DALTON TRANSACTIONS
·
2017
·Vol. 46
·期 6
·1996-2006
·
IF 4.029
Xuan Yang,Shuangshuang Deng,Fumin Peng,Tao Luo
A novel Ce(III) ion-implanted aluminum-trimesic metal–organic framework (Ce–MIL-96) was synthesized for the first time via alcohol-solvent incipient wetness impregnation. Compared to previously reported Ce-contained adsorbents, the fluoride adsorption performance of the new ion-implanted metal–organic framework demonstrated much higher adsorption capacity and more efficient regeneration of Ce. In a wide pH range of 3 to 10, Ce–MIL-96 maintained constant adsorption performance for fluoride, and the residual Ce and Al in the treated solution were below the safe limits in drinking water. The maximum adsorption capacity of Ce–MIL-96 was 38.65 mg g−1 at 298 K. Excluding the contribution of MIL-96, the maximum adsorption capacity of Ce ions was 269.75 mg g−1, which demonstrated that the service efficiency of cerium in Ce–MIL-96 is about 6 times that in Ce2O3, nearly 10 times that in Ce-mZrp, and double that in Mn–Ce oxides. There was no significant influence on fluoride removal by Ce–MIL-96 due to the presence of chloride, nitrate, sulfate, bicarbonate or phosphate. Moreover, the adsorption capacity of Ce–MIL-96 remained at more than 70% after nine cycles of adsorption–desorption. Due to this excellent adsorption performance and its regeneration properties, Ce–MIL-96 is a promising adsorbent for the removal of fluoride from groundwater.
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DALTON TRANSACTIONS
·
2022
·Vol. 51
·期 34
·13085-13093
·
IF 4.569
Lijun Guo,Feifei Li,Jianxin Liu,Zehui Jia,Rui Li,Zhuobin Yu,Yawen Wang,Caimei Fan
The scaling relations between nitrogen adsorption and NHx destabilization are key challenges to the widespread adoption of the photocatalytic synthesis of ammonia. In this work, a FeII-rich MIL-101(Fe) (MIL-101(FeII/FeIII)) was synthesized using a one-step solvent thermal method with ethylene glycol (EG) as a reducing agent, which can break the scaling relationship by photoinduced FeII (high nitrogen adsorption ability) and FeIII (high NHz destabilization ability) cycling. XPS was used to detect the change in iron valence state in the MIL-101(FeII/FeIII) material. The photocatalytic nitrogen fixation efficiency of MIL-101(FeII/FeIII) under visible light without any sacrificial agent was 466.8 μmol h−1 g−1, five times that of MIL-101(Fe). After photocatalytic experiments, MIL-101(FeII/FeIII) retained an unchanged FeII/FeIII rate, indicating that this FeII/FeIII cycling can be maintained. DFT modeling of the FeII-rich MOF material showed that a FeII1 FeIII2 system has a higher N2 activation capacity than a FeIII3 system. The catalytic mechanism was further proved by in situ infrared spectra and N15 isotopic tracers. Therefore, the improvement of photocatalytic activity was mainly attributed to the change in the nitrogen adsorption capacity during the photoinduced FeII/FeIII cycling.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2025
·
IF 5.4
Zhengtao Zhu,Xi Deng,Yongqiang Ye,Na He,Bihe Yuan,Fei Xiao,Kaiyuan Li
To address the challenge of balancing fire safety and mechanical properties in thermoplastic polyurethanes (TPU), this study developed a CP@MIL-101 hybrid by confining liquid cyclic phosphates within the pore structure of MIL-101 using a hierarchical design strategy. The results demonstrated that the introduction of CP@MIL-101 slightly improved the thermal stability of TPU. Notably, the residual char yield increased significantly from 0.1 % to 9.3 % with only 0.5 % loading. With just 2 wt% loading of CP@MIL-101, the TPU composite achieved a UL-94 V-0 rating (3 mm) and exhibited a 20.4 % increase in the limiting oxygen index (LOI), reaching 26.0 %. Furthermore, significant reductions in peak heat release rate, total heat release, and fire growth rate index were observed, indicating enhanced fire safety of the TPU composites. Characterization analyses suggested that the improved fire retardancy resulted from the synergistic effects of MIL-101 and cyclic phosphates in both the condensed and gas phases, through the formation of a protective char layer and free radical quenching. Additionally, incorporating 2 wt% CP@MIL-101 endowed the TPU matrix with exceptional ultraviolet shielding properties due to unique electron transitions absorption. Simultaneously, the tensile strength of the TPU increased by 15.85 % compared to neat TPU, demonstrating mechanical reinforcement. This work establishes a strategic approach for developing multifunctional flame retardants and fire-safe TPU composites, paving the way for their application in high fire-safety environments.
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Nanoscale
·
2020
·Vol. 12
·期 7
·4552-4561
·
IF 6.895
Jing Yang,Bo Wang,Fan Jin,Yu Ning,Hao Luo,Jian Zhang,Fei Wang,Dianlong Wang,Yu Zhou
Lithium–sulfur batteries are promising candidates for the next generation of energy storage systems owing to their high energy density, low toxicity and abundant reserves of sulfur. However, sulfur has poor conductivity, large volume change during charge/discharge, and more importantly, the intermediate polysulfide (Li2Sn, 3 ≤ n≤8) produced in the cycling process is easily soluble in the electrolyte resulting in the “shuttle effect”, which have greatly limited the commercialization of lithium–sulfur batteries. Therefore, it is of great value to develop optimized sulfur cathode materials to improve electrode conductivity, buffer volume change and restrain the diffusion of polysulfide. In this work, we construct a V-MOF (MIL-47) derived V2O3@C hollow microcuboid with a hierarchical lasagna-like structure through hydrothermal synthesis followed by calcination, and employ it as a sulfur host for the first time. The fast anchoring of polysulfide by V2O3 nanoparticles and the high electronic conductivity of the 3D carbon framework can simultaneously inhibit the “shuttle effect” in the charge–discharge process and accelerate the kinetics of the redox process. Moreover, the special lasagna-like structure with appropriate voids generated during calcination not only provides many sites for sulfur loading, but also effectively alleviates the volume expansion problem during the electrochemical reaction. Therefore, the final fabricated sulfur cathode via the melt impregnation method exhibits good cycling stability (62.3% after 1000 cycles at 1C) and rate performance (663 mA h g−1 at 2C) at a relatively high sulfur loading of 3.7 mg cm−2.
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ENVIRONMENTAL RESEARCH
·
2024
·
IF 7.7
Xueyan Li,Lei Wang,Xin Zheng,Xiang Tu,Anhong Cai,Jing Deng
In this study, a UV-driven photocatalytic activation of peroxymonosulfate (PMS) system was constructed using bimetallic metal-organic frameworks to degrade pharmaceuticals and personal care products (PPCPs). Mn-MIL-53(Fe) was successfully synthesised by adjusting the doping ratio of Mn using solvothermal method. The removal of ibuprofen (IBP) by UV/Mn-MIL-53(Fe)/PMS process was as high as 79.7% in 30 min with a Mn doping ratio of 1.0 (molar ratio of Mn to Fe), and the reaction rate constant was 26.9% higher than undoped. Mn-MIL-53(Fe) had been systematically characterized in terms of its physical structure, microscopic morphology, surface functional groups and photoelectric properties. The mechanism investigation revealed that the cycling of Mn and Fe accelerated the rate of electron transfer in the system, which significantly increased the activation efficacy of PMS to generate more hydroxyl and sulfate radicals for IBP degradation. A total of 13 transformation products were detected during the degradation of IBP by the UV/Mn-MIL-53(Fe)/PMS process. Theoretical calculations were used to predict the sites on the IBP molecule that were vulnerable to attack, and four possible degradation pathways were deduced. The excellent stability and efficient catalytic properties of Mn-MIL-53(Fe) provided a promising solution to the problem of water treatment contaminated with PPCPs.
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高影响因子
LANGMUIR
·
2025
·
IF 3.9
Changhua Li,Wei Liu,Yuquan Jing,Hao Yang,Qiuping Tang,Yongxu Cui,Chao Zhang,Wei Ren,Jing Zhang,Yi He
Metal–organic framework materials with large specific surface areas are ideal choices for storing corrosion inhibitors in organic coatings. Existing reports focus on materials such as ZIF-8 and ZIF-67, which release corrosion inhibitors by disintegrating themselves upon external stimuli. This release mechanism may lead to the formation of holes within the coating, providing channels for penetration into corrosive media. In this study, NH2-MIL 101 (Cr), which is stable under acidic/alkaline conditions, was grown on Ti3C2Tx surface via a hydrothermal method. Its porous structure was utilized to load environmentally friendly MoO42– corrosion inhibitors, and a stimulus-responsive TEOS shell was wrapped as a valve to control the release of the corrosion inhibitors. The synthesis of the Ti3C2Tx-MIL 101-MoO42–-TEOS (TMIT) composite material was verified by FT-IR spectroscopy and XPS, respectively. The TMIT-epoxy (TMITP) composite coating was prepared through a solid–liquid mixing method. The surface-active groups of NH2-MIL 101 (Cr) (−NH2) enhanced the interfacial strength with the resin and the crosslinking density, significantly increasing the tensile strength and adhesion strength of the composite coating. Due to the improved interfacial strength, the low-frequency impedance value remained at 4.14 × 108 Ω cm2 after 6 cycles of accelerated cyclic electrochemical tests (−4.0 V, 30 min), which greatly shortening the evaluation period of the coating performance. Additionally, the stimulus-responsive release mechanism of the TMIT filler endowed the coating with self-healing effects, achieving corrosion inhibition in damaged areas. Notably, the acid/alkali stability of NH2-MIL 101 (Cr) ensured that few holes would form within the coating after the release of corrosion inhibitors, preventing the penetration of corrosive media. This study utilized the pores of NH2-MIL 101 (Cr) to load corrosion inhibitors and prepare self-healing composite coatings, achieving intelligent release and enhancing the corrosion resistance of coatings, thus broadening the application strategy of MOF materials in corrosion protection coatings.
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高影响因子
APPLIED SURFACE SCIENCE
·
2026
·
IF 6.6
Qianxun Liu,Jiawei Ding,Chaowei Wang,Hao Fu,Xuetong Yang,Sitao Zhu,Hongyu Zhao,Yang Hu
MNA@DE composites were fabricated via in situ growth with high BTA loading capacity. MNA@DE composites were fabricated via in situ growth with high BTA loading capacity. • BTA-MNA@DE-M showed excellent corrosion-inhibition performance in simulated mine leach liquor. • MNA@DE exhibited pH-responsive BTA release for sustained inhibition of carbon steel corrosion. To address the susceptibility of carbon steel rock bolts to corrosion in complex mine environments and the limited long-term protection provided by conventional corrosion inhibitors, MIL-53-NH 2 (Al)@diatomite composites were prepared via in situ hydrothermal growth. The corrosion-inhibition performance of the benzotriazole (BTA)-loaded composites for carbon steel rock bolts in simulated mine leach liquor was systematically investigated. MNA@DE exhibited a considerably higher BTA adsorption capacity than pristine diatomite, with MNA@DE–H showing the highest value (134.48 mg g −1 ) at pH 5.0. Electrochemical measurements indicated that 0.10 wt% BTA-MNA@DE-M exhibited the best corrosion-inhibition performance, with a corrosion current density of 1.76 μA cm −2 and a polarization-based inhibition efficiency of 82.94%. The R ct -based inhibition efficiency increased from 20.77% to 87.56% over 168 h, indicating that the corrosion-inhibition performance of the material steadily improved with increasing of immersion time. Mechanistic analysis revealed that under weakly acidic conditions, hydrogen bonding and cation–π interactions between the surface - NH 3 + groups in the composites and BTA facilitated the efficient loading and immobilization of BTA. In a weakly alkaline simulated mine leach liquor, BTA molecules were slowly released because of weaker interactions between the carrier and BTA. The released BTA was subsequently adsorbed on the carbon steel surface, suppressing interfacial charge transfer and thereby progressively enhancing the corrosion-inhibition performance with the extension of immersion time. Therefore, this study provides a new strategy for the design and development of long-lasting corrosion-inhibiting materials for carbon steel rock bolts in complex mine environments. Slow release of BTA in weakly alkaline mine leach liquor enables sustained adsorption on carbon steel, suppresses charge transfer, and provides long-term corrosion protection. Download: Download high-res image (260KB) Download: Download full-size image
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Jin Liu,Zhirui Fan,Wenzhe Zhao,Peipei Song
Recently, escalating antibiotics contamination in aquatic environments has become a critical global threat to public health. In this study, a novel cathode catalyst (NH 2 -MIL-101(Fe)@Mel-MoPc/BC) was fabricated via hydrothermal method for efficient degradation of ofloxacin (OFX) through an electro-activated peroxymonosulfate (PMS) system. The incorporation of Mo-C and Fe/Mo-N substantially enhanced the electrocatalytic performance. The influence of various parameters, including the internal mass ratio of the catalyst, current, PMS concentration, OFX concentration, pH, as well as electrolyte concentration and type on OFX degradation were systematically evaluated. Under optimal conditions, OFX degradation reached 92.6 %, with 84.2 % total organic carbon removal, outperforming previous studies. The free radical quenching experiment and electron paramagnetic resonance analysis identified singlet oxygen ( 1 O 2 ) as the dominant active species. In situ Raman spectroscopy, high performance liquid chromatography-mass spectrometry and density functional theory calculation elucidated the degradation mechanism and pathways of OFX, including demethylation, decarboxylation, hydroxylation, and dehydrogenation, ultimately forming water, carbon dioxide, and inorganic ions. Furthermore, computational toxicology and seed germination tests confirmed significantly reduced wastewater toxicity after treatment by electro-activated PMS system based on NH 2 -MIL-101(Fe)@Mel-MoPc/BC cathode. Additionally, it also exhibited superior cyclic stability and excellent performance in various real water matrices and for other organic pollutants such as Rhodamine B, phenol, tetracycline, and dimethyl phthalate, demonstrating great application potential. This work provides valuable insights into cathode catalyst design and establishes a sustainable technology for antibiotic wastewater treatment.
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DESALINATION
·
2026
·
IF 9.9
Linkai He,Xingqiang Wu,Yun Tian,Yixin Pan,Faquan Wu
The release and dispersion of uranium during mining activities and fuel/waste management processes in nuclear power plants pose serious environmental risks, particularly in aqueous systems. In such environments, uranium exhibits high solubility and strong mobility, leading to severe radioactive contamination of groundwater, soil, and ecosystems. Therefore, remediating uranium-contaminated environments remains a significant scientific and technological challenge. To address this issue, the present study exploits the high specific surface area and tunable pore architectures/functional sites of metal-organic frameworks (MOFs). Using a controlled synthesis strategy, a core-shell (Fe-Ni) galvanic cell structure was constructed and integrated with MIL-100(Fe) to fabricate the Ni-Fe-MIL-100(Fe) composite, enabling highly efficient and synergistic removal of U(VI) via an “adsorption-reduction-complexation” mechanism. Experimental results demonstrate that the maximum uranium uptake capacity reached 3038.19 mg·g −1 at 303 K and pH = 5, with a significantly enhanced removal efficiency. The kinetic analysis indicates that the uranium adsorption process is well described by the pseudo-second-order model. Combined with density functional theory (DFT) calculations, the electronic transfer channels of the structure were elucidated, revealing that they drive the reduction of U(VI) and facilitate its coordination and immobilization at multi-metal and oxygen-containing sites. These findings confirm that U(VI) removal by the composite material proceeds via a coupled chemical reduction and complexation process, thereby clarifying the underlying adsorption mechanism. Moreover, in mixed-ion solutions and real seawater, the composite maintains high adsorption capacity and excellent selectivity, demonstrating strong potential for uranium immobilization and recovery in the remediation of radioactive wastewater.
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CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Hafiz Nabeel Ahmad,Yueyuan Yong,Noshaba Munawar,Xinxin Huang,Anzal Akbar,Jie Zhu
MIL-100(Fe) was successfully synthesized at room temperature and incorporated in bilayer film matrix. • MOFs and betalain generate molecular interactions within the film matrix as a filler. • Active films exhibited strong barrier, antioxidant and antibacterial properties. • These films prolonged the shelf life of beef and can be used for beef freshness monitoring. • This study offers novel insights into the development of active, smart food packaging. Meat is prone to microbial spoilage and faces significant risks from foodborne illnesses. This study introduces an innovative approach utilizing metallic organic frameworks (MOFs) as antibacterial agents and beetroot extract (BTE) for pH sensitivity to address existing challenges. Furthermore, this study utilized tri-polymeric concept via protein-polysaccharide combination, which includes sodium alginate to stabilize betalain, and gelatin and chitosan to give strong mechanical properties. The MOFs were synthesized using green synthesis, confirmed through structural and multispectral analysis. Betalain extracted from beetroot was incorporated into these tri-polymeric films. The developed films demonstrated excellent antioxidant and antibacterial properties. Furthermore, the pH sensitivity of betalain renders these films suitable for use as biosensors, with the quality stage of beef successfully assessed. Moreover, the films exhibited strong UV, water, and oxygen barrier properties. Atomic force microscopy revealed differences in surface morphology, with a uniform distribution, and films showed high mechanical strength. Concurrently, the addition of MOFs and BTE extract potentially extended the shelf life of beef by up to three days compared to control tri-polymeric films. These multifunctional films present new strategies employing novel antibacterial materials and tri-polymeric combinations which can efficiently preserve beef quality, while BTE indicates spoilage in real time. Download: Download high-res image (362KB) Download: Download full-size image
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Analytical Methods
·
2026
·
IF 3
Xinwen Hu,Yong Zhang,Zhihao Chen,Mengqian Xiao,Litao Wang,Guihua Gao
In this study, the spray phase inversion method was employed for the first time to prepare MIL-68@Fe3O4@PVDF. The preparation process involved dispersing Fe3O4 in a PVDF/DMF solution; when the Fe3O4-loaded PVDF solution was atomized and sprayed into ethanol containing dispersed MIL-68, PVDF underwent phase inversion to form magnetic solid microspheres, with MIL-68 simultaneously immobilized on their surface. The procedure is facile, convenient, and suitable for the synthesis of various magnetic composites. The MIL-68@Fe3O4@PVDF composite exhibited favorable adsorption performance toward methylene blue (MB). The adsorption kinetics and isotherm data were well fitted to the pseudo-second-order kinetic model and the Langmuir isotherm model, respectively, indicating monolayer chemisorption on homogeneous adsorption sites. Based on this, a magnetic solid-phase extraction (MSPE) method coupled with high-performance liquid chromatography (HPLC) was established using MIL-68@Fe3O4@PVDF as the adsorbent for the determination of five parabens and bisphenol A (BPA) in water samples. After optimizing the MSPE conditions, the established method showed a good linear relationship for parabens and BPA in the concentration range of 1.5–400.0 ng mL−1 (r > 0.9996). It also achieved low limits of detection (LODs, 0.4–1.0 ng mL−1) and limits of quantitation (LOQs, 1.3–4.0 ng mL−1), along with high spiked recoveries (80.0–107.3%) and acceptable precision (RSD ≤ 8.81%). In conclusion, the spray phase inversion method provides a simple and efficient strategy for fabricating magnetic composites. Furthermore, it offers a novel approach to improve the application efficiency of nano-adsorbents in MSPE, laying a foundation for their broader use in the trace analysis of complex samples.
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Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 3
·122692
·
IF 7.5
Huanggen Yang,Shulun Yin,Pei Zhang,Qi Zheng,Faisal Alresheedi,Imran Shakir,Saleem Raza,Duofu Li,Yan Sui
The energy crisis calls for eco-friendly alternatives, and hydrogen production presents a viable solution. As a clean energy source, hydrogen can be produced from water using renewable power, decreasing dependence on fossil fuels and substantially cutting greenhouse gas emissions paving the way for a greener future. This work involves the fabrication of Ti 3 C 2 T x and NH 2 -MIL-125(Ti) by hydrothermal procedures. Ti 3 C 2 T x material served as the substrate for the immobilization of NH 2 -MIL-125(Ti), which were then incorporated into sodium alginate to generate (Ti 3 C 2 T x @NH 2 -MIL-125(Ti)-SA). The electrocatalytic efficacy of Ti 3 C 2 T x @NH 2 -MIL-125(Ti)-SA was evaluated for the hydrogen evolution reaction (HER) under alkaline factors using a 1 M KOH electrolyte. The material demonstrated exceptional capacitance, impressive rate capability, and sustained stability during 1000 cycles over a 24 and 48 h. The Ti₃C₂Tₓ@NH₂-MIL-125(Ti)-SA composite exhibits excellent HER catalytic activity in alkaline media, delivering a low overpotential of 14 mV at 10 mA cm⁻² and a Tafel slope of 56.4 mV dec⁻¹ . Although the benchmark Pt/C catalyst shows slightly superior performance (12 mV, 41.1 mV dec⁻¹), the developed composite demonstrates comparable activity, along with advantages of structural stability and cost-effectiveness compared to noble metal-based catalysts. Overall, Ti 3 C 2 T x @NH 2 -MIL-125(Ti)-SA demonstrates excellent electrode performance in alkaline conditions, as compared with pristine Ti 3 C 2 T x and NH 2 -MIL-125(Ti), which marked by remarkable stability, low Tafel slope values, and minimized overpotentials, underscoring its significant promise for efficient water splitting applications.
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