MOFs基材料用于环境污染控制文献整理（2025.01.05-2025.01.11）

为较全面地展示MOFs材料在环境污染控制领域的研究进展并服务于同行，NMTer课题组每周收集整理“MOFs基材料用于环境污染控制”方面的文献资料，通过“MOFs帮助环境”公众号推送。欢迎各位老师和同学关注！同时，欢迎各位老师将您的相关成果在本公众号做专题推送宣传。“赠人玫瑰，手有余香”！

题 目：Efficient radon removal using a Metal–Organic framework with high density of unsaturated Co²⁺ sites

作 者：Kwang Hyun Oh, Seungho Yu, Jung Sub Kim, Kijun Kim, Hyug Hee Han, Yujin Choi, Ki Chul Kim*, Youn-Sang Bae*

摘 要：Rn removal from indoor air is an important issue because Rn is a class ‘A’ carcinogen. Herein, a series of isostructural metal–organic frameworks (MOFs) with a high density of unsaturated metal (M²⁺) sites (M = Mg, Co, Cu, and Zn) were investigated for adsorptive Rn removal from indoor air. Among these MOFs, MOF-74(Co) showed the best Rn removal performance, which is attributed to the strong interactions between Rn and unsaturated Co²⁺ sites. The experimental results matched well with the binding energies from first-principles calculations. Notably, MOF-74(Co) exhibited the highest dynamic adsorption coefficient (14.2 L/g) for Rn adsorption reported to date and better hydrothermal and radioactive stability than other MOFs. These results indicate that a MOF with highly dense Co²⁺ sites is promising for adsorptive Rn removal from indoor air.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2025.159450

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题 目：Recent advances in adsorptive removal of hazardous VOCs by metal-organic-framework-based materials

作 者：Sadia Rehman*, Xianming Zheng, Muhammad Ikram Aujla, Tariq Mehmood

摘 要：Growing concern exists over removing volatile organic compounds (VOCs) from the air due to their carcinogenic/hazardous nature. Considering diverse emission sources and concentrations, VOC removal via adsorption is feasible using porous adsorbents like activated carbon, zeolites, and metal–organic frameworks (MOFs). MOFs surpass others due to their large surface area, pore volume, superior thermal and chemical stability, abundant functional groups, and tunable structure. This review aimed to summarize the state-of-the-art developments made to increase the efficient VOCs removal from air by metal–organic frameworks, their derivatives (metal–organic gel, porous carbon), and composite materials. To begin, this review discusses the fundamental structural properties and surface functionalities of MOFs and MOF-based materials, which serve as primary features in VOCs capture. Secondly, this review emphasizes extensive fabrication strategies (linker functionalization, hierarchical porosity, hydrophobicity, open metal sites, etc.) that have been opted successfully to increase VOC adsorption in MOF-based materials. Finally, we discuss the current challenges faced by MOF-based materials including experimental gaps and constraints, as well as future perspectives in the field of VOC adsorption. This review represents the best effort to invite and engage more researchers to advance air pollution control research.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2025.159257

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题目：Highly efficient unsymmetrical dimethylhydrazine adsorption using alginate microspheres encapsulated with ZIF-67-derived carbons

作者：Jun Su, Ying Jia^*, Menglin Shi, Haiqiang Wang, Qiaorui Wang, Yuanzheng Huang^*, Keke Shen, Jiqing Zhang, Xinyu Zhu

摘要：Demand for efficient methods to remove unsymmetrical dimethylhydrazine (UDMH) from wastewater is driven by concerns regarding its harmful effects on humans and ecosystems. Herein, we designed magnetic ZIF-67@C-ACPs microspheres by encapsulating ZIF-67-derived carbons (ZIF-67@Cs) into alginate/Ca²⁺/poly(acrylic acid) (ACP) double-crosslinked networks for UDMH removal. The batch adsorption experiments demonstrated that the adsorption of UDMH on ZIF-67@C-800 and ZIF-67@C-ACPs primarily involved chemical processes, and the maximum adsorption capacities reached 644.24 and 351.96 mg/g, respectively. ZIF-67@C-ACPs exhibited good resistance to the interferences of pH, coexisting substances, and actual water bodies. Furthermore, ZIF-67@C-ACPs demonstrated excellent reusability and magnetic separation properties, maintaining their adsorption capacity over six cycles without significant loss. The Co leaching from ZIF-67@C-ACPs was significantly lower under acidic conditions than that from ZIF-67@C-800. The adsorption mechanisms included pore filling, hydrogen bonds, and surface complexation. Importantly, an all-in-one device with triple-stage tandem columns was constructed by serially connecting the ZIF-67@C-ACPs filters, ensuring that the residual UDMH content in the effluent complied with China’s discharge standard (<0.5 mg/L). Overall, this study introduces a novel potential for MOF-derived carbons to efficiently treat UDMH wastewater in large-scale applications.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2025.159378

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题目：Carboxyl-rich UiO-66-(COOH)₂ MOF-modified ceramic membranes with anti-fouling resistance toward oil-in-water emulsions based on surface charge

作 者：Shengkai Yang, Jianxian Zeng*, Sicong Yan, Rui Zhang, Xiaoping Huang, Zhengqiu Yuan, Guoqing Liu

摘要：Metal-organic frameworks (MOFs) are increasingly utilized to Improve the separation performance of membranes by adjusting their structure and pore dimensions. However, MOF-modified membranes suffer from unsatisfactory permeate flux during the treatment of oily wastewater. In this study, we present a straightforward and potent methodology for fabricating MOF-modified ceramic membranes with high permeation flux, good hydrophilicity, and strong surface zeta potentials. A special missing linker, UiO-66-(COOH)₂ with an incomplete-coordination linker structure, was achieved through solvent modulation. This modulation variant has a greater abundance of carboxyl groups than the other UiO-66-(COOH)₂ variants, resulting in greater anti-fouling resistance of the modified membrane. Moreover, a ceramic membrane modified with this variant was used to reject emulsified oils. The modified membrane demonstrated a remarkable selectivity (∼95.8 ± 0.7 % of oil rejection) in the separation of anionic oil-in-water emulsions, while maintaining a superb pure water flux (∼1534.3 ± 91.3 L m⁻²h⁻¹), about one-third of the pure water flux of the base membrane (∼4884.7 ± 88.2 L m⁻²h⁻¹). After hydraulic cleaning, the anionic emulsion flux and rejection of the membrane was recovered to 65.0 L m⁻²h⁻¹ and 99.0 %, respectively. In particular, the membrane possessed good anti-fouling resistance to emulsions that carry the same charge as the membrane surface, which was attributed to electrostatic repulsion. These findings show that MOF membranes can be customized to suit different emulsions. Therefore, the MOF-modified ceramic membrane has potential applications in the separation of oily wastewater.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131334

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题目：Designing PMIA/MOF nanofiber membranes for heat-resistant nanofiltration and its application in dye/salt separation

作者：Xiongfei Du, Yumin Sun , Yuxin Zhang , Pu Zhang , Mingxing Chen*, Qinglin Huang*

摘要：Nanofiltration (NF) membranes, prepared using nanofiber membranes as substrate, often face limitations in thermal stability and separation precision. This study presents a novel method for fabricating thermostable NF membrane with a consecutive ZIF-8 functional layer deposited on poly (m-phenylene isophthalamide) (PMIA) nanofiber substrate. Aminated graphene oxide (AGO) nanosheets were fabricated by a nucleophilic ring-opening reaction between triethylenetetramine (TETA) and the graphene oxide (GO). The AGO was then introduced into the PMIA nanofiber membrane surface using an air-electrospray process for the in-situ growth of the ZIF-8 functional layer. The effects of TETA concentrations and AGO integration on the performance of the ZIF-8 functional layer were investigated. The fabricated membrane was utilized for the separation of dye/salt under high-temperature conditions, where, it demonstrated excellent performance, achieving high dye rejection (＞99.1 % for CR), low salt rejection (＜10.0 %), and high permeate flux (68.7 L·m⁻²·h⁻¹·bar⁻¹) during continuous operation for 12 h at 60 ℃. Additionally, the membrane exhibited excellent structural stability, maintaining integrity under twisting and folding, which showed good prospects for industrial preparation and application.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2025.13142

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题目：In³⁺-doped Bi/BiOCl/Bi(In³⁺)-MOF composite for accelerating photocatalytic elimination of antibiotic-resistant bacteria and genes under co-effect of nanoconfinement and reactive oxygen species

作者：Zhengkun Yu , Yunlei Zhou*, Xingyu Liu , Shuqi Gong , Tianyi Sun , Huanshun Yin*, Jingting Kang

摘要：A Bi/BiOCl/Bi(In³⁺)-MOF Z-scheme heterojunction enriched with positive electric charges on the surface caused by In³⁺ doping was prepared by a one-step solvothermal method. Photodegradation of antibiotics (tetracycline, amoxicillin, ceftriaxone), antibiotic-resistant Escherichia coli (AR E. coli), the tetA gene they carried, and Fusarium graminearum was investigated. The experimental results showed that Bi/BiOCl/Bi(In³⁺)-MOF sample possessed efficient photodegradation activity, with a removal of 107.34 CFU·mL⁻¹ against AR E. coli in 80 min, 83.0 % and 4.89 log10 copies·mL⁻¹ for tetracycline and tetA gene in 120 min, respectively. Zeta potential test and adsorption capture experiment confirmed that Bi/BiOCl/Bi(In³⁺)-MOF surface was rich in positive charges and had a strong nanoconfinement effect on negative-charged bacteria and ARGs, which shorten the time for the active substances produced by photocatalysis to come into contact with bacteria and ARGs, thereby improving the photocatalysis degradation effect. Finally, Bi/BiOCl/Bi(In³⁺)-MOF sample was applied and discussed for the removal of complex colonies from duck farm wastewater.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131318

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题目：Multifunctional MOFs-polymer composite nanofibrous membrane for radioactive iodine aerosols efficient purification

作者：Cheng Liu , Chuan Tan Yangzhou Fan , Yipeng Yan , Chuan Shan , Jingsong Xu , Guangyuan Chen , Renren Wang , Kai Du*, Xin Chen*, Tao Duan*

摘要：The efficient purification of radioactive iodine aerosols is essential in developing nuclear energy. Using existing materials and processing processes, it is hard to efficiently purify iodine aerosols and iodine gas simultaneously. Membranes with excellent adsorption and filtration properties are suitable candidates for efficient purification. A simple one-step synthetic strategy developed from the electrospinning method fabricates a multifunctional composite nanofibrous membrane material (ZIF-8@PVP/PAN). The ZIF-8 crystals coated the fiber surface, and some were embedded into the PVP/PAN fiber without significantly changing the fiber diameter distribution. The ZIF-8@PVP/PAN membrane shows outstanding adsorption properties with a maximum adsorption capacity of 2898 mg/g for iodine gas and 456 mg/g for methyl iodide. In addition, at a face velocity of 5 cm/s, it exhibits excellent filtration efficiency of 99.91 % for PM_0.3 with a much lower pressure drop of 79 Pa. Combine the DFT theoretical calculations and characterization results, it can be considered that active adsorption sites provided by the PVP/PAN fiber framework and the loaded ZIF-8 enhanced the iodine adsorption together. The efficient filtration results from the synergistic effect of interception, adsorption, and electrostatic attraction. The ZIF-8@PVP/PAN composite membrane with excellent multifunctional performance and outstanding thermal and radiation stability provides a potential material for efficiently purifying iodine aerosols and iodine gas in reprocessing plants under practical working conditions.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131335

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题目：Robust and anti-biofouling bio-based aerogel with Schiff base network stabilized MOFs for efficient removal of tartrazine dye and U(VI) ions

作者：Cuiyun Liu*, Menghui Zhao , Hui Liu , Jun Zhang , Zihao Hu , Yuhan Zhang , Xinchang Pang*

摘要：Tartrazine (TAR), widely used as a synthetic food dye, and U(VI), primarily originating from nuclear industry effluents, pose serious environmental and health risks due to their toxicity and persistence. However, many existing adsorbents suffer from low capacity, poor stability, and limited reusability. Herein, A bio-based aerogel adsorbent (NDC) with a stable three-dimensional porous network structure was prepared through a Schiff base reaction between dialdehyde-functionalized nanocellulose fibrils (DNCFs), chitosan (CS), and aminated metal–organic frameworks (MOFs). The synergistic effect of MOFs, DNCFs, and CS resulted in high adsorption capacities of 689.66 mg/g for TAR and 285.72 mg/g for U(VI) at a temperature of 303 K, respectively. Additionally, the Schiff base chemical bonds firmly anchored the MOFs in the NDC aerogel, providing a compressive strength of 547.4 kPa at 70 % strain. Furthermore, due to the antibacterial properties of the amino groups on CS and MOFs, the NDC aerogel demonstrated excellent anti-biofouling performance. The results suggest that bio-based NDC aerogel is an efficient and prospective for the removal of TAR and U(VI) from wastewater as an adsorbent.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131277

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题目：Strategic tuning of GO ratios in CuBTC-GO nanocomposites for next-generation tetracycline adsorption: A deep dive into isotherms, kinetics, and thermodynamics

作者：Palkaran Sethi , Sanghamitra Barman* , Soumen Basu*

摘要：The increasing environmental persistence of tetracycline antibiotics demands effective removal solutions to safeguard water quality. This study investigates the adsorption of tetracycline hydrochloride using a copper benzene-1,3,5-tricarboxylate (Cu-BTC) hybridized with graphene oxide (GO). The CuBTC-GO composite, synthesized in varying ratios (1:1, 1:3, 3:1), was extensively characterized using field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA), zeta potential analysis, and Brunauer-Emmett-Teller (BET) surface area analysis, confirming its robust structure, thermal stability, and high porosity. Adsorption experiments were optimized by systematically varying key parameters, including adsorbent dosage, pollutant concentration, temperature, pH, stirring speed, and time. The composite achieved a remarkable removal efficiency of 97.7 % for 25 ppm tetracycline at pH 10 within 90 min. Reusability tests confirmed consistent performance over six cycles, while real-world medical wastewater treatment demonstrated 65 % removal efficiency. The adsorption process was comprehensively analyzed using six equilibrium isotherm models (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Halsey, and Harkins-Jura). The Langmuir model provided the best fit (R² = 0.99725), indicating monolayer adsorption with chemisorption as the dominant mechanism (adsorption energy:12.121 kJ/mol). Additionally, π-π stacking, hydrogen bonding, electrostatic interactions, and pore filling contributed significantly to adsorption confirmed by post-adsorption characterizations (XRD, FTIR, BET, FESEM-EDS). Kinetics were evaluated using five models (pseudo-first-order, pseudo-second-order, Elovich, intraparticle diffusion, and liquid film model) and the pseudo-second-order model best described the adsorption (R² = 0.99989), with a rate constant of 0.0151 min−1, indicating a chemical reaction-controlled process. Thermodynamic studies revealed the endothermic nature of the process (ΔH = 82.361 kJ/mol), its spontaneity (ΔG = -1.3077 kJ/mol), and less randomness at the solid–liquid interface (ΔS = -0.251 kJ/mol K). This study provides a comprehensive chemical engineering approach to adsorption process design, integrating detailed isotherm, kinetic, and thermodynamic analyses. The CuBTC-GO composite exhibits superior adsorption performance for a very high concentration of tetracycline, faster kinetics, and enhanced reusability, compared to the existing literature positioning it as a promising material for the sustainable remediation of antibiotic-contaminated wastewater.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131311

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题目：Efficient bimetallic metal–organic framework derived magnetic Co/N-PC-800 nanoreactor for peroxymonosulfate activation and carbamazepine degradation

作  者：Qiao-Qiao Huang, Yu-Mei Wang, Xun Fu, Xiao-Li Hu, Jia-Wei Wang*, Zhong-Min Su*

摘 要：Co/N-PC-T precursors were obtained in this study using solvent heating and immersion methods. Subsequently, simple pot calcination of Co@Zn-MOF (metal–organic framework) and dicyandiamide green precursors was carried out to prepare N-doped magnetic carbon materials, known as Co/N-PC-T. Co/N-PC-T were employed to activate peroxymonosulfate (PMS) and degrade developing pollutants. The Co/N-PC-800 catalyst exhibited excellent catalytic activity. When Co/N-PC-800 was used for PMS activation, carbamazepine (CBZ) degradation could exceed 98% within 30 min, with a degradation rate of 0.23 min^-1, which was 4.77, 5.73, and 1.28 times higher than that of Co/N-PC-600 (0.05 min^-1), Co/N-PC-700 (0.04 min^-1), and Co/N-PC-900 (0.18 min^-1), respectively. The Co/N-PC-800/PMS system contained radical and non-radical pathways, which were further confirmed by electron paramagnetic resonance (EPR) tests, and the corresponding catalytic reaction mechanisms were proposed. The breakdown pathways of CBZ in the Co/N-PC-800/PMS system were described, and the ecotoxicity of CBZ and its degradation by-products was assessed. After five cycles, Co/N-PC-800 was shown to be stable and recyclable. This study proposes a novel synthetic technique for developing MOF-derived environmental functional materials.

期刊信息：Environmental Science: Nano

DOI：10.1039/D4EN00898G

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本期编辑

付乙兰，女，北京建筑大学资源与环境专业2024级硕士研究生。主要研究方向为金属-有机框架材料及其衍生物的设计、制备及其在水环境修复领域的应用。

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