MOFs基材料用于环境污染控制文献整理（2024.9.21-9.27)

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：Recognizing the relevance of non-radical peroxymonosulfate activation by co-doped Fe metal-organic framework for the high-efficient degradation of acetaminophen: Role of singlet oxygen and the enhancement of redox cycle

作者：Xinran Li, Jian Chen, Zaiyu Liu, Chengyu He, Jian Pang, Lilei Zhang, Fenglin Tang*, Xiupei Yang*

摘要：A bimetallic MOF derivative consisting of Fe and Co (Fe/Co₂-MOF) by Co-doping MIL-101(Fe) was successfully synthesized for peroxymonosulfate (PMS) activation in acetaminophen (N-Acetyl-Para-Amino-Phenol, APAP) degradation. The presence of Co significantly accelerated the transfer of electrons due to the synergistic effect between Fe and Co bimetallic sites. Specifically, the reaction rate constant of APAP in the Fe/Co₂-MOF + PMS system was three orders of magnitude higher than that of MIL-101(Fe) alone and 90 times higher than that of the MIL-101(Fe) + PMS system, respectively. At room temperature, 100 % of the APAP was degraded in 15 min with a Fe/Co₂-MOF concentration of 0.05 g/L and a PMS concentration of 0.8 mmol/L across a wide pH range from 3 to 9. High-valence metal species (Co^Ⅳ and Fe^Ⅳ) and electron transfer-dominated nonradical processes were responsible for the APAP degradation. Although singlet oxygen (¹O₂) was identified as the main active species in our study, the relative contribution of ¹O₂ was negligible. The catalytic performance was particularly notable in the practical implementation of hospital sewage treatment. However, it is still urgent to seek ways to relieve cobalt leaching of Fe/Co₂-MOF. This strategy of Co-doping provides a clear illustration of modulating MIL-101(Fe) ultimately maximize their catalytic efficiency in PMS activation for water purification.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.156081

论文链接：

题目：Incorporating hydrophilic amino-modified UiO-66 nanoparticles into polyphenylsulfone membrane for improved dye/salt separation

作者：Panpan Liu, Qinglei Xing, Runqing Huang, Jiafei Lyu*, Peng Bai^*

摘要：This study explores the incorporation of three Zr-based MOFs with varying pore structures (UiO-66, NU-906, and NU-1008) into a polyphenylsulfone (PPSU) matrix for dye and salt separation, highlighting that UiO-66/PPSU membrane exhibits superior permeability and separation performance. To enhance the compatibility of the MOF with the matrix and improve the antifouling performance, hydrophilic diethylenetriamine was grafted onto UiO-66. The strengthened hydrogen bonding between DETA-UiO-66 and PPSU improved its dispersibility in the polymer matrix and increased the mechanical strength of the MMMs. Moreover, the incorporation of hydrophilic DETA-UiO-66 nanoparticles enhanced the pore structures and hydrophilicity of the DETA-UiO-66/PPSU membranes, enabling them to exhibit higher permeability and antifouling performance. The 1.0wt.%DETA-UiO-66/PPSU membrane exhibited a substantial increase in water flux to 16.52 LMH·bar⁻¹, threefold and double higher than the pure PPSU membrane and UiO-66/PPSU membrane. Meanwhile, high rejection rates of 99.3 % for reactive orange 16, 99.6 % for brilliant blue G, and 99.7 % for rose Bengal were demonstrated with low NaCl retention rate of 7.69 % at a high salt concentration of 5000 mg/L, achieving a high salt/dye separation factor of 184.6 under the size sieving and the Donnan exclusion mechanisms. Moreover, integrating DETA-UiO-66 significantly improved the antifouling performance with the flux recovery rate increased from 71.6 % to 95.2 % and the irreversible fouling ratio decreased to 4.8 %. DETA-UiO-66/PPSU membrane also exhibited excellent stability where the mechanical integrity and separation performance were maintained in the 100-hour dye/salt separation process. This research highlights the promising application of DETA-UiO-66 in the fabrication of advanced mixed matrix nanofiltration membranes and offers valuable insights into the integration of various modified hydrophilic MOFs for the design of efficient water treatment membranes.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.156096

论文链接：

题目：Highly Mesoporous Zr-Based MOF-Fabric Composites: A Benign Approach for Expeditious Degradation of Chemical Warfare Agents and Simulants

作者：Mai O. Abdelmigeed, John J. Mahle, Gregory W. Peterson, Gregory N. Parsons

摘要：Recent research has demonstrated the degradation of organophosphonates through hydrolysis using microporous UiO–66–NH₂-fabric composites. Yet, challenges remain due to the limitations of organophosphonates accessing active sites in large, engineered granules. To address this, an innovative approach to integrate mesoporous UiO–66–NH₂ onto various fabrics is provided, thereby overcoming previous mass transfer limitations. Mesoporosity in the UiO–66–NH₂-fabric is attributed to the amphoteric cocamidopropylbetaine (CAPB) surfactant which templates the mesochannel construction. Unexpectedly, because the synthesis is aqueous, benign, low temperature (60 ^oC), and avoids strong acids and toxic solvents, it is compatible with fragile supports such as untreated cotton. The UiO–66–NH₂-fabric composite formed using treated polypropylene (PP) attains a BET specific surface area of 360 m² g⁻¹_comp. Remarkably, the mesoporous UiO–66–NH₂-composites exhibit a pore volume as large as 0.2 cm³ g⁻¹_comp, 33% in the mesoporous range, which is higher than other previous reports. Practically, the mesoporous UiO–66–NH₂-treated PP composite enhances the rate of methyl paraoxon (DMNP) degradation, showing a t_1/2 value that is 15 times faster than microporous UiO–66–NH₂ composites measured under the same conditions. Similar trends are observed in the degradation of actual nerve agents. These composites hold significant potential across diverse applications, including filtration, protection, and catalysis.

期刊信息：Small

DOI：10.1002/smll.202405831

论文链接：

题目：Amino functionalized zeolitic imidazolate framework-8 coated cellulose aerogel for enhanced air purification

作者：Zhongguo Wang , Qing He , Yang Liu , Changshuo Yu, Xiong-Fei Zhang*, Xiangjin Kong*

摘要：Human activities generate large quantities of air pollutants, and particulate matter (PM) in the air poses a serious threat to public health. Nanofiber filters with surface-loaded metal–organic frameworks (MOFs) are promising materials for the capture of PM. Herein, this work creatively fabricated an air filter by anchoring amino-functionalized ZIF-8 on the surface of cellulose aerogel (NZCA) by in situ growth approach. The excellent compatibility between ZIF and cellulose was demonstrated by XRD, FT-IR, SEM and XPS characterization techniques. The functionalized ligand introduces –NH₂, and the polar –NH₂ group enhances the electrostatic interaction between ZIF-8-NH₂ and PM, resulting in NZCA with superior PM filtration performance (filtration efficiency and quality factor: PM_2.5: 92%, 0.054; PM₁₀: 96%, 0.068) compared to ZCA without sacrificing the pressure drop. Furthermore, ZIF-8-NH₂ modified cellulose filters were easy to regenerate and exhibited excellent reusability. This work paves the way for the rational design of ligand-modified MOF/cellulose filters for the efficient removal of PM from air, which has important implications for solving environmental problems and energy crises.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.129741

论文链接：

题目：Energy-efficient removal of trace VOCs from humid air using metal-organic gel derived porous carbon

作者：Sadia Rehman, Xianming Zheng, Pengyi Zhang*

摘要：The development of granular adsorbents for the efficient capture of low-concentration volatile organic compounds (VOCs) from humid air are highly desirable. Herein, we report the synthesis of granular ZIF-8 monolith (_monoZIF-8) featuring high surface area (2312 m²/g) and mesoporous structure by shortening the synthesis time and optimizing the reactant concentrations, which was further carbonized at 1000 ^oC to obtain porous granular carbon. As-prepared ZIF-8-C1000 exhibited high surface area (1623 m²/g), hierarchical porous structure (0.5–10 nm) and hydrophobicity (water contact angle 145.8°), thus it showed very high adsorption performance for trace VOCs like toluene and hexanal under both dry and humid conditions (relative humidity 30 %-80 %) at 25 ^oC, much higher than commercial activated carbon (AC) such as BPL-AC, coconut shell AC, and representative MOFs including HKUST-1, _monoHKUST-1, _monoMIL-100(Fe), MIL-101(Cr) and MOF-235. Additionally, ZIF-8-C1000 could be rapidly regenerated under mild temperatures (60 ^oC to 80 ^oC), while BPL-AC requires a higher desorption temperature and more time due to disordered porosity. The exceptional adsorption and desorption performance of granular ZIF-8-C1000 over BPL-AC can be attributed to its interconnected micropores and mesopores.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.129695

论文链接：

题目：Fe(III)-incorporated UiO-66(Zr)–NH₂ frameworks: Microwave-assisted scalable production and their enhanced photo-Fenton degradation catalytic activities

作者：Thi Minh Nguyet Bui*, The Ky Vo*, Nguyen Hoang Yen Phuong, Van Hung Nguyen, Van Cuong Nguyen, Quoc Hung Nguyen, Nhan Thi Thanh Dang

摘要：In this work, the photocatalytic feasibility of UiO-66(Zr)–NH₂ was tuned by combining a scalable producing approach and incorporating Fe³⁺. Different contents of Fe³⁺ were effectively incorporated into the UiO-66(Zr)–NH2 frameworks utilizing a microwave-assisted continuous flow tubular reactor within 10 min. It was observed that with increasing the Fe³⁺ content from 0.5 to 1.0, 2.0 and 3.0 M %, the production rate diminished from ∼ 1.72 to 1.65, 1.55, and 1.46 g/h, respectively. The hybrid Fe@UiO-66-NH₂ (Fe@UON) showed enhanced light absorption and charge carrier separation efficiency owing to the newly formed heterostructures, Zr-O-Fe linkages, and –H₂N:→ Fe³⁺ chelating. The optimal Fe@UON catalyst achieved the highest photo-Fenton degradation efficiency of ∼ 96 % towards tetracycline (TC) under energy-saving visible LED light (VLEL) conditions. The photodegradation was predominantly governed by the photo-induced species of ·O₂^–, h⁺, and •OH and facilitated by the Fe³⁺/Fe²⁺ cycles. At the same time, LC/MS analyses detailedly revealed the reaction pathways for the degradation. After several consecutive tests, the constructed hybrid Fe@UiO-66-NH₂ catalysts maintained good catalytic durability, and there was an insignificant Fe leak to the environment. The findings showed that hybrid Fe³⁺@UiO-66(Zr)–NH₂ derived from energy-effective, environmentally and scalable methods could be a good material for treating antibiotic-polluted effluents.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.129723

论文链接：

题目：Magnetic nano-networked graphene@metal-organic framework derived iron oxide with enhanced adsorption and photocatalytic performance for wastewater treatment

作者：Haiyang Fu , Yuan Qiao , Bo Gao* , Zhuang Liu , Gaoyu Wei , Xin Lan , Yue Liu , Shuhui Wei , Amor Abdelkader , Ali Reza Kamali*

摘要：This study presents a simple mechanical exfoliation-thermal treatment process to produce iron oxide embedded into nano-networked graphene with abundant surface oxygen vacancies. The nano-networked graphene@iron oxide product is characterised as a high-performing adsorbent for removing organic dye malachite green from wastewater, exhibiting an adsorption capacity of 240.22 mg/g, following the pseudo-second-order kinetic adsorption model. Notably, the excellent dual adsorption - photocatalysis performance of the nano-networked graphene@iron oxide can be attributed to its large specific surface area (184 m²/g) and high porosity (2.37 cm³/g). Under LED light (385 nm) irradiation, the 0.4 g/L nano-networked graphene@iron oxide material at pH=9 exhibits photocatalytic performance with 99.4 % MG degradation after 3 h of photocatalysis. Free radical trapping experiments show that electrons and vacancies are the main reactants in photocatalysis. The moderate band gap of the material (1.41 eV) combined with the presence of conductive graphene contributes to the efficient generation of active radicals. The fabrication of this dual adsorbent - photocatalyst is simple, inexpensive and controllable, providing an economic and efficient option for degrading organic pollutants.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.129482

论文链接：

题目：Zeolitic imidazolate frameworks (ZIF-8 & ZIF-67): Synthesis and application for wastewater treatment

作者：Muhammad Altaf Nazir*, Sami Ullah, Muhammad Umar Shahid, Ismail Hossain, Tayyaba Najam, Mostafa A. Ismail, Aziz ur Rehman, Md Rezaul Karim*, Syed Shoaib Ahmad Shah*

摘要：Taking appropriate measures for waste-water treatment is important in order to respect everyone’s fundamental right to clean and safe water on Earth. Current review encapsulates the newest approaches of fabricating Zeolitic imidazolate frameworks (ZIFs)-based nanocomposites for wastewater treatment. (ZIFs) are a typical type of porous materials with zeolitic topology that syndicate the benefits of zeolite and traditional metal–organic frameworks (MOFs). In recent years, much attention has been devoted to the fabrication and application of ZIFs-based nanocomposites due to their outstanding chemical and thermal stabilities, tunable porosity and considerably high surface area. Furthermore, coalescing the benefits of ZIFs with other materials and compounds which have better results than that of pristine and pure ZIFs. The exceptional properties of ZIFs endue its outstanding adsorption capability and virtuous host aptitude for materials used as photocatalysis, which makes it be a prestigious material in the decontamination of polluted water. The current research development of ZIFs (ZIF-8 and ZIF-67) nano-composites as photocatalysts and adsorbents for the exclusion of contaminants from water is critically reviewed. Various factors which affect its performance and mechanism of action are also debated. This review endeavors to lay the systematic awareness for the application of ZIFs (ZIF-8 and ZIF-67) nano-composite in real industrial wastewater treatment and delivers new ideas for fabricating highly competent ZIFs based photocatalysts and adsorbent materials. For the purpose of enlightening the whole capability of ZIFs based nanocomposites in wastewater treatment recycling water, current challenges are presented and future research possibilities are anticipated at the end.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.129828

论文链接：

题目：Hydrogel-involved portable ratiometric fluorescence sensor based on Eu³⁺/CDs-modified metal-organic framework for detection of ofloxacin and tetracycline

作者：Junxue Liu, Wen Li, Jianyun Li, Jiyang Li*

摘要：Highly selective and sensitive monitoring ofloxacin and tetracycline residues is meaningful for food safety and environmental protection. Herein, benefitting from strong coordination capability and good porosity of metal-organic framework UiO-67b, the dual-functional fluoroprobes were developed based on UiO-67b post-modified by luminescent Eu³⁺ and carbon dots (CDs). Eu³⁺/CDs-modified UiO-67b exhibited dual recognition sites with controllable red and blue emissions, which could be quenched by ofloxacin and tetracycline through internal filtering effect resulting in distinct color change from red to blue. Based on this, the ratiometric fluorescent assay was first established towards ofloxacin and tetracycline in the ranges of 0–60/0–10 µM, reaching a low limit of detection of 22/27 nM. Satisfactory recoveries of 98.5–103.7 % in real samples as well as visual analysis endow such intelligent sensing platform great potential on practical evaluating antibiotic residues in food.

期刊信息：Sens. Actuators, B

DOI：10.1016/j.snb.2024.136573

论文链接：

题目：Precisely controlling structure defects of Quasi-MIL-125 for improving its catalytic performance

作者：Shasha Hong, Peng Wang*, Erdong Li, Shang Guo*

摘要：Quasi-Metal-Organic Frameworks (Quasi-MOFs) are a class of promising porous materials with unique structural defectives. It is of significant importance to probe into the systematic relationship between catalytic performance of Quasi-MOFs and porous structure, metal nodes and ligands. Herein, a solvent-assisted strategy was developed to finely fabricate Quasi-MIL-125 with various structure defects by varying reaction temperature, where the ligands were removed by controlled esterification to create hierarchical pore and the metal nodes were transformed into TixOy to enrich catalytic active sites. Meanwhile, a morphological transformation of Quasi-MIL-125 was observed from disk-shape to nanosheets during this process. As a result, Quasi-MIL-125-130 displayed high catalytic performance in photocatalytic Cr(VI) reduction due to the strong synergistic effect between exposed metal active sites and ligands. What is more, Pd/Quasi-MIL-125-130 exhibited significantly enhanced catalytic activity in styrene hydrogenation reaction owing to its enriched porous structure. More importantly, functional Quasi-MOF crystals with different structural defects could be gently fabricated and used to enhance target functions.

期刊信息：Appl. Surf. Sci.

DOI：10.1016/j.apsusc.2024.161318
论文链接：