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题目：Microcystis aeruginosa removal over MOFs-based materials and the evaluation methods: state-of-the-art review

作者：Hong-Yu Chu, Guang-Chi Liu , Fu-Xue Wang, Lian-Sheng Cui, Chong-Chen Wang *

摘要：The harmful algal bloom primarily caused by Microcystis aeruginosa (M. aeruginosa) has become one of the serious biological pollution issues in actual water, which has received intense attention worldwide. Over the past years, increasing number of publications have reported that metal-organic frameworks (MOFs) based functional materials exhibited significant inhibition against M. aeruginosa via multiple mechanisms, but no review papers systematically presented progresses regarding MOFs-based materials for M. aeruginosa control up to now. With this review paper, we summarized the state-of-the-art studies of MOFs-based materials for M. aeruginosa removal, comparing and discussing the design strategies of MOFs-based materials and their antimicrobial mechanisms. Meanwhile, we discussed methods for evaluating the water purification performances of MOFs-based materials against M. aeruginosa. Finally, the perspectives for design of novel MOFs-based functional materials and application scenarios were proposed to provide an outlook on areas where greater efforts should be made in the future.

期刊信息：Chin. Chem. Lett.

DOI：10.1016/j.cclet.2024.110745

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题目：UiO-67: A versatile metal-organic framework for diverse applications

作者：Ji Zhou,Shuangxi Gu,Yuqin Xiang,Yun Xiong, Genyan Liu*

摘要：UiO-67 species, a prominent class of metal-organic frameworks (MOFs) within the UiO (University of Oslo) subgroup, possess unique features. These include diverse synthetic methods, a wide variety of structures, host-guest chemistry, large and uniform pores, tunable surfaces, and flexible network topology, geometry, dimension, and chemical functionality. Due to these features, UiO-67 demonstrates remarkable potential applications in various scientific and life science fields. Literature surveys show that UiO-67 exhibits competitive and promising applications compared to other MOFs and even its close relatives, UiO-66 and UiO-68. Despite the rich chemistry and rapidly growing research on UiO-67, particularly in recent years, a comprehensive review of its applications is lacking. This review aims to fill this gap by providing the first systematic and complete classification of Zr-based UiO-67 MOF applications, synthetic methods, design and structures since 2008. The contents are categorized into key areas: design and synthesize, structural landscape, applications including, catalysis, adsorption, separation, sensing, medicine/drug delivery, and energy storage/conversion. Each category is further subdivided for specific applications. While the primary focus is on applications, the review also incorporates discussions on synthetic pathways and comparative studies. Finally, future perspectives for Zr-UiO-67 applications are explored, aiming to contribute to their wider use in multidisciplinary chemistry. Future research should focus on expanding the application of Zr-UiO-67 MOFs in diverse fields. This includes further exploration of their potential in CO₂ capture and conversion, organic transformations, and C-C bond formation catalysis. Additionally, the development of UiO-67-based materials for water treatment, environmental remediation, biosensing, drug delivery, and energy storage will be crucial.

期刊信息：Coord. Chem. Rev.

DOI：10.1016/j.ccr.2024.216354

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题目：Removal of Trace Benzene from Cyclohexane Using a MOF Molecular Sieve

作者：Rui-Chao Zhao, Lin-Hua Xie*, Xiao-Min Liu, Zhe Liu, Xiang-Yu Li, Jian-Rong Li*

摘要：Cyclohexane (Cy), commonly produced by the catalytic hydrogenation of benzene (Bz), is used in large quantities as a solvent or feedstock for nylon polymers. Removing trace unreacted Bz from the Cy product is technically difficult due to their similar molecular structures and physical properties. Herein, we report that a metal–organic framework (MOF) adsorbent shows a molecular sieving effect for Bz and Cy with record-high Bz/Cy adsorption selectivities (216, 723, and 1027) in their liquid mixtures (v/v = 1:1, 1:10, and 1:20), and traps Bz molecules effectively even at low partial pressure in the vapor phase (e.g., 2.49 mmol/g at 8.2 Pa) or at low content in liquid-phase Cy (e.g., 128 mg/g at 20 ppm). Over 99% removal of trace Bz (1000 ppm) from liquid Cy could be achieved in one simple stripping step at room temperature using this sorbent, producing a Cy with >99.999% purity. Single-crystal structure analyses for guest-free and Bz-loaded phases of the MOF disclosed that a narrow slit-like pore aperture and the strong uniting of multiple weak host–guest and guest–guest interactions are the co-origin of its distinct adsorption property for Bz and Cy.

期刊信息： J. Am. Chem. Soc.

DOI：10.1021/jacs.4c13208

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题目：A hybrid LMO MOF catalytic membrane with PMS activation for efficient degradation of pharmaceutical micropollutants and nanoplastics removal

作者：Afia Sharmin, Muhammed A. Bhuiyan, Biplob Kumar Pramanik*

摘要：In this study, a novel hybrid CoFe layered metal oxide (CoFeLMO) membrane was developed by integrating metal–organic framework (MOF) MIL(100)Fe and polyethylene glycol (PEG), designed specifically for peroxymonosulfate (PMS)-based advanced oxidation processes. The uniqueness of this research lies in the innovative incorporation of LMO, MOF, and PEG nanosheets onto a polyethersulfone (PES) substrate, creating a highly efficient catalytic membrane for the simultaneous removal of pharmaceutical micropollutants and nanoplastics (NPs).Among various configurations, the LMO-MOF-PEG membrane, with 20 % MOF (0.025 M) and 0.5 g of PEG, demonstrated superior performance, achieving remarkable removal efficiencies of 99.5 % for ranitidine and 98.5 % for NPs. This membrane also exhibited outstanding operational efficiency, achieving a flux of 1600 L/m²/hr/bar at a low PMS concentration of 0.2 mM. The degradation of ranitidine was driven by both reactive species (•SO₄^-, •OH and •O₂^-) and non-reactive species (singlet ¹O₂), with •SO₄^- playing a dominant role. Post-activation analysis revealed the presence of Co²⁺ and Fe²⁺ in both + II and + III oxidation, indicating the active participation of metal plots in the degradation process and confirming the membrane’s reusability. The membrane demonstrated exceptional durability, maintaining a flux recovery ratio of 97–99 % across 10 filtration cycles, even under harsh chemical conditions and across a wide pH range (2–12). Furthermore, Co leaching was minimal (2–21 µg/L) over a broad pH spectrum, even after 15 days of immersion in water.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130881

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题目：Hole transfer promotion on La-MOF@MXene by valence band structure regulation for the efficient photocatalytic degradation

作者：Daoxin Wu , Zhuo Tong , Jun Wang , Gao Chen , Aolin Zhu , Haixia Tong* , Mingming Dang*

摘要：La-MOF has excellent thermal and chemical stability. Therefore, it can be used in the field of photocatalysis. However, the sluggish hole transfer, which is caused by low valence band position hinders its application prospects in photocatalysis, especially in hole-driven processes. In this work, we have proposed a strategy to adjust the VB structure on La-MOF, by modifying the two-dimensional (2D) conductor MXene electron-withdrawing. XRD, Raman, and HRTEM analysis indicated that the three-dimensional La-MOF was uniformly encased by the 2D MXene, and the distinct interface substantiated the successful construction of the Schottky heterojunction. XPS and UPS characterization revealed that the electron transfer from La-MOF to MXene induces an upward shift in the valence band of La-MOF to promote hole transfer. As a result, the optimized La-MOF@MXene achieved a photocatalytic degradation constant of 0.00773 min−1 for tetracycline hydrochloride within 120 min, which is 5.3 and 20 times higher than that of pure La-MOF and MXene, respectively, outperforming most previously reported works. This work can expand the application of La-MOF materials in the field of photocatalysis, providing a fresh avenue to regulate the slow hole transport.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130873

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题目：In situ prepared ionic liquids containing moisture-resistant bismuth-based perovskite crystals enhance the photocatalytic water purification and H₂ production of MOF

作者：Yao-Yao Wang* , Yu-Qing Wang , Li-Xia Bao* , Chunfeng Wang*， Zhaoyang Wang , Hongjie Zhu , Hui-Juan Wang

摘要：Perovskite materials have been found to enhance the photocatalytic performances of metal–organic frameworks (MOFs) through the formation of heterojunctions. In this study, two novel perovskite crystals: N-methylbenzothiazoleBiI4 (BtzBiI₄) and 1,3-dimethylbenzimidazoleBiI4 (MpiBiI₄) were obtained by in situ alkylation of 1-methylbenzimidazole and benzothiazole to prepare 1,3-dimethylbenzimidazole iodide and N-methylbenzothiazolium iodide ionic liquids. BtzBiI₄ and MpiBiI₄ crystals exhibit remarkable stability in aqueous solutions and broad UV–visible light absorption properties within 680 nm and 640 nm, respectively. Subsequently, a post-modification strategy was employed to integrate these perovskites with the zirconium-based MOF NH₂-UiO-66 (U6N) and small-sized Pt clusters, resulting in the fabrication of perovskite quantum dots/Pt@U6N composite heterojunction photocatalysts for hydrogen production and water purification. Consequently, under visible light irradiation, the reduction efficiency of Cr (VI), degradation efficiencies rhodamine B (Rh B) and tetracycline (TC) of BtzBiI₄ QDs modified Pt@U6N (BPU) can reach 93.4 %, 98.9 % and 99.4 %, respectively. The H₂ production rate in water could be further boosted to 1044.25μmol g^-1h⁻¹ by using BPU. Using MpiBiI₄ QDs modified Pt@U6N (MPU), the photocatalytic hydrogen production efficiency can reach 955.37μmol g^-1h⁻¹. This work comprehensively explores the role of ionic liquid-assisted preparation of moisture-resistant perovskites and their charge transfer dynamics in heterojunctions with MOFs, and introduces efficient photocatalysts for waste water purification.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130998

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题目：Novel honeycomb 3D Co/In-MOF with rigid ligand are used for efficient C₁-C₃ light hydrocarbons adsorption separation, fluorescence sensing and selective dye adsorption

作者：Shuai Liu, Li-Na Zheng*, Si-Wei Dong, Yun-Zhuo Sun, Qian-Wen Xue, Ning Xue, Bin Liu,Yan-ping Du, Jing Zhao, Tao Ding*

摘要：Gas adsorption and separation, fluorescence sensing and dye adsorption have always attracted much attention and discussion as hot areas of applied research on metal–organic frameworks (MOFs). In this study, two structurally distinct three-dimensional (3D) MOFs, {[NH₂Me₂]₂[Co₃(L1)₂]·6DMA·8H₂O}n (Co^-1) and {[NH₂Me2]₂[In₂(L1)₂]·7DMF·4H₂O}n (In-1), were successfully synthesized by the reaction of rigid ligand L1 (L1 = 4-(2,6-bis(4′-carboxy-[1,1′-biphenyl]-4-yl)pyridin-4-yl)isophthalic acid) with Co2+ and In3+ under solvent-heated conditions, both of which have unique honeycomb structures. Co-1 exhibits high adsorption capacity for C3H6 and C3H8 (298 K: C3H6, 142.88; C3H8, 136.66 cm3·g−1). Meanwhile, it shows selective adsorption properties as high as 39.63, 42.94, 9.07, 4.12 and 3.04 for C₃H₆/CH₄, C₃H₈/CH₄, C₂H₂/CH₄, CO₂/CH₄ and C₂H₂/CO₂. The C₂H₂/CO₂ breakthrough experiment has validated the practical separation potential of Co^-1 for binary mixtures, with a dynamic separation coefficient reaching up to 2.34. Furthermore, the intrinsic mechanism for the differences in the adsorption and separation properties caused by the framework structures on the microscopic scale are revealed by the density functional theory (DFT). In-1 is a bifunctional MOF capable of rapidly and accurately detecting CrO₄2− and Cr₂O₇2− ions in water via fluorescence sensing, and selectively adsorbing the cationic dye methylene blue (MB) through electrostatic interaction with high efficiency. 21.74 mg·g⁻¹ of MB (10 mg·L−1, 24 mL) is adsorbed by 10 mg In^-1 in 50 min. Kinetic, adsorption isotherm and thermodynamic analyses show that the adsorption process of MB on In^-1 is mainly driven by chemisorption, which exhibits a homogeneous monomolecular layer adsorption, and that the process is a spontaneous and heat-absorbing reaction.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130898

论文链接：

题目：One-step electrochemical synthesis of Zn-MOFs/NF composite electrodes for efficient electrosorption of organic dyes

作者：Yi-Jun Cao , Zi-Ying Chen , Hai-Long Peng , Hui-Ping Chen* , Chun-Fang Xie* , Jie-Ping Fan*

摘要：The escalating environmental contamination by toxic organic dyes necessitates efficient emergency removal strategies. We introduce an electrochemical approach for the removal of toxic organic dyes using Zinc-based Metal-Organic Frameworks (Zn-MOFs) integrated with Nickel Foam (NF) electrodes. The ZME/NF composite electrode, synthesized via electrochemical methods, and the ZMS/NF composite electrode, prepared by solvothermal synthesis, were evaluated for their electrosorption capacities towards methyl orange (MO) and methylene blue (MB). The ZME/NF electrode, with its positively charged surface due to the Zn-MOFs’ structure, exhibited a superior electrosorption capacity of 934.76 mg/g for the anionic dye MO at 1 V, attributed to its structural affinity for anionic species. Conversely, the ZMS/NF, featuring a negatively charged surface, showed a lower electrosorption capacity of 131.75 mg/g for MO, highlighting the influence of surface charge on selectivity. Zeta potential measurements confirmed the surface charge differences, explaining the minimal electrosorption capacity of MB by ZME/NF. Both electrodes achieved adsorption equilibrium within 20 min, with ZME/NF maintaining high removal efficiency after five cycles, underscoring its potential for MO electrosorption. Adsorption mechanisms, identified through experimental data and material characterization, include π-π interactions, electrostatic interactions, pore filling, and hydrogen bonding, which are influenced by the structural characteristics of the Zn-MOFs.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131020

论文链接：

题目：Zn-MIL53(Fe) as an electro-Fenton catalyst: Application in organic pollutant degradation and pathogen inactivation

作者：D. Terrón*, J.P. Holgado-Vázquez*, E. Rosales*, M.A. Sanromán*, M. Pazos*

摘要：In this study, the potential of a bimetallic Metal-Organic Framework Zn-MIL53(Fe) for electro-Fenton catalysis was evaluated. After the material characterisation, its catalytic activity was validated in Fenton reaction to degrade a model organic pollutant: Rhodamine B. After that, the evaluation of Zn-MIL53(Fe) as electro-Fenton catalyst was performed and improved outcomes were reached by electro-Fenton regarding anodic oxidation. Then, electro-Fenton treatment optimisation was carried out using response surface methodology assays considering different catalyst dosages (7.2–43.2 mg), current intensities (5–45 mA) and treatment time (30–90 min) in a volume of 0.1 L. Under optimal conditions, a degradation rate over 90 % for Fluoxetine and Sulfamethoxazole in synthetic wastewater was achieved within 90 min, using graphite sheet as anode and nickel foam as cathode (25 mA), with a catalyst dosage of 43.2 mg in a volume of 0.1 L. Additionally, its application in the pathogen inactivation was evaluated using different gram-negative and gram-positive bacteria. Complete eliminations of both types of bacteria were reached in 5 min using the optimal conditions. In the end, Zn-MIL53(Fe) was proven as a reusable material, capable of performing 3 complete cycles of electro-Fenton treatment for both types of pollutants bacteria and pharmaceuticals, which makes it a promising candidate for more efficient wastewater treatment applications which involve the Fenton reaction.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130881

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题目：Simulation study on the impregnation of ZIF-8 with Pd nanoparticle, fullerene C₆₀, and metallofullerene Sc₃C₂@C₈₀ guests: Analyzing guest effectiveness for enhancing CO₂ uptake capacity

作者：Hamed Akbarzadeh*, Mohsen Abbaspour, Arezoo Estiri, Sirous Salemi, Esmat Mehrjouei, Cobra Izanloo

摘要：Today, it is accepted that CO₂ from the burning of fossil fuels plays a major role in global warming. Therefore, in recent years, to reduce the CO₂ concentration in the atmosphere, the synthesis and design of porous materials such as ZIFs have attracted the attention of many researchers. Improving the adsorption capacity of the synthesized ZIFs is very necessary to make them suitable for industrial applications. For this purpose, various strategies such as modification of linkers, catenation, introduction of open-metal sites and impregnation with fullerene and metallic nanoparticles have been proposed and investigated. In this study, using Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations, the effect of ZIF-8 impregnation with different guest molecules such as Pd nanoparticles, C₆₀ fullerene and Sc₃C₂@C₈₀ metallofullerene on CO₂ adsorption capacity has been investigated and the performance of the guest molecules are compared. The simulation results show that the pristine ZIF-8 has three special adsorption sites I, II and III in its structure. While increasing the concentration of guest molecules (i.e. the number of 1 and 3 guest molecules) in ZIF-8 by creating a new and more active IV site and thus increasing the number of adsorption sites from 3 to 4, increases the CO₂ adsorption capacity. While higher concentrations of guest molecules (i.e. 6 and 9 guest molecules) decrease the CO₂ adsorption capacity by blocking the pores of ZIF-8 and reducing the pore volume and surface area. The simulation results also show that the role of guest molecules in increasing gas adsorption capacity can be determined as the trend of Sc₃C₂@C₈₀ > C₆₀ ≥ Pd. The simulation results show that despite having a lower gas adsorption capacity, Pd nanoparticles have stronger interactions with CO₂ molecules and cause stronger CO₂ gas adsorption. In this study, the role of guest molecules in increasing the strength of interaction with CO₂ gas was determined as Pd > Sc₃C₂@C₈₀ > C₆₀. The results of this study provide a new and broad view of the impregnation phenomenon of ZIFs as well as the function of different guest molecules in the impregnation phenomenon. It is expected that the results of this study can help researchers in this field to choose the appropriate guest molecule in the impregnation phenomenon in order to improve the gas adsorption capacity.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2024.161991

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题目：ZIF-67 as the Co source for the preparation of composite hollow CoO/Co/carbon nanofibers and their application in advanced oxidation process

作者：Haowei Sun, Qiaohong Peng, Guangzhen, Zheng Chen, Xiaoyu Huang, Hua Yuan*

摘要：Advanced oxidation technology based on sulfate radical has great potential in the oxidation removal of refractory organic pollutants. Carbon materials with higher surface area, which are utilized to support transition metal catalyst such as Co, can effectively inhibit metal leaching and reduce the degree of secondary pollution. Herein, ZIF-67 as a Co source was doped in the polymer fiber matrixes of polyacrylonitrile and poly(methyl methacrylate), and CoO/Co/carbon nanofibers (CoO/Co/CNFs) composites with hollow structure was obtained after carbonization. The experimental results show that Co exists in the form of Co⁰ and Co²⁺ in the CoO/Co/CNFs. Using the CoO/Co/CNFs as Fenton catalysts and Rhodamine B as a simulated pollutant, the degradation rate of the pollutant could reach 95% within 10 min. After five cyclic degradation tests, the degradation rates only slightly decreased. In addition, The (CoO/Co/CNFs)/PMS system also showed a remarkable ability to degrade methylene blue.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2024.161991

论文链接：

题目：MOF-on-MOF-derived hollow tubular ZnFe₂O₄/Er-ZnO heterojunctions for the efficient degradation of tetracycline by visible light photocatalysis

作者：Jun Yu, Hao Yang, Xiangyu Li, Xupeng Chen, Wenyue Li, Xingang Li*, Chun Zhang*

摘要：Semiconductor photocatalytic technology is recognized as one of the effective technologies for using solar energy to solve current environmental problems. In this study, a Z-scheme heterojunction ZnFe₂O₄/Er-ZnO hollow nanotube composite was prepared by hydrothermal method. The results show that the degradation efficiency of tetracycline (TC) in ZnFe₂O₄ is only 51 %, while the degradation efficiency of ZnFe₂O₄/2% Er-ZnO hollow tube composites is as high as 97 %. At the same time, ZnFe₂O₄/2% Er-ZnO has a larger specific surface area (specific surface area of 224.39 m²·g⁻¹), which is 27 times that of ZnFe₂O₄ (specific surface area of 8.30 m²·g⁻¹). Density functional theory (DFT) calculations and experimental analysis show that the doping of Er, the unique hollow structure and the formation of heterojunction make ZnFe₂O₄/2% Er-ZnO have a large specific surface area, efficient carrier separation ability and strong redox ability, so the Z-scheme heterojunction ZnFe₂O₄/2% Er-ZnO hollow tubular composites have strong degradation ability for tetracycline. In addition, the liquid chromatography-mass spectrometry (LC-MS) analysis technique was used to propose the possible degradation pathways of antibiotics, which provided ideas for the treatment of water pollution.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2024.161634

论文链接：

题目：High-performance photocatalytic degradation of aromatic compounds using Co-MOF-74/ZnIn2S4/CNF aerogels with enhanced charge separation and photothermal synergy

作者：Chen Hou*, Shengyang Zou, Junyi Gao, Liang Yuan, Jianzhi Wang, Yang Wang*

摘要：Although photocatalytic degradation using semiconductor materials has been widely studied, there are still challenges such as slow reaction kinetics and complex synthesis process. To overcome these problems, Co-MOF-74@ZnIn₂S₄@CNF composite aerogel was developed in this study, which significantly improved the photocatalytic efficiency. This novel structure integrates three key functions: 1) the one-dimensional Co-MOF-74-NTs nanotube enhances carrier mobility based on its high aspect ratio; 2) the Co-MOF-74@ZnIn₂S₄ heterojunction facilitates charge separation for efficient generation of reactive oxygen species; 3) the porous cellulose aerogel promotes the adsorption of substrates and improves the photothermal effect due to its intrinsic thermal conductivity and insulation, and will facilitate effective charge separation. This combined functionality resulted in highly efficient degradation of paraxylene, with 91.6% of degradation efficiency and 68.79% of mineralization rate within 3h under simulated sunlight. Several experiments demonstrated that the Co-MOF-74@ZnIn₂S₄@CNF aerogel possessed strong stability and effective catalytic properties for a variety of aromatic compounds. This study introduces a new photocatalytic system combining heterogeneous structure and photothermal effect to enhance charge transfer, providing an efficient solution for photothermal-assisted Aromatic Compounds degradation.

期刊信息：J. Cleaner Prod.

DOI：10.1016/j.jclepro.2024.144393

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本期编辑

姜欣，女，北京建筑大学环境工程专业2024级硕士研究生，主要从事金属-有机骨架材料及衍生物/复合物的设计与可控制备及其环境应用研究。

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