CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2023
·Vol. 39
·期 6
·1084-1091
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IF 3.1
Gao Zhuangzhuang,Li Baoju,Ou Shuxian,Li Dongsheng,Fang Qianrong,Qiu Shilun,Xue Ming
M etal-organic frameworks (MOFs) are attractive in membrane separation due to their special pore structure and suitable aperture size. The fabrication of defect-free and robust MOF membranes with excellent durability is highly demanded but remains challenging. In this work, we report a one-step active γ -alumina conversion strategy for the facile and reliable fabrication of an MIL-96 membrane. In this case, the γ -Al 2 O 3 sol was dip-coated and sintered on the α -Al 2 O 3 disc as the active aluminum source and substrate for the nucleation and growth of MOF. A continuous and well-intergrown MIL-96 membrane was generated with exceptional stability due to the strong adhesion to the substrate. The resultant MIL-96 membrane yielded a satisfactory H 2 /CO 2 permselectivity and high-temperature resistance, delivering a selectivity of 12.35 with H 2 permeance of 6.20×10 −7 mol·m −2 ·s −1 ·Pa −1 at 150 °C. Moreover, the probe membrane presented remarkable durability and recyclability under harsh hydrothermal conditions. This method paves the way for constructing highly stable and selective MOF membranes and could accelerate the development of advanced membrane separation technologies for gas purification and recycling in addressing the severe energy and environmental problems.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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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.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2021
·
IF 8.742
Sixing Chen,Yi Liu,Yanwei Sun,Guoliang Xu,Taotao Ji,Xiongfu Zhang,Fei Wang,Yi Liu
Concurrent manipulation of orientation and thickness of MOF membranes has become a reliable approach for improving their separation performances. In terms of oriented seeded growth, oriented deposition of MOF nanosheets during seeding process and sealing all intergranular gaps with no discernible increase in membrane thickness during secondary growth have become indispensable. In this study, we pioneered the fabrication of uniform hexagonal-shaped, 20–40 nm thick MIL-96 nanosheets through solvent composition optimization (V H2O /V FA = 1/2). Subsequently, spin coating was employed for c -oriented deposition of uniform MIL-96 seed layer, during which the addition of PVP in the suspension was found to be critical for obtaining qualified seed layer. Finally, well-intergrown, highly c -oriented ultrathin MIL-96 membrane was prepared upon employing NMF as the solvent during secondary growth. Gas permeation results implied that prepared MIL-96 membrane exhibited superior gas separation performance compared with that of a -& b -oriented counterpart.
研究领域:
材料科学
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化学工程
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膜技术
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2021
·Vol. 28
·期 48
·68513-68522
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IF 4.223
Zhang
Beibei,Tian Ye,Liu Junshen,Gao Xuezhen,Zheng Hui
As an emerging class of nitrogenous disinfection by-products, halonitromethanes have caused public health concerns owing to their high toxicity. More and more attention has been paid to the new materials and technologies for the removal of halonitromethanes. In this study, a novel material, nanoscale zero-valent iron (nZVI) supported on MIL-96 (nZVI@MIL-96) with favorable stability and reusability, was synthesized and applied to the adsorption-degradation of trichloronitromethane (TCNM) in the water. The results revealed that almost all the TCNM could be removed under 20 mg/L nZVI@MIL-96 dosage with a wide temperature range. The optimum mass ratio of nZVI to MIL-96 was 1:2, and the TCNM adsorption-degradation followed a pseudo-first-order model. The coexisting ions, such as SO 4 2– , PO 4 3– , and NO 3 – , with high concentration brought adverse effects on the removal of TCNM; however, the effects of Cl – and CO 3 2– were insignificant. The concentrations of aluminum and iron ions in water were all within the standard value after adsorption with the nZVI@MIL-96. The degradation mechanism of TCNM by nZVI@MIL-96 included two steps, namely, adsorption and degradation, and methylamine was the terminal dechlorination and denitration products. In a word, the as-prepared nZVI@MIL-96 nanoparticles demonstrated the capabilities as a material of adsorption-degradation of TCNM in the water.
研究领域:
环境科学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Ning Yao,Jinfeng Chen,Ren Feng,Zhipeng Liu,Yu He,Zhuwu Jiang
N -nitrosodiethylamine (NDEA) is a disinfection by-product (DBP) and is classified as a probable carcinogen by the International Agency for Research on Cancer. Its concentration is lower but its toxicity is higher than other DBPs. Designing a new adsorbent with a high adsorption effect on low concentrations of NDEA instead of traditional materials will be useful. To the best of our knowledge, this is the first study to investigate metal-organic frameworks (MOFs) for the adsorption of NDEA. Two novel Al-based MOFs were synthesized by modifying MIL-96 with amino and thiol groups. Their adsorption performances at low concentrations of NDEA in water were compared using adsorption kinetics and isotherm models. It was observed that MIL-96 modified with thiol groups (MIL-96-M) followed the Langmuir and pseudo-second-order models and exhibited the best adsorption performance. Owing to the well-matched pore size and hydrophobicity, the Langmuir adsorption capacity of MIL-96-M for NDEA was achieved at 1004.71 μg/g. The parameters of the adsorption performance were investigated using the Box-Behnken response surface methodology, and on the basis of which, the performance under different conditions was predicted. The experimental data suggested that the increase in temperature and time was beneficial for the adsorption performance, whereas an increase in dosage was not beneficial. It was identified that the adsorption mechanism between MIL-96-M and NDEA involves van der Waals forces, electrostatic interactions, and nucleophilic reactions by characterization and density functional theory (DFT).
研究领域:
环境科学
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材料科学
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毒理学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2024
·
IF 3.7
Sixing Chen,Xinmiao Jin,Yuyang Wu,Taotao Ji,Fei Wang,Yi Liu
ABSTRACT Preferential orientation control of metal–organic framework (MOF) films is advantageous for maximizing pore uniformity and minimizing grain-boundary defects. Nonetheless, the preparation of MOF films with both in-plane and out-of-plane orientations remains a grand challenge. In this study, we reported the preparation of three-dimensionally oriented MIL-96 layers through combining morphology control of MIL-96 seeds with addition of polyvinylpyrrolidone surfactants and arachidonic acids. The three-dimensionally oriented MIL-96 film was readily obtained through in-plane epitaxial growth. It is anticipated that the aforementioned protocol can be effective for obtaining diverse MOF films with a three-dimensionally oriented organization.
研究领域:
材料科学
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化学工程
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纳米技术
✓ 已验证
产品关联
DOI
高影响因子
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.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2017
·
IF 6.216
Yijun Xue,Wei Sun,Qian Wang,Limei Cao,Ji Yang
MOFs (metal-organic frameworks) are stable materials with both organic and inorganic pores, and possess high surface area fascinating structures. Owing to the unique octahedral of aluminum center and strong Al–O bonds, Al-based MOFs show excellent thermal stability. In this paper, MIL-96(Al) is proved to be effective at dispersing Pt particles evenly and sparsely as it is employed as catalyst support. MIL-96(Al) is synthesized via a water based route and different contents of Pt particles are directly deposited on the surface of MIL-96 in one step by hydrothermal method to prepare Pt X MIL-96 (x represents Pt content) catalysts. The catalyst are sprayed evenly on carbon paper, with Pt content of 0.03%, 0.11%, 0.27% and 0.41%, respectively, and are applied in a gas diffusion reactor with snakelike flow field for low temperature H 2 -SCR. For Pt 5 MIL-96/CP, the NO removal efficiency can reach up to 100% at 60 °C. Electron transfer between Pt and MIL-96 is observed via X-ray photoelectron spectron (XPS). It reveals that the deposited Pt is in metallic state. Meanwhile, the electronic structure of MIL-96 is kept intact in the process of Pt depositing. The excellent performance of Pt 5 MIL-96/CP catalyst strongly suggests its potential application.
研究领域:
材料科学
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环境科学
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催化化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yue Xiao,Haodong Huang,Shangpu Zhuang,Dong Yang
Metal oxide cluster MOF nodes are a good platform to understand the reactivities and catalysis. MIL-96, MIL-100 and MIL-110 are drastically different in their node structures. Following our previous reported results for MIL-100, we report the modified synthesis and characterization of the node sites of MIL-110 and MIL-96 and their catalytic sites by using methanol dehydration as probe reaction. We show that these MOFs can be synthesized from the same solution by adding various amounts of formic acid as modulator. Herein, the chemistry of hydroxyl, formate and methoxy groups were used to probe the three MOFs’ node sites. IR data show the bonding structures of these ligands are highly diverse, with reactivities and flexibilities depending on node sites. We identified terminal OH group and various µ 2 -OH groups in single, paired or hydrogen bonded modes on the MOF nodes. Formate ligands were introduced to the node sites during the synthesis or by a post treatment in formic acid/DMF solution. Surprisingly, the bonding modes of formate ligands on Al 3 (OH) 3 node structure of MIL-96 can be reversibly switched between monodentate and bidentate through a process induced by water molecules. Further, methoxy ligands—likely to be the intermediate for catalytic reaction—were also observed on the node sites under methanol dehydration conditions at 250 ℃. The activities of MIL-100 and MIL-96 for methanol dehydration determined by TOF per node were similar, both approximately 3-fold higher than that of MIL-110. The data suggests that catalytic sites incorporate adjacent vacancy and defect node sites, which constitute a minority among all observed MOF node sites. We foresee the opportunities in expanding the chemistry and understanding into other MOFs with metal oxide cluster nodes.
研究领域:
材料科学
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催化
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化学工程
·
无机化学
✓ 已验证
产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2015
·Vol. 44
·期 13
·6212-6218
·
IF 4.197
Lan Wen,Xiaoqiong Du,Jun Su,Wei Luo,Ping Cai,Gongzhen Cheng
Well-dispersed bimetallic Ni–Pt nanoparticles (NPs) with different compositions have been successfully grown on the MIL-96 by a simple liquid impregnation method using NaBH4 as the reducing agent. Powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, N2 adsorption–desorption, and inductively coupled plasma-atomic emission spectroscopy measurements were employed to characterize the NiPt/MIL-96. Catalytic activity of NiPt/MIL-96 catalysts was tested in the hydrogen generation from the aqueous alkaline solution of hydrazine at room temperature. These catalysts are composition dependent on their catalytic activity, while Ni64Pt36/MIL-96 exhibits the highest catalytic activity among all the catalysts tested, with a turnover frequency value of 114.3 h−1 and 100% hydrogen selectivity. This excellent catalytic performance might be due to the synergistic effect of the MIL-96 support and NiPt NPs, while NiPt NPs supported on other conventional supports, such as SiO2, carbon black, γ-Al2O3, poly(N-vinyl-2-pyrrolidone) (PVP), and the physical mixture of NiPt and MIL-96, all of them exhibit inferior catalytic activity compared to that of NiPt/MIL-96.
研究领域:
催化
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材料科学
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化学工程
·
纳米技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2014
·
IF 4.058
Nantong Zhang,Xuan Yang,Xinyao Yu,Yong Jia,Jin Wang,Lingtao Kong,Zhen Jin,Bai Sun,Tao Luo,Jinhuai Liu
In this study, adsorption potential of a typical aluminum-based metal–organic frameworks (MOFs), Al 12 O(OH) 18 (H 2 O) 3 (Al 2 (OH) 4 )(BTC) 6 ·24H 2 O (referred as MIL-96), was investigated for defluoridation of drinking water using batch experiment. The effects of different parameters such as pH, contact time, initial fluoride concentration, and competing anions were studied to understand the adsorption behavior of the adsorbent under various conditions. Optimum removal of fluoride ions occurred in a pH range of 3–10. The results indicated that the defluoridation efficiency and aluminum residual of MIL-96 were far superior to that of activated alumina (AA) or nano-alumina (NA). The Langmuir equilibrium model was found to be suitable for describing the fluoride sorption on MIL-96. The maximum fluoride uptake capacity for MIL-96 was calculated to be 31.69 mg g −1 at the temperature of 298 K. Moreover, there were no significant influence on fluoride removal by MIL-96 in the presence of chloride, nitrate, sulfate, bicarbonate and phosphate. Temperature study was carried out at 298 K, 308 K and 318 K revealed that the adsorption process was endothermic reactions. In column tests using real groundwater as influent, about 140 bed volumes (BVs) of groundwater were treated before breakthrough was reached under space velocities (SVs) of 4 h −1 . Results from this study demonstrated the MIL-96 is a promising adsorbent that can be potentially used into drinking water processes.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
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