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SCIENCE OF THE TOTAL ENVIRONMENT · 2021 · IF 7.963

Efficient capture of ReO4− on magnetic amine-functionalized MIL-101(Cr): Revealing from selectivity to mechanism

Yawen Cai,Jinghua Feng,Xiaoli Tan,Xin Wang,Zhimin Lv,Weiwei Chen,Ming Fang,Haining Liu,Xiangke Wang

The efficient decontamination of pertechnetate ( 99 TcO 4 − ) is an essential task for managing radioactive 99 Tc in nuclear wastes . Perrhenate, (ReO 4 − ), as a nonradioactive analog, exhibits almost identical physicochemical properties as 99 TcO 4 − . Herein, a novel magnetic amine-functionalized MIL-101(Cr) (NH 2 -MIL-101(Cr)@Fe 3 O 4 ) was prepared and used to efficiently remove ReO 4 − from solution for the facile magnetic separation. A series of environmental parameters were considered to investigate the adsorption performance of NH 2 -MIL-101(Cr)@Fe 3 O 4 . Experimental results suggested that NH 2 -MIL-101(Cr)@Fe 3 O 4 has reached a satisfied adsorption capacity (~401 mg/g) and a very fast adsorption kinetics at pH 7.0. The selectivity for ReO 4 − was maintained even in the presence of interfering anions with relatively high concentrations. ReO 4 − were mainly captured by N-donor sites of the surface-decorated amine via complexation and were trapped in the cavities of modified MIL-101(Cr). NH 2 -MIL-101(Cr)@Fe 3 O 4 exhibits satisfactory adsorption performance for ReO 4 − and can be conveniently separated from wastewaters after adsorption.

研究领域: 环境科学 · 材料科学 · 放射化学
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AICHE JOURNAL · 2022 ·Vol. 69 ·期 4 ·e17933 · IF 4.167

Hydrophobicity regulation by a facial bromine substitution in MIL-47(V) for highly selective adsorptive desulfurization

Wei Xie,Yiping Guo,Jianping Li,Honglai Liu,Jun Hu

Metal organic frameworks (MOFs) have shown promising adsorptive desulfurization (ADS) capacity yet remains great challenges to maintain excellent performance in presence of water. Guided by the density function theoretical (DFT) calculations, we select bromine modified linkers with different substitution degrees to construct MIL-47-xBr to regulate the porosity and hydrophobicity. The optimized MIL-47-Br exhibits the highest saturation dibenzothiophene (DBT) capacity of 179.2 mgS g −1 from the hydrous oil, surpassing the record of all ADS adsorbents. Meanwhile, the excellent selectivity, adsorption kinetics, and recycle stability endow MIL-47-Br with superior ADS performance from the commercial hydrous gasoline. With the DBT capacity decreases by only 12.3% from the commercial gasoline, a continue flow ADS is successfully achieved on the fixed-bed of MIL-47-Br column. Therefore, this facial strategy of simple substitution can fully exploit the functions of open metal sites for enhancing the task-specific selectivity, and has a promising application prospect in industrial ADS.

研究领域: 材料科学 · 化学工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Optimal adsorption of pefloxacin antibiotics from aqueous solutions: Improved performance with metal-organic framework MIL-101(Cr)

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.

CAS / MDL: 7664-39-3 70458-92-3
研究领域: 环境科学 · 材料科学
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ENVIRONMENTAL POLLUTION · 2019 · IF 5.714

Mechanistic insight into the adsorption of diclofenac by MIL-100: Experiments and theoretical calculations

Shuting Zhuang,Yong Liu,Jianlong Wang

The development of high-efficiency adsorbents and the exploration of their adsorption mechanisms are major challenges in environmental remediation. Herein, MIL-100 was prepared, characterized, and utilized for the adsorptive removal of diclofenac sodium (DCF) from aqueous solutions. A high monolayer adsorption capacity of 773 mg g −1 was recorded. The adsorption mechanism was proposed based on different contributions of two types of pore structure of MIL-100 to the adsorption of DCF from aqueous solutions according to the experimental results and theoretical calculation. During adsorption process, DCF (5.2 × 7.4 × 10.3 Å) diffused through the free area of hexagonal pores (8.6 × 8.6 Å) into the cages of MIL-100, whilst it was adsorbed by the pentagonal pores (4.8 × 5.8 Å) preferentially. Internal mass transfer resistance, which was identified as one of the dominant rate-limiting steps by the mass transfer resistance kinetic models based on the Sips model, will be derived from the diffusion process, which was affected by the size-sieving effect of the pore structure of MIL-100. The successful diffusion of DCF into the interior of MIL-100 and the stable configuration between MIL-100 and DCF accounted for the high adsorption capacity. The capture of DCF into MIL-100 also resulted in the pore size distribution variation of adsorbent, which provided vital experimental evidence for the proposed mechanism. This study may offer deeper insights into other pollutants removal by metal-organic frameworks type adsorbents.

研究领域: 环境科学 · 材料科学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Efficient photocatalytic degradation of phenolic pollutants using MIL-100(Fe)@Zn3In2S6 Z-scheme heterojunction

Shuyu Chen,Zhengkai Wu,Xueying Cheng,Lu Chen,Yunning Chen,Yingna Guo,Changhua Wang,Qingkun Shang

In this work, we used a simple hydrothermal method to in-situ grow Zn 3 In 2 S 6 on MIL-100(Fe) octahedra, and obtained a MIL-100(Fe)@Zn 3 In 2 S 6 Z-scheme heterojunction photocatalyst. We systematically studied its performance in degrading phenol and p-nitrophenol (PNP) under visible light. MIL-ZIS 6 -2 can remove 89.1 % of phenol within 120 min and nearly 100 % of PNP within 60 min. Its photocatalytic activity to the degradation of phenol is 30.7 times and 1.7 times higher than that of MIL-100(Fe) and Zn 3 In 2 S 6 , respectively. And the photocatalytic activity to degrade PNP is 18.2 times and 1.4 times higher than MIL-100(Fe) and Zn 3 In 2 S 6 . Further research was conducted on its band structure and photocatalytic response mechanism through photoelectric performance, ultraviolet photo-electron spectroscopy, and electron spin resonance spectrometer testing. The results showed that the formation of Z-scheme heterojunction not only increased the specific surface area of the composite photocatalyst, enabling it to provide more reaction sites, but also effectively suppressed the recombination of photogenerated holes and electrons, improving the redox ability of the photocatalyst. This work provides a new perspective for constructing efficient Zn 3 In 2 S 6 -based composite photocatalysts and addressing environmental issues.

研究领域: 材料科学 · 环境科学
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Catalysts · 2024 ·Vol. 14 ·期 8 ·528 · IF 3.8

Defective TiO2/MIL-88B(Fe) Photocatalyst for Tetracycline Degradation: Characterization and Augmented Photocatalytic Efficiency

Dongsheng Xiang,Zhihao Wang,Jingwen Xu,Hongdan Shen,Xiaodong Zhang,Ning Liu

Photocatalysts, such as TiO2, are widely used in photoreduction. However, drawbacks like their wide band gap and short carrier lifetime lead to lower efficiencies with their use. Introducing defects and forming heterostructures of TiO2could extend the carrier’s light-harvesting range from UV to visible light and enhance its lifetime. Herein, an electron-beam irradiation-defected TiO2was induced in MIL-88B(Fe). The structure of the material was characterized using XRD, FT-IR, TEM, HRTEM, and XPS techniques. Remarkably, TiO2under 300 kGy electron-beam irradiation performed the best with a series of 0, 100, 300, and 500 kGy irradiation ratios. PL and UV–vis DRS were utilized to measure the material’s optical properties. The introduction of MIL-88B(Fe) expanded the light response range, reduced the optical band gap, and lengthened the carrier lifetime of the defective TiO2composite photocatalysts, resulting in superior TC photoreduction capabilities of 88B5%300, which degraded 97% of tetracycline (10 mg/L) in water after 120 min.

CAS / MDL: 10025-77-1 100-21-0
研究领域: 环境科学 · 材料科学
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APPLIED SURFACE SCIENCE · 2020 · IF 6.182

ZnIn2S4 decorated Co-doped NH2-MIL-53(Fe) nanocomposites for efficient photocatalytic hydrogen production

Fangxu Dai,Ying Wang,Xinran Zhou,Ruiyang Zhao,Jishu Han,Lei Wang

An efficient visible light responsive ZnIn 2 S 4 @NH 2 -MIL-53(Fe/Co 0.75 ) nanocomposite was prepared for photocatalytic hydrogen production application. Under visible light irradiation, the ZnIn 2 S 4 @NH 2 -MIL-53(Fe/Co 0.75 ) photocatalyst displayed improved photocatalytic performance and the hydrogen production rate reached to 161724.8 μmol/g in 6 h. The nanocomposite with large specific surface area and mesoporous structure increased the light absorption, improved the electrons transfer and suppressed the recombination of photogenerated electron-hole pairs, thus exhibiting efficient photocatalytic hydrogen production performance. The controllable synthesis of ZnIn 2 S 4 @NH 2 -MIL-53(Fe/Co 0.75 ) nanocomposite as a high-efficiency photocatalyst would have broad prospect for water splitting hydrogen production application.

研究领域: 材料科学 · 能源科学
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RSC Advances · 2017 ·Vol. 7 ·期 68 ·42819-42825 · IF 3.108

Enhanced photocatalytic CO2 reduction over Co-doped NH2-MIL-125(Ti) under visible light

Yanghe Fu,Huan Yang,Rongfei Du,Gaomei Tu,Chunhui Xu,Fumin Zhang,Maohong Fan,Weidong Zhu

Co-doped NH2-MIL-125(Ti) catalysts [Co/NH2-MIL-125(Ti)] are developed for the photocatalytic reduction of CO2 upon visible-light irradiation. Compared with NH2-MIL-125(Ti), Co/NH2-MIL-125(Ti) exhibits a significantly enhanced activity in CO2 reduction, due to the fact that the doping of Co nanoparticles onto NH2-MIL-125(Ti) can promote the visible-light harvesting and electron transfer. In addition, when benzylic alcohols as electron donors, instead of triethanolamine (TEOA) which is often used as a sacrificial agent, are added into the reaction system, Co/NH2-MIL-125(Ti) can simultaneously catalyze CO2 reduction to formic acid (HCOOH) and the selective oxidation of the benzylic alcohols to the corresponding aldehydes, making the proposed process more economical and environment-friendly.

研究领域: 材料科学 · 环境科学 · 化学工程
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Tuning Photoactive MIL-68(In) by Functionalized Ligands for Boosting Visible-Light Nitrogen Fixation

Qiufan Sun,Yuxiang Zhu,Xiang Zhong,Meng Jiang,Yanchen Fan,Jianfeng Yao

In this work, MIL-68(In) functionalized with various ligand substitutions including amine, hydroxyl, bromine, nitro, and methyl groups was prepared, via a one-pot solvothermal reaction for visible-light photocatalytic ammonia synthesis. The diversity of ligands tunes the morphology, geometry, pore environment, and electronic structure of MIL-68(In)-based photocatalysts due to the polarity and intraframework interactions. Amine-inserted MIL-68(In) outperforms its counterparts, presenting a boosted nitrogen photofixation rate of 140.34 μmol gcat–1 h–1 with an apparent quantum efficiency of 5.69% at 420 nm. Further, the size of the batch solvothermal reactor and the amine group content also influence the photocatalytic activity. The combined experimental and theoretical results reveal that amine substituents improve the chemisorption of nitrogen molecules and the conversion of nitrogen into ammonia follows a dual pathway, i.e., a Mars–van Krevelen process and a ligand-to-metal charge transfer mechanism. This work provides a molecular engineering strategy via dual catalysis toward efficient ammonia production.

研究领域: 材料科学 · 化学工程 · 环境科学
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MICROPOROUS AND MESOPOROUS MATERIALS · 2023 · IF 5.2

Synergistic desulfurization over Ni(II) and Fe sites in adsorbent Ni@MIL-100(Fe)

Ning Gu,Yueyang Xu,Yan Yin,Xuzhao Gao,Yongping Zeng

SO x released from the combustion of sulfur-containing compounds in fuels pollute the environment and have a serious impact on human health. Adsorption desulfurization is an effective and environmentally friendly technique for removing sulfur-containing compounds from fuels. Metal-organic frameworks (MOFs) have high specific surface areas and can be easily modified and functionalized, making them excellent candidates for adsorption desulfurization in fuels. In this work, the precursor MIL-100(Fe)-SA was prepared using the hydrothermal method , and the adsorbent Ni@MIL-100(Fe)-SA was obtained by doping Ni 2+ into the resulting MIL-100(Fe)-SA using the impregnation method. FT-IR, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption isotherms were used to analyze the samples. The results indicated that Ni 2+ was successfully loaded onto MIL-100(Fe)-SA, and the MOF's structure remained stable. The adsorption performance of benzothiophene and thiophene was evaluated through batch adsorption experiments. The adsorption capacities of Ni@MIL-100(Fe)-SA for thiophene and benzothiophene were 23.68 mg S/g and 49.58 mg S/g, respectively. These observations could be ascribed to the π-complexation interactions between Ni 2+ of the framework and thiophenic compounds. The regeneration experiments demonstrated that the spent 11Ni@MIL-100(Fe)-SA-1.5 reach 86% of the adsorption capacity of fresh adsorbent after four cycles. Additionally, the regenerated adsorbent maintained good crystallinity after recycling.

研究领域: 材料科学 · 环境科学
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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

Humidity sensing properties of FeCl3-NH2-MIL-125(Ti) composites

Ying Zhang,Bo Fu,Kuixue Liu,Yupeng Zhang,Xu Li,Shanpeng Wen,Yu Chen,Shengping Ruan

FeCl 3 -NH 2 -MIL-125(Ti) with different FeCl 3 content was prepared and characterized by XRD , SEM and XPS . The humidity sensing properties of FeCl 3 -NH 2 -MIL-125(Ti) have been investigated. Compared with NH 2 -MIL-125(Ti), FeCl 3 -NH 2 -MIL-125(Ti) was more effective in the humidity sensing. The optimal mixing ratio was FeCl 3 -NH 2 -MIL-125(Ti) (8   wt%), which exhibited the best linearity. The impedance of FeCl 3 -NH 2 -MIL-125(Ti) (8   wt%) decreases by almost three orders of magnitude in the range of 11%-95% RH. The response time and recovery time of the humidity sensor by FeCl 3 -NH 2 -MIL-125(Ti) (8   wt%) are 11   s and 86   s respectively. These results indicate the potential application of FeCl 3 -NH 2 -MIL-125(Ti) in humidity sensors.

研究领域: 材料科学 · 传感器技术 · 纳米材料 · 功能材料
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JOURNAL OF POROUS MATERIALS · 2025 · IF 3.2

Degradation of tetracycline by MIL-101(Fe)/CoFe2O4 activated persulfate under visible light

Rui Guofen,Hu Zihao,Wu Huiqi,Ma Jianfeng

Composites of MIL-101(Fe)/CoFe 2 O 4 were prepared by a simple solvothermal approach and these composites were explored for tetracycline (TC) degradation by using light and persulfate (PS). MIL-101(Fe)/CoFe 2 O 4 catalyst showed superior catalytic performance when combined with photocatalysis and chemical catalysis. Experimental results suggest that the degradation efficiency reached 83% within 40 min. The TC adsorption ability of MIL-101(Fe)/CoFe 2 O 4 was tightly associated with pH, which can be interpreted through isoelectric point. Oxygen-active species, containing singlet oxygen ( 1 O 2 ) or superoxide radicals (O· 2‾), were also generated when there was dissolved oxygen, which could decompose the TC organic contaminant in solution. To be specific, MIL-101(Fe)/CoFe 2 O 4 /PS/Vis catalytic system was capable of eliminating TC through forming h + , 1 O 2 , O· 2‾, hydroxyl radicals (·OH) and sulfate radicals (·SO 4 ‾) species. Moreover, MIL-101(Fe)/CoFe 2 O 4 composite material showed outstanding stability.

研究领域: 环境科学 · 催化材料
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