MICROPOROUS AND MESOPOROUS MATERIALS
·
2024
·
IF 4.8
Mengting Xu,Zeyu Chen,Yeyang Ni,Wanyong Yang,Xihua Xu,Qing Liu,Zhaoyang Fei,Mifen Cui,Xu Qiao
MIL-126(Fe) shows great potential for aqueous phase drug adsorption due to its permanent porosity and easy modification. Herein, we utilized the ligand installation method to introduce two ligands, 2-amino terephthalic acid (NH 2 -BDC) and 2-nitro terephthalic acid (NO 2 -BDC), into MIL-126(Fe) to prepare MIL-126(Fe)-NH 2 and MIL-126(Fe)-NO 2 , respectively. Various analytical tools were used to confirm the successful installation of the 1, 4-phthalic acid (BDC) series of ligands, as well as the successful introduction of amino (-NH 2 ) and nitro (-NO 2 ) groups. The presence of both -NH 2 and -NO 2 groups improved the adsorption of TC by the adsorbent material, with -NH 2 groups having a stronger influence on the enhancement. The experimental results indicated that MIL-126(Fe)-NH 2 had the highest adsorption performance at the optimal pH of 7, achieving a static adsorption capacity of 326.5 mg/g, which was about twice the adsorption capacity of the original MIL-126(Fe). X-ray photoelectron spectroscopy (XPS) determined that the adsorption of TC by MIL-126(Fe)-NH 2 relies mainly on π-π interaction and Fe-N coordination bonds. Furthermore, the higher adsorption capacity of MIL-126(Fe)-NH 2 can be attributed to the O-H⋯N hydrogen bonds interaction between -NH 2 and the phenolic hydroxyl group (Ph-OH) in the TC molecule.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Lu Liu,Yajie Chen,Jiajia Zhang,Fanze Zeng,Jinyu Bao,Wenpeng Li,Guohui Tian
The rational construction of heterojunctions with surface defects and localized surface plasmon resonance (LSPR) effect is a promising strategy for improving CO 2 photoreduction performance. Herein, the one-dimensional/two-dimensional (1D/2D) S-scheme heterostructures integrated with non-stoichiometric 1D W 18 O 49 nanowires (H-W 18 O 49 NWs) and 2D ultrathin MIL-125(Ti) nanosheets (MIL-125(Ti) NSs) were constructed by self-assembly for photocatalytic CO 2 reduction. In situ X-ray photoelectron spectroscopy (XPS), electron spin resonance spectra (ESR), and photoluminescence (PL) spectroscopy characterizations confirm the construction of S-scheme heterojunction and the solid internal electric field at the heterointerface enables effective spatial charge separation while keeping a strong redox capability. The hot electrons generated from the LSPR effect of visible-near-infrared light-excited H-W 18 O 49 NWs can be injected into MIL-125(Ti) NSs to increase the electron density and accelerate the reaction rate. Thus, the optimized H-W 18 O 49 NW/MIL-125(Ti) NS heterostructure exhibited good performance, achieving a CO yield of 202.37 μmol g -1 h −1 . This study enriches the diversity and architecture of available heterostructures for photocatalytic applications.
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Journal of Energy Chemistry
·
2024
·
IF 14
Jinzhi Jia,Jinhua Zhang,Kailu Guo,Lanyue Zhang,Gening Du,Hao You,Junfeng Huang,Mudong Tu,Hua Li,Yong Peng,Wei Dou,Cailing Xu
Designing highly active and stable electrocatalysts of oxygen evolution reaction (OER) is one of the crucial challenges. In this study, a novel OER electrocatalyst, NiFe-MIL-53 modified with ultra-low rhodium (Rh@NiFe-MIL-53), is successfully prepared via the hydrothermal method. In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species. More importantly, the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH) 2 after doping Rh is beneficial for improving the electrochemical stability of the catalyst. X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH. Furthermore, theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap, regulates the d -band center ( ε d ), accelerates the charge transfer, and optimizes the adsorption behavior of oxygen-containing intermediates, thereby lowering the energy barrier of rate-determining steps. Consequently, the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity (240 mV) with a small Tafel slope of 48.2 mV dec −1 and long-term durability (over 1270 h at 10 mA cm −2 and 110 h at 200 mA cm −2 ). This work presents a new perspective on designing highly efficient OER electrocatalysts.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Yuhao Yang,Chunhua Wang,Jiani Cai,Ying-Ya Liu,Zhiquan Yu,Zhichao Sun,Yao Wang,Anjie Wang,Chong Peng
Selective hydrogenation of phenol to cyclohexanone is of great significance for the production of value-added chemical intermediates and products. Pd/MIL-100(Cr), featuring highly dispersed Pd nanoparticles (∼2.5 nm), were synthesized using a double-solvent impregnation method followed by NaBH4 reduction. During aqueous-phase phenol hydrogenation, the catalyst achieved full conversion with 98.3% selectivity toward cyclohexanone within 1 h at 0.1 MPa and 100 °C. The catalyst exhibited high stability, maintaining performance up to 5 cycles without deactivation. The Lewis acidity of MIL-100(Cr) significantly influenced the phenol hydrogenation selectivity. By incorporation of Al, V, and Ce species into the MIL-100(Cr) framework, cyclohexanone selectivity in phenol hydrogenation was found to increase with the amount of Lewis acid sites (LAS). The acid properties of the Pd/MIL-100 catalysts were investigated using NH3-TPD, pyridine-adsorbed FT-IR, and EPR probe molecules. The interaction between Pd nanoparticles and the coordinatively unsaturated sites from the trimeric clusters of MIL-100 was found to be crucial in determining the Lewis acidity of the Pd/MIL-100 catalysts. Demonstrating a synergistic effect between the Pd and LAS, Pd/MIL-100(Cr) emerges as a promising candidate for the selective hydrogenation of phenol to cyclohexanone.
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CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Qian Yu,Bilin Liang,Siqi Jia,Fang Li,Qiming Li
A novel approach was developed to fabricate defect-free MIL-96 membranes on an α-Al 2 O 3 support by combining aluminum isopropoxide coating with mixed-solvent regulation. The aluminum isopropoxide gel on the support functions as an active Al source, directing MIL-96 crystal nucleation and growth. A subsequent secondary crystallization can produce a well-intergrown MIL-96 membrane. Here, the gel coating inhibits the preferential crystallization of MIL-96 particles in the support pores, optimizing the microstructure and diminishing inter-crystal defects. By accurately adjusting the formic acid to N-methylformamide ratio in synthesis solution, a balance between membrane crystallinity and formation is achieved. Membrane separation property evaluation revealed an outstanding H 2 permeance of 1800 GPU and an H 2 /CO 2 separation factor of over 24.0, outperforming some advanced polycrystalline MOF membranes. This approach provides a potentially cost-efficient method for the large-scale preparation of MIL-96 membranes, holding great potential for practical applications in membrane separation.
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Biomedical Physics & Engineering Express
·
2024
·Vol. 10
·期 4
·045004
·
IF 1.3
Mingjia Feng,Yan Li,Yanfang Sun,Tianqi Liu,Khaydar E Yunusov,Guohua Jiang
The transdermal drug delivery based on microneedles (MNs) provides a suitable and painless self-administration for diabetic patients. In this work, the hydrogel-forming MNs were firstly fabricated using poly(vinyl alcohol) (PVA) and chitosan (CS) as matrix. A hypoglycemic drug, metformin (Met), had been loaded into MIL-100(Fe). Then, both of free Met and Met-loaded MIL-100(Fe) were integrated into hydrogel-forming MNs for regulation of blood glucose levels (BGLs) on diabetic rats. After penetrated into the skin, the free Met could be firstly released from MNs. Due to the absorption of interstitial fluid and subsequent release of loaded Met from MIL-100(Fe), leading to a sustainable and long-term drug release behaviors. A notable hypoglycemic effect and low risk of hypoglycemia could be obtained on diabetic rat models in vivo. The as-fabricated hydrogel-forming MNs expected to become a new type of transdermal drug delivery platform for transdermal delivery of high-dose drugs to form a long-term hypoglycemic effect.
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Surfaces and Interfaces
·
2024
·
IF 5.7
Qian Cheng,Xiaohan Liu,Chuhan Huang,Hongman Sun,Fazle Subhan,Xinyi Zhou,Yuankai Liu,JiaHui Yang,Qi Li,Youhe Wang,Zifeng Yan
Recently, there has been a growing interest in the fundamental understanding of the mechanism of how MIL-101(Fe)/g-C 3 N 4 heterojunctions facilitate the occurrence of photocatalytic nitrogen fixation reactions, especially the electron transfer mechanism has attained increasing attention in photocatalysis. Herein, we implemented a "triple win scenario" strategy to fabricate the S-scheme MIL-101(Fe)/g-C 3 N 4 heterojunction through a straightforward solvothermal process. The MC-6 heterojunction minimizes the recombination of photogenerated carriers, enhances light utilization efficiency, and activates the N≡N bond, thus boosting photocatalytic nitrogen fixation efficiency. The transition metal iron activates the N≡N bond, while S-scheme heterojunctions reduce the photogenerated carrier recombination. In addition, the decrease in band gap (E g ) leads to an increase in visible light utilization efficiency. ISIXPS proved the mechanism of interelectron transfer of MIL-101(Fe)/g-C 3 N 4 heterojunction under illumination. Upon the creation of the heterojunction, electrons migrate from g-C 3 N 4 to MIL-101(Fe), establishing an inherent electric field due to the disparate Fermi levels between the two materials. The electrons (e - ) on the g-C 3 N 4 CB with a more negative reduction potential and the holes ( h + ) on the MIL-101(Fe) VB are retained, which increased the redox capacity to a great extent required for the reduction of N 2 to NH 3 . The ammonia production efficiency of MC-6 photocatalyst was 160 µmol g cat -1 h -1 , representing an 8-fold and 2.8-fold improvement over pristine g-C 3 N 4 (20 µmol g cat -1 h -1 ) and MIL-101(Fe) (57 µmol g cat -1 h -1 ), respectively.
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ACS Applied Nano Materials
·
2024
·
IF 5.3
Baixin Liu,Xuelian Chen,Guojuan Hai,Wenwen Zhao,Kai Li,Zhicong Yuan,Xiaoyong Zhang
The design and synthesis of metal–organic frameworks (MOFs) for direct use as electrode materials are crucial for enhancing the electrocatalytic oxygen evolution reaction (OER). Herein, the ultrathin MIL-53(Fe) nanosheet arrays with enriched coordinatively unsaturated metal sites (denoted as MIL-53(Fe)/NF-B0.2-2) are obtained under the inhibition and modulation of benzoic acid (BA) ligands via a substitution-suppression process. The results confirm that this unique ultrathin structure effectively increases the electrochemical active surface areas (ECSA) and exposes the coordinatively unsaturated metal sites. More importantly, the enriched coordinatively unsaturated metal sites acting as active sites facilitate the adsorption of OH– during the OER process. Additionally, MIL-53(Fe)/NF-B0.2-2, with its optimized energy band structure, exhibits superior charge transfer ability and diffusion processes, significantly improving the reaction kinetics in alkaline electrolytes. As a result, the MIL-53(Fe)/NF-B0.2-2 electrode only requires extremely low overpotentials of 190 and 229 mV to reach current densities of 10 and 100 mA cm–2 for OER, respectively. This research not only proposes a novel strategy for designing efficient electrocatalysts but also provides insights into the structure–activity relationship, advancing the rational design of MOFs as effective electrode materials.
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IEEE SENSORS JOURNAL
·
2024
·Vol. 24
·期 23
·38685-38692
·
IF 4.3
Shan Tang,Jingcai Xu,Xinqin Lu,Weijie Chen,Hongwei Chen,Bo Hong,Xinqing Wang
Metal-organic frameworks (MOFs) have potential applications in gas sensing due to their abundant porosity and unique surface properties. In this study, Fe2O3 hexagonal spindles (Hgs) derived from MIL-88B(Fe) were successfully prepared using an oil bath method, followed by calcination treatment at an optimized temperature of
$450~^{\circ }$
C. The high-purity porous Fe2O3 Hgs showed excellent acetone gas-sensing performance in the range of 0.4–50-ppm acetone concentration. The Fe2O3 Hgs-450 obtained the high sensing response (Ra/Rg =23,
$\tau _{\text {res}} =17$
s, and
$\tau _{\text {rec}} =2059$
s), excellent selectivity, and stability over 120 days to 10-ppm acetone at an operating temperature of
$220~^{\circ }$
C. The sensing response value was still 1.88 even at 0.4-ppm acetone and the theoretical detection limit (DL) was calculated to reach 3.59-ppb acetone. These excellent acetone gas-sensing properties were attributed to the uniform porous structure, abundant adsorbed oxygen, and small grain size of Fe2O3 Hgs, making them an excellent candidate for screening diabetic patients through exhaled gas analysis.
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POLYMER ENGINEERING AND SCIENCE
·
2024
·
IF 3.2
Wenlong Ma,Tianxu Hao,Xinya Wang,Wei Zhang,Yonggui Li,Mingxing Chen
In this paper, a high-performance composite nanofiber membrane with excellent air filtration and dye degradation properties was prepared by incorporating MIL-53(Fe) nanoparticles into the electrospinning solution. The results showed that the filtration efficiency for PM2.5 of the PP/PVDF-HFP/MIL-53(Fe) composite nanofiber membrane reached up to 99.3% with the addition of 2 wt% MIL-53(Fe). Moreover, the composite nanofiber membrane exhibited steady filtration efficiency across different parameters, including air velocity, PM2.5 concentration, and extended testing time. Furthermore, the incorporation of MIL-53(Fe) significantly enhanced the removal efficiency of the composite nanofiber membrane toward Rh B, resulting in a remarkable 91% removal rate. The polymer/MOF composite nanofiber membranes prepared by simple and cheap electrospinning technology have a wide range of practical applications in the field of environmental protection. Highlights PPM composite nanofiber membrane was prepared via electrospinning method. MIL-53(Fe) nanoparticles were introduced to PPM composite nanofiber membrane. PPM composite nanofiber membrane showed excellent removal efficiency for PM2.5. PPM composite nanofiber showed a good removal performance for RhB in solution.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2024
·
IF 4.9
Tien Tran Nguyen,Minh Kim Nguyen,Vipin Kumar,Ha Huu Do,Anh Thi Kim Le,Anh Van Nguyen,Jin Seog Gwag,Pham Cam Nam,Le Gia Trung
The widespread use and subsequent release of antibiotics by humans and animals pose health and environmental risks, compelling their removal from aquatic ecosystems. MIL-101(Cr), a metal-organic framework (MOF), exhibits versatile applications in antibiotic adsorption owing to its exceptional structural characteristics. In this context, MIL-101(Cr) nanoparticles are successfully prepared via the hydrothermal method to remove pefloxacin (PEF) from aqueous solutions. The resulting MIL-101(Cr) adsorbents showcase high crystallinity (97.6%), a large surface area (3166 m 2 /g), broad nanopore sizes, good thermal stability, and efficient reusability. Factors including initial PEF concentration, pH, dosage of adsorbent, and temperature are thoroughly investigated. The findings reveal a good adsorption capacity (254.3 mg/g) with an optimal removal efficiency (99.7%) at 308 K in a neutral pH of 7.0 when the adsorbent dosage is 250 mg/L and the initial PEF concentration is 200 mg/L within 80 min of contact. Among the three adsorption isotherms (Langmuir, Freundlich, Temkin models), the Langmuir equation best fits the studies, indicating a maximum adsorption capacity of 253.8 mg/g at 25°C, while the experimental equilibrium adsorption capacity is 229.2 mg/g at the same temperature. Adsorption kinetics aligns with the pseudo-second-order model. Thermodynamic parameters and activation energy affirm the endothermic and spontaneous behavior of the adsorption process, attributed to both physisorption and chemisorption. This study highlights the promising potential of synthesized MOF nanocrystals as an effective adsorbent for antibiotics in wastewater treatment and environmental remediation.
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CARBOHYDRATE POLYMERS
·
2025
·
IF 12.5
Sa Liu,Yapeng Chen,XinKuan Li,Yijia Yao,Huashan Wang,Meiyi Wang
Food packaging films containing antimicrobial reagents play a crucial role in preventing bacterial-induced fruit decay. This study proposes a bilayer film consisting of an internal amino-modified starch hydrophilic layer and an external amino-modified polyvinyl alcohol/polylactic acid hydrophobic layer, embedding alliin@MIL-101(Fe) as an antibacterial agent, utilizing the pH reduction of fruit decay sites to achieve pH-responsive release, enhancing antibacterial performance. Fourier transform infrared (FTIR) and scanning electron microscopy (SEM) analyses confirm successful crosslinking between amino and aldehyde groups, resulting in the formation of imine bonds and a mesh-like structure conducive to adsorption. Under acidic conditions, the cumulative release rate of alliin reached 74 % within 36 h. Compared to a simple mixture, the tensile strength of the alliin@MIL/NST-NPVA/PLA film reached 34.771 MPa, and transmittance in the wavelength range of 200–370 nm decreased to 0. The scavenging rate of DPPH free radicals in the film can reach 83 %. In addition, the water vapor permeability and oxygen permeability of the film are approximately 7.62 × 10 −16 [g/ (m 2 ‧24 h‧0.1 mm)] and 6.83 (m 2 ‧24 h‧0.1 MPa), respectively; moisture content and water solubility decreased to 10.99 % and 20.77 %. This composite film extended the shelf life of strawberries from 2 to 7 days, significantly enhancing freshness.
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