen bonding, π-π stacking, and Lewis acid-base interactions. Under optimized conditions, the method exhibited excellent linearity (R 2 ≥ 0.9990), and the limit of quantifications (LOQs) ranging from 0.07 to 0.37 μg/L, with recoveries in the range of 76.2%-108.3% and relative standard deviations (RSDs) below 9.8%. this study aims to bridge this gap by utilizing UHPLC-MS/MS to develop a robust method for the high-sensitivity and high-accuracy quantification of ATs in prepared dishes. Furthermore, the adsorption mechanism of MIL-101(Fe) for target toxins was elucidated by grand canonical Monte Carlo (GCMC) simulation and Density Functional Theory (DFT) calculation.
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TALANTA
·
2022
·
IF 6.556
Lin Li,Yingying Li,Sijia Zhang,Ting Wang,Xiaohong Hou
In this study, MIL-101(Cr)/cellulose aerogel/melamine sponge composite was fabricated through a simple soaking method. The composite was packed in the syringe barrel and used as the sorbent for microextraction in packed syringe. Coupled to UPLC-MS/MS, the proposed method was employed for the analysis of trace nitroimidazoles in water samples. The parameters affecting the extraction efficiency, including sorbent type, pH value of sample solution, sample solution volume and elution solvent were optimized. Under the optimal conditions, good linearity (r > 0.99 for five analytes), high sensitivity (limit of detection: 8.250–16.33 ng L −1 ), ideal precision (intra-day precision: 1.1%–5.3%, inter-day precision: 1.8%–6.7%) and satisfactory accuracy (recovery: 70.4%–96.7%) were achieved. The proposed method was proved to be efficient, easily operative and environmentally friendly.
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Nanoscale
·
2022
·Vol. 14
·期 18
·7055-7074
·
IF 8.307
Rutong Song,Jun Yao,Mei Yang,Zhongbin Ye,Zhuang Xie,Xiang Zeng
Water pollution control is one of the major challenges currently faced. With the development of photocatalytic technology, an increasing number of new and efficient catalysts have been developed, but most of the catalysts have limited light capture ability and catalytic degradation efficiency. Therefore, in this work, hydrogen peroxide was further introduced to establish a photo-Fenton system to improve the photocatalytic effect by constructing a Z-scheme, and the degradation ability of the catalyst was maximized. Moreover, we successfully adhered bismuth tungstate nanosheets onto the surface of a MIL-101(Fe) framework and changed the number of active sites with iron ions of different doping amounts. We found that the number of active sites in the photo-Fenton system does not increase linearly, but increases and decreases regularly, which is similar to the change in band structure after doping. In addition, the results of the radical scavenger experiment and electron paramagnetic resonance (EPR) revealed that both hydroxide radical (˙OH) and superoxide radical (˙O2−) participated in methylene blue (MB) degradation, of which ˙OH was the main active species for pollutant degradation. Based on high-performance liquid chromatography-mass spectrometry (HPLC-MS) analysis, the possible degradation pathways were proposed. We believed that this work will provide insights into the heterojunction photo-Fenton system.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yarui Wang,Chengzhuo Yu,Sen Wang,Jin Xu,Fanglan Geng,Silong Wang,Jitao Lv,Lixia Zhao,Yawei Wang
Humic acids (HA) released during algal bloom poses a key challenge for efficient photocatalytic degradation of Microcystin-LR (MC-LR) due to their scavenging function on active species. Herein, MIL-101(Fe)/TiO 2 -P25 (M/P) was constructed to diminish the inhibitory effect of HA on the photocatalytic degradation of MC-LR. Results showed that MC-LR could be efficiently removed assigning to the photogenerated holes (h + ) and superoxide radical (O 2 •− ) oxidation under visible light irradiation, where the carboxy groups of D -glutamic acid (Glu) and methyl- D -aspartic acid (MeAsp), and Adda side chain related to MC-LR biotoxicity were selectively destroyed to achieve MC-LR detoxication. More importantly, HA exerted non-inhibitory effect on MC-LR removal by M/P. The counteracting mechanisms were studied. Firstly, the location of TiO 2 in the pore structure of MIL-101(Fe) could occupy the adsorption sites of HA, and decrease the HA adsorption on M/P. Furthermore, XPS analyses suggested the coordination of unsaturated Fe metal sites on the surface of M/P hybrids complexed with –OH and –COOH of HA, which could accelerate the electron transfer and reduce hole consumption. Thus, the inhibitory effect of HA was alleviated during photocatalytic MC-LR treatment. This work offers a possible way to remove MC-LR in an abundant HA matrix water system efficiently.
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ELECTROPHORESIS
·
2017
·Vol. 38
·期 19
·2521-2529
·
IF 2.744
Yue Liu,Jia Hu,Yan Li,Yun-Tao Shang,Jia-Qi Wang,Ye Zhang,Zhong-Liang Wang
In this work, a CE method was developed to separate five anthraquinones: aloe-emodin, rhein, emodin, chrysophanol, and physcion. The CE method used a nano-sized metal organic framework MIL-101 (nMIL-101) as pseudostationary phase (PSP) and sorbent for dispersed particle extraction (DPE). The nMIL-101 was synthesized by microwave technique and was characterized by UV-vis, TEM, Zeta potential, X-ray diffraction spectrometry and micropore physisorption. In this method, anthraquinones were adsorbed by nMIL-101 of a fast kinetics within 10 min and then separated by CE. The CE conditions were optimized considering time, pH, buffer ionic strength, and nanoparticles concentration. The optimal CE condition is using 20 mM sodium borate buffer (pH 9.1) containing 15% methanol (v/v) and 400 mg/L nMIL-101 as additives within 8 min. The LODs varied from 24 to 57 μg/L, which were lower than those previously reported. Our method has been successfully applied to determine trace anthraquinones in environmental water samples.
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JOURNAL OF CHROMATOGRAPHY A
·
2024
·
IF 3.8
Tianci Lv,Fubin Liu,Mengqian Xiao,Ying Liu,Litao Wang,Guihua Gao
In this study, a novel hierarchical pore MIL-101(Cr) foam (HPF-MIL-101) was designed and prepared using the sacrificial template method with NaCl as the sacrificial template. This method involved grinding, heating, and washing the NaCl template to produce HPF-MIL-101, with PVDF as the binder and MIL-101(Cr) as the adsorbent. This preparation process is both straightforward and cost-effective, avoiding the use or generation of any organic reagents, thereby offering an environmentally sustainable approach for producing metal-organic framework (MOF) composites. The prepared HPF-MIL-101 exhibited excellent adsorption capabilities for both anionic dye (methyl orange, MO) and cationic dye (methylene blue, MB). The adsorption process followed a pseudo-second-order kinetic model and Friedrich isotherm model, indicating a multilayer adsorption. This is further supported by the Weber-Morris intraparticle diffusion model, which divided the adsorption process into three stages. Furthermore, the adsorption process was consistent with the Freundlich isotherm model, with a correlation coefficient ( r ) greater than 0.96. HPF-MIL-101 can also be used as an adsorbent for solid phase extraction (SPE). Therefore, an SPE method combined with high-performance liquid chromatography (HPLC) was developed using HPF-MIL-101 as the adsorbent to analyze five fluoroquinolones (FQs) in water samples. This analytical method showed good linearity in the range of 30–2000 ng·mL −1 , with excellent linear correlation coefficient ( r = 0.9991–0.9999), reasonable extraction recoveries ranging from 80.39 to 112.7 % (RSD ≤ 7.9 %), and low limits of detection (8–30 ng·mL −1 ). Overall, the results indicated that HPF-MIL-101 not only had a simple, environment-friendly, and pollution-free preparation process but also can be reused for enrichment and detection of trace FQs in water. Thus, HPF-MIL-101 exhibits immense application potential in environmental pollutant removal and also provides a valuable reference for the preparation and application of other MOF composites.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Liping Liang,Fenfen Xi,Jinhui Zhao,Gunel Imanova,Sridhar Komarneni,Jianfeng Ma
nZVI was immobilized on MIL-101(Cr), a metal–organic framework (MOF), and subsequently utilized for the removal of U(VI) from aqueous solution. This composite was also tested for its toxicity to Escherichia coli ( E. coli ). The results demonstrated that MIL-101(Cr) and nZVI had a significant synergistic effect. This composite material is excellent for removing U(VI) and the optimal ratio of MIL-101(Cr) to nZVI was found to be 1.2:1 on mass basis. Adsorption data exhibited excellent fitting to the Freundlich and pseudo-second-order kinetic models, and a maximum removal capacity of 526.32 mg/g of U(VI) was achieved by M-Fe at 298 K (pH = 6.0). The removal mechanisms were clarified by the X-ray absorption near edge structure (XANES), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). Results reveled that U(VI) was mainly removed through chemisorption, forming a bidentate mononuclear edge-sharing linkage between UO 3 pyramid and iron(hydro)oxide. Through free radical quenching experiments and EPR analysis, it was indicated that the existence of reactive oxygen species (ROS) accelerates the oxidation of nZVI, generating more iron oxides or hydroxides for U(VI) adsorption, while inhibiting the reduction of U(VI) to U(IV). Furthermore, immobilized nZVI on MIL-101(Cr) mitigated the biotoxicity of Escherichia coli ( E. coli ). Direct contact played a crucial role in inactivating E. coli cells by nZVI/ E. coli system. Extracellular reactive oxygen species (ROS) played a vital role in inactivating E. coli in the M-Fe/ E. coli system where OH is the main ROS. These findings enhance our understanding of the mechanism of U(VI) removal and bactericidal effect on organisms using ZVI-based composites, which will broaden the application scope of the two materials in pollution removal, especially in radioactive decontamination.
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