MOFs基材料用于环境污染控制文献整理（2025.1.19-2025.1.25）

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题目：Single-atom Ni-N₄ decorated zeolitic imidazolate framework-67 (ZIF-67) for enhanced catalytic activation of peroxymonosulfate: A case study on levofloxacin degradation in water matrices

作者：Van-Re Le, Thanh-Binh Nguyen, Chiu-Wen Chen, Ruey-an Doong, Wei-Hsin Chen, Linjer Chen, Cheng-Di Dong *

摘要：In this study, the single-atom sized Ni-N₄ was incorporated into zeolite imidazole framework (ZIF-67) resulting in (Ni-CN@ZIF-67), to activate peroxymonosulfate (PMS) toward degradation of levofloxacin (LVF) in water. The findings revealed that an optimal ratio of Ni-CN to ZIF-67 at 0.5:1 achieved the highest degradation efficiency of LVF, reaching up to 97.6 %, with a corresponding rate constant of 0.652 min⁻¹ within a 10-minute reaction period, compared to single catalysts. Reactive oxygen species (ROS) such as O₂^●-, ^●OH, SO₄^●-, ¹O₂, and high-valent metal oxo species were identified in the 0.5:1 Ni-CN@ZIF-67/PMS system, with ¹O₂ playing a crucial role in enhancing LVF degradation. The pathways of LVF degradation were examined based on LC-MS and DFT results, revealing two plausible degradation processes. The toxicity of intermediates was evaluated using TEST analysis, and algal growth studies indicated that the treated LVF solution exhibited reduced toxicity compared to the original LVF. Furthermore, comprehensive evaluations were conducted on the stability, practicability, mechanisms, and mineralization of the 0.5:1 Ni-CN@ZIF-67/PMS system.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2025.159829

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题目：An efficient catalyst for carbamazepine degradation that alkali-etched silicon carbide Synergy effect with ZIF-67 (ZIF-67/AE-SiC) in peroxymonosulfate system

作者：Zhencong Liu, Zhiqi Zhu, Pengyuan Chen, Xiang Zhu, Fangdi Huang, Nannan Wang*, Yan Qiu Zhu *

摘要：Addressing the   agglomeration issue of ZIF-67 is of great significance for its application in advanced oxidation processes (AOPs) targeting organic macromolecule pollutants. In this study, we etched commercially available silicon carbide (C-SiC) in an alkaline solution to obtain alkali-etched silicon carbide (AE-SiC). Using a co-precipitation method, we synthesized a composite material where ZIF-67 is surface-modified by AE-SiC (ZIF-67/AE-SiC). After alkali etching, AE-SiC particles become smaller, with increased porosity and larger pore size. These modifications allow AE-SiC to chemically bond to the surface of ZIF-67, effectively reducing its surface energy and thus resolving the issue of self-agglomeration. Meanwhile, the introduction of AE-SiC allows peroxymonosulfate (PMS) to enter ZIF-67 more rapidly, facilitating dynamic redox cycling in ZIF-67. This enhances the forming of reactive species like SO4^·−, O₂^·−, and ¹O₂, leading to the production of additional free radicals that effectively degrade organic macromolecular pollutants. The optimized ZIF-67/AE-SiC(0.08) composite exhibited excellent catalytic activity in PMS-mediated carbamazepine (CBZ) degradation, achieving over 95% degradation within 8 min. A comprehensive investigation into the degradation pathways of CBZ was conducted, concurrently with an evaluation of the toxicity of itself and its degradation intermediates. This study expands the potential applications of silicon carbide and ZIF-67 materials in the development of PMS-based advanced oxidation processes.

期刊信息：Chem. Eng. J

DOI：10.1016/j.cej.2025.159685

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题目：Diethylenetriaminepenta-acetic acid (DTPA) grafted UiO-66-NH₂/PES composite membrane for efficient removal of heavy metal ions

作者：Guowei Shan , Xiao Xiao , Hong Gao, Qi Zhang, Houyi Peng, Weixing Li*

摘要：Heavy metal ion (HMI)-contaminated wastewater is a great threat to public health. Membrane separation is an efficient and green technology for HMI removal. Here, the strategy of nanoparticle in-situ growth combined with molecule grafting was proposed to fabricate the UiO-66-NH₂-g-DTPA/PES composite membrane. The UiO-66-NH₂ nanoparticles bound within the PES membrane substrate uniformly brought a significant number of primary amino groups, providing abundant graft sites for DTPA molecule. Numerous carboxyl groups and tertiary amine groups were introduced as the result of DTPA grafting, enabling the formation of M−DTPA complexes with HMIs. The fabricated UiO-66-NH₂-g-DTPA/PES membranes exhibited excellent performances. The pure water flux arrived at 6208 L·m⁻²·h⁻¹ and the efficiencies of removing Cu²⁺, Pb^2+, Cr³⁺ and Cd²⁺ were 99.73%, 99.79%, 96.91% and 98.33%, respectively. Moreover, the UiO-66-NH₂-g-DTPA/PES membrane also showed a remarkable stability in pH conditions ranging from 3 to 10 and remained a relatively high performance in the cyclic test.

期刊信息：Sep. Purif. Technol

DOI： 10.1016/j.seppur.2025.131650

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题目：Shape, morphology, and components-dependent motion and water purification performance study of multi-metal–organic frameworks based micromotors

作者：Jiawei Lin, Wenfeng Zhou, Qing Wu, Kunchen Li, Yulong Ying*, Sheng Wang*

摘要：The integration of micro/nanomotors (MNMs) with metal–organic frameworks (MOFs) demonstrated substantial potential for advancing environmental remediation. However, most MOF-based micromotors (MOFtors) are limited by having only a single metal node, primarily functioning as motile adsorbents with enhanced purification efficiency over their static counterparts, which significantly suppresses their potential. Bimetallic or multi-metallic catalysts typically have synergistic effects to allow them to operate effectively across a wider range of environmental conditions. In response to these challenges, we developed multi-metallic MOFtors based on CoMn-PBAs (CoMn-C and CoMn-S) and their derivates, focusing on their shape, morphology, and components-dependent motion and catalytic application. Various modes of motion, including light-driven, bubble-propelled, and magnetically controlled motions, were explored. CoMn-S based MOFtors exhibited a characteristic clustering behavior under blue and ultraviolet light while CoMn-C-T micromotors, derived from the light-insensitive CoMn-C, displayed spinning motion at different speeds in H₂O₂ of different concentrations. Incorporating with Fe₃O₄ nanoparticles, these micromotors can realize the spiral motion with customizable trajectories under an external magnetic field. Furthermore, in combination with sulfate radical-advanced oxidation processes (SR-AOP), these micromotors achieved excellent degradation performance against organic pollutants such as malachite green (MG) and chlortetracycline (CTC). Our study highlights the development of CoMn-based multi-metallic PBAs MOFtors and their derivatives as cost-effective, easily synthesized micromotors with recyclability, offering significant promise for advancing water treatment technologies.

期刊信息：Sep. Purif. Technol

DOI： 10.1016/j.seppur.2025.131559

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题目：Solar-driven interfacial evaporation coupling with photo-Fenton of floating Prussian blue/polypyrrole/paper film for volatile organic compounds-containing wastewater treatment

作者：Chengpeng Qiu , Jianhua Zhou*, Xiaoyun Hu , Meng Kang , Xiaojiang Mu , Zhixiang Zhang , Yang Long , Yanqing Zhu , Jie Gao , Gang Xu ,Lei Miao

摘要：Solar-driven water evaporation can generate clean steam through phase change and mass transfer processes. However, when dealing with volatile organic compounds (VOCs) contaminated water sources, VOCs tend to volatilize into the vapor during the evaporation process, making separation difficult. This issue can be effectively addressed by utilizing photo-Fenton technology to assist the solar-driven water evaporation process. A novel photothermal catalytic film was successfully prepared by incorporating Prussian blue (PB) and polypyrrole (PPy) onto a slow filter paper substrate. The photothermal conversion ability of PPy was further enhanced by PB, and the temperature increase induced by PPy accelerated the photo-Fenton catalysis process, indicating a synergistic action between photothermal evaporation and photo-Fenton catalysis. The film exhibited outstanding catalytic performances in degrading various VOCs in wastewater, including phenol, methyl orange, methylene blue, and rhodamine B. Notably, the film reached an impressive degradation rate of 99.5 % for methyl orange within 2 h. The assembled 2D interfacial evaporator achieved an evaporation rate of 1.58 kg m^-2h⁻¹ under one sun irradiation (1 kW m⁻²). After 40 cycles, the evaporation rate remained constant. This photothermal catalytic film effectively degrades VOCs while stably producing steam, demonstrating significant potential in the treatment of volatile organic wastewater.

期刊信息：Sep. Purif. Technol

DOI： 10.1016/j.seppur.2025.131735

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题目：Synthesis of single-crystal UiO-67-(NH₂)₂ for effective SO₂ adsorption and separation from flue gas

作者：Xiao-Hong Xiong , Liang Song , Jia-Liang Liang , Zi-Ye Qin , Xin-Xin Huo , Zhi-Min Liang , Li-Lin Tan*, Zhang-Wen Wei*, Mian Li , Xiao-Chun Huang , Cheng-Yong Su*

摘要：The synthesis of stable and efficient porous adsorbents for adsorptive capture and recovery of SO₂ from flue gas is of great importance for minimizing air pollution and reducing costs. Herein, by choosing trifluoroacetic acid as modulator, the single crystal UiO-67-(NH₂)₂ has been successfully synthesized benefitting crystal structure determination. The stability tests, gas adsorption measurements, and breakthrough experiments demonstrated that single-crystal UiO-67-(NH₂)₂ possesses moderate acid-base and hydrothermal stability, and exhibited high SO2 uptake (19.72 mmol/g, 298 K and 1 bar), good SO2/CO2 separation selectivity (110.3～33.3, SO₂/CO₂ = 10/90), and excellent SO2 recovery purity (93.3 %). However, the instability of the UiO-67-(NH₂)₂ framework, combined with the strong corrosive and reactive properties of SO₂, can lead to partial collapse of the framework during the adsorption and capture process. This ultimately results in a decreased SO₂ capture performance over time. In-situ DRIFT, GCMC simulation and DFT calculations revealed that the μ3-OH of Zr₆O₄(OH)₄ clusters and the —NH₂ groups of the ligand can form multiple hydrogen bonds with SO₂ molecules. This ensures that SO₂ molecules are firmly grasped by UiO-67-(NH₂)₂ framework and facilitate the efficiently selective capture of SO₂ at low concentration.

期刊信息：Sep. Purif. Technol

DOI： 10.1016/j.seppur.2025.131560

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题目：Improving synergistic effects within metal–organic framework by modulating structural interpenetration for boosted photocatalytic peroxydisulfate activation

作者：Zhi-Yong Liu, Tao An, Kun Yu*, Xue-Meng Jia, Yu-Hui Luo*

摘要：Metal-organic frameworks (MOFs) have shown significant potential in the photocatalytic activation of peroxydisulfate (PDS). Although many MOFs have been investigated for their ability to activate PDS, the impact of structural interpenetration on this process remains underexplored. In this study, MIL-88D(Fe₂Ni) and MIL-126(Fe₂Ni) were selected to systematically study this effect. Both MOFs are composed of 4,4’-biphenyldicarboxylic acid and [Fe₂NiO(COO)₆] clusters (abbreviated as Fe₂Ni), while the framework of MIL-126(Fe₂Ni) can be considered as a two-fold interpenetrating MIL-88D(Fe₂Ni) networks. The study shows that interpenetration not only enhances the structural rigidity and stability, but also facilitates the exposure of active sites. The structural interpenetration reduces the distance between Fe₂Ni clusters to 0.6 nm, which is thermodynamically favorable for PDS activation. Consequently, the photocatalytic activation of PDS by MIL-126(Fe₂Ni) is significantly promoted. The MIL-126(Fe₂Ni)/PDS system achieved a 96.5 % removal efficiency of ofloxacin (OFL) within 30 min, with a high degradation rate constant (k) of 0.10 min⁻¹. In addition, the MIL-126(Fe₂Ni)/PDS system can effectively remove various organic pollutants from different water bodies, even under outdoor sunlight irradiation. Fascinatingly, MIL-126(Fe₂Ni)@polyurethane sponges also can remove 98.4 % of OFL in 60 min, highlighting its potential for practical applications.

期刊信息：J. Colloid. Interf. SCI

DOI：10.1016/j.jcis.2025.01.123

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题目：Ab Initio Predictions of Adsorption in Flexible Metal–Organic Frameworks for Water Harvesting Applications

作者：Ruben GoeminneVeronique Van Speybroeck*

摘要：Metal–organic frameworks such as MOF-303 and MOF-LA2–1 have demonstrated exceptional performance for water harvesting applications. To enable a reticular design of such materials, an accurate prediction of the adsorption properties with chemical accuracy and fully accounting for the flexibility is crucial. The computational prediction of water adsorption properties in MOFs has become standard practice, but current methods lack the predictive power needed to design new materials. Limitations stem from the way the interatomic potential is described and the inadequate consideration of the framework flexibility. Herein, we showcase a methodology to obtain chemically accurate adsorption isotherms that fully account for framework flexibility. The method relies on very accurate and efficiently trained machine learning potentials and transition matrix Monte Carlo simulations to account for framework flexibility. For MOF-303, quantitatively accurate adsorption isotherms are obtained, provided an accurately benchmarked electronic structure method is used to train the machine learning potential, and local and global framework flexibility is accounted for. The broader applicability is shown through the study of MOF-333 and MOF-LA2–1. Analysis of the water density profiles in the MOFs gives insight into the factors governing the shape and origin of the isotherm. An optimal water harvester should have initial seeding sites with intermediate adsorption strength to prevent detrimental low-pressure water uptake. To increase the working capacity, linker extension strategies can be used while maintaining the initial seeding sites, as was done in MOF-LA2–1. The methodology can be applied to other guest molecules and MOFs, enabling the future design of MOFs with specific adsorption properties.

期刊信息：J. Am. Chem. Soc.

DOI：10.1021/jacs.4c15287

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题目：Mechano-thermochemical synthesis of chiral multicentre fluorescent MOFs for chiral VOCs detection and adsorption

作者：Jiaqiang Liu ,Xin Su ,Yan Xu ,Weiwei Tang*,Junbo Gong*

摘要：Volatile organic compounds (VOCs) in wastewater pose a serious threat to human health and the environment. With the increasing demand for chiral pharmaceuticals and the development of the chiral industry, the identification, detection and removal of chiral VOCs has become an urgent challenge. Here, we have constructed chiral fluorescent metal-organic frameworks (MOFs) composites for the first time using single chiral amino acids as a chiral source and in situ carbonation of precursors, integrating both chiral and heterologous multiluminescent centres in the composite system. The blue-green-red luminescence system is composed of heterologous multi-luminescent centres, i.e. ligands, carbon quantum dots and rare earth metals. This heterologous nature allows efficient and accurate qualitative identification of VOCs species and quantitative detection of chiral VOCs concentrations. In particular, its monochiral structure enables enantiomeric excess values detection of chiral enantiomeric mixtures. In addition, the solvent-free synthesis process with competitive coordination of amino acids successfully constructed the multilevel pore structure of the composites, which effectively increased the adsorption rate of the materials by 30 times. The present work provides an efficient method to introduce chirality into multi-centre luminescent MOFs systems, and provides a guiding direction and material design ideas for chiral pollutant detection and removal technologies.

期刊信息：Sens. Actuators, B

DOI：10.1016/j.snb.2025.137277

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题目：Development of metal-organic framework-based systems for H₂S removal: A comprehensive review

作者：Thi Linh Giang Hoang ,Duy Tuan Doan ,Sonil Nanda ,Renaud Lavoie ,Phuong Nguyen-Tri*

摘要：Biogas is recognized as a source of renewable energy that can substitute for fossil fuels, especially natural gas. Biogas is produced from various organic resources, and it contains mainly methane (CH₄) and carbon dioxide (CO₂). However, several contaminants are found in the biogas flow such as hydrogen sulfide (H₂S), water (H₂O), ammonia (NH₃), and volatile organic compounds (VOCs). Therein, due to its high corrosion, toxicity, and bad odor, H₂S must be eliminated first and intensively to avoid equipment damage and health risks. Among H₂S removal technologies, using the solid adsorbent is viewed as a friendly and effective way. Recently, metal-organic frameworks (MOFs) have been studied with increasing attention for H₂S adsorption thanks to their high surface area, good thermal stability and structural tunability. Although many MOFs-based systems have been designed for H₂S removal, an intensive study to summarize them is missing. This work aims to revise the development of MOFs-based networks for H₂S removal in literature including pristine MOFs, functionalized MOFs, MOF composites, and mixed-metal MOFs. We focus on explaining H₂S adsorption mechanism of MOFs, and material engineering factors that directly affect the H₂S adsorption capacity, the selectivity over other gases, and the ability to regenerate. Furthermore, several perspectives to enhance the removal performance of MOFs are also proposed. Together, this study will provide a comprehensive document on current technologies and perspective development of MOF-derived H₂S adsorbent.

期刊信息：Coord. Chem. Rev.

DOI：10.1016/j.ccr.2025.216466

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本期编辑

  史骁阔，男，北京建筑大学环境工程专业2024级硕士研究生。主要研究方向为金属-有机骨架材料的设计与制备及其在水环境修复方面的研究。

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