MOFs基材料用于环境污染控制文献整理（2024.11.10-2024.11.16）

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：Versatile POMOF-based materials: Synthesis, mechanism, topology and 

catalytic applications

作者：Zhengxiang Sun,Rui Wang*,Ivan V. Kozhevnikov

摘要：The interactions and contradictions among energy, resources, environment, human health and social development are perennial subjects of scientific research. Multifunctional, adjustable, and high-performance composite catalysts are an effective means of coordinating and resolving the tensions between social development, energy and the environment. Polyoxometalate chemistry, represented by polyoxometalates (POMs), has made a breakthrough due to its superior catalytic activity and wide range of applications. This has significantly promoted the combination of catalytic chemistry and production practice. Metal-organic frameworks (MOFs) are a class of porous materials that combine organic and inorganic properties. MOFs are highly crystalline and have a flexible structure with a large surface area. Combining POMs with MOFs to form POMOF-based materials offers the advantages of both materials and a synergistic effect greater than the sum of its parts. Although there have been several reviews on POMOF composites, especially in the field of catalysis, comprehensive discussions on the latest advances and specific applications remain limited. To promote the development of the field and explore the conformational relationship in depth, this review focuses on the frontiers of catalysis of POMOF-based materials. It discusses the composition, coupling strategy, and reaction mechanism of these materials using pioneering classifications and descriptions. A comprehensive review of research work in the field, classified by application areas, is presented to stimulate catalysis research and provide a new framework, new perspectives, and new horizons.

期刊信息：Coord. Chem. Rev.

DOI: 10.1016/j.ccr.2024.216302

论文链接：

题目：Host-guest interactions in the confined spaces of metal–organic frameworks: Design principles, characterizations, and applications

作者：Yifang Zhao, Lian Wu,Kun Wu,Heng Zeng,Rong-Jia Wei,

Hao Pang*,Weigang Lu*, Dan Li*

摘要：Metal–organic frameworks (MOFs) are revolutionizing porous materials with their incredible structures and functionalities that have been extensively explored in many fields. Unlike traditional porous materials, MOFs offer a unique opportunity for precise design and modification of the porosities and pore environments. Their nanoscale confined spaces with specific shapes and surface functionalities can selectively interact with certain guest molecules through host-guest interactions, unlocking enhanced performance and related mechanisms that were previously undiscovered. Through advanced experimental and theoretical techniques, the high crystallinity of MOFs allows for detailed and in-depth studies of the structure-performance relationships, leading to breakthroughs in design and optimization. This review delves into recent advancements in the construction, characterization, and host-guest applications of MOF-based systems, showcasing their design strategies for remarkable functionality, porosity, and flexibility. The latest progress in adsorption, separation, catalysis, energy storage, crystalline sponge (CS), and sensing are discussed, unraveling the endless possibilities of MOFs and their challenges.

期刊信息:Coord. Chem. Rev.

DOI:10.1016/j.ccr.2024.216302

论文链接:

题目：In-situ immobilization of Fe PBA in the zeolite structure for efficient degradation of benzalkonium chloride: Towards compressed reaction site loss and promoted PMS utilization

作者：Qing Zhong, Ting Zhang, Zhi Huang, Longhui Su, Yuwei Xue, 

Ran Gao, Han Feng*, Junming Hong*

摘要：Advanced oxidation processes based on peroxymonosulfate (PMS) for the removal of quaternary ammonium compounds have challenges, including high metal leaching and excessive oxidant consumption, which limit their practical application. In this work, Fe atoms were firstly intercalated into the structure of the zeolite through ion exchange and then transformed into Fe prussian blue analog (Fe PBA) in-situ through coprecipitation followed by a calcination process. Through immobilizing the reactive catalytic center to a specific site, the leaching rate of Fe was compressed to about 0.25 mg·L^-1, accounting for only 6 % of the Fe PBA without zeolite immobilization. The incorporation of zeolite has triggered increased hydrophilicity while retaining the negatively charged property of Fe PBA, implying enhanced dispersity of the catalyst in the aqueous environment and attraction towards benzalkonium chloride (BAC) and PMS molecules. Intuitively, the reactive oxidative species (ROS) generated through PMS activation require less diffusion distance to encounter BAC molecules, as they are confined within the microenvironment around the surface due to this weak electrostatic attraction. Therefore, an increase in ROS utilization efficiency was observed with a significant reduction in PMS dosage. Remarkably, 99.83 % of BAC (10 mg·L^-1) was eliminated within 60 min with only 0.5 mM PMS, which is much lower than the reported 5–100 mM PMS. More importantly, the post-annealing brought an increased amount of graphitic carbon, which enhanced singlet oxygen production and further improved the degradation efficiency of BAC molecules due to its unique selectivity. This study presents a feasible strategy for simultaneously enhancing PMS utilization and reducing metal ion leaching.

期刊信息：Chem. Eng. J.

DOI:10.1016/j.cej.2024.157655

论文链接:

题目：Rhombic dodecahedral ZIF-8-supported CuFe₂O₄ triggers sodium percarbonate activation for enhanced sulfonamide antibiotics degradation: Synergistic roles of heterostructure and photocatalytic mechanisms

作者：Junge Xu, Weihao Yu, Ziwei Zhang, Fubin Deng, Shengkong Wang, Rusen Zou*, Yingmu Wang*, Baoling Yuan

摘要：Pollution from extensive sulfonamide antibiotic use is a critical research focus, particularly in the remediation of these antibiotics using composite materials. This study employed a CuFe₂O₄/ZIF-8 composite to activate sodium percarbonate (SPC) for the photo-Fenton-like degradation of the sulfonamide antibiotic sulfamethoxazole (SMX). The optimal conditions for SMX degradation were determined using the CuFe₂O₄/ZIF-8/SPC/Vis system: a ZIF-8 composite ratio of 40 %, catalyst dosage of 0.15 g/L, SPC concentration of 0.8 mM, and initial pH of 3.0, achieving complete SMX removal within 30 min. After five cycle tests, the leaching rates of copper and iron ions were 0.179 mg/L and 0.376 mg/L, respectively, significantly lower compared to the use of CuFe₂O₄ alone as the catalyst (Cu: 0.46 mg/L, Fe: 1.43 mg/L). The radicals present in the system were identified, with their contribution rates ranked from highest to lowest as follows: ·OH > h⁺> ·O₂^– > CO₃·^– > ¹O₂. Further mechanistic investigations revealed that the heterogeneous structures in CuFe₂O₄/ZIF-8 enhanced the efficiency of the photo-Fenton-like reaction by facilitating electron transfer. This study introduced an innovative approach for antibiotic treatment using the CuFe₂O₄/ZIF-8 composite under visible light irradiation and broadened the technical framework of SPC-based advanced oxidation processes (AOPs) for treating wastewater.

期刊信息：Chem. Eng. J.

DOI:10.1016/j.cej.2024.157650

论文链接:

题目：Facile synthesis of Metal-Organic Framework/Chitosan cryogel as a robust Scavenger for Diclofenac sodium

作者：Yanke Shi, Lijin Huang*, Yu Bai, Lei Ouyang, Huiyu Zhao, Xinquan Wang, Qin Shuai*

摘要：Diclofenac sodium (DS), a commonly detected contaminant in aquatic environments, poses a a significant risk to both the ecological balance and the safety of aquatic products. Therefore, efficient removal of DS from water is ergently needed but remains a major challenge. In this study, an environmentally friendly Fe-based metal–organic framework/chitosan (NH₂-MIL-53(Fe)/CS) cryogel was prepared through a Schiff base condensation reaction under mild conditions. Taking advantage of the catalytic role of the MOF in accelerating the reaction between CS and 1,3,5-triformylphloroglucinol, NH₂-MIL-53(Fe) powders were incorporated into the polymeric networks within 30 s. Owing to the rich binding sites, the resulting NH₂-MIL-53(Fe)/CS cryogel demonstrated remarkable efficacy in eliminating DS from water. The adsorption process reached equilibrium within 120 min with a maximum adsorption capacity of 728.6 mg·g⁻¹. A comprehensive mechanistic investigation revealed that the exceptional adsorption capability of the NH₂-MIL-53(Fe)/CS cryogel for DS was attributed to the synergistic effect of multiple interactions, including favorable hydrophilicity, electrostatic forces, π-π stacking, hydrogen bonding, and coordination. Thus, this study provides a straightforward and rapid synthesis route for MOF/CS cryogel, offering a promising adsorbent that combines exceptional adsorption performance with ease of separation. The resulting MOF/CS cryogel holds great potential for the treatment of DS-contaminated wastewater.

期刊信息：Chem. Eng. J.

DOI:10.1016/j.cej.2024.157593

论文链接:

题目：Iron-based nitrogen-rich metal-organic framework structure for activation of hydrogen peroxide and peroxymonosulfate for ultra-efficient tetracycline degradation

作者：Si-Han Zhou, Yun Yang, Rui-Dong Wang, Yujie Cui, Siping Ji, 

Lin Du, Feng-zhi Jiang*

摘要：Fe-based metal–organic frameworks (Fe-MOFs) have been used to catalyze the degradation of organic pollutants; however, the underlying mechanism remains unclear. In this study, we prepared Fe-MOF catalysts featuring a three-dimensional ordered structure and active Fe-N₄ coordination centers using self-designed polypyrazole compounds as ligands. Because the coordination centers are similar to the classical single-atom Fe-N₄ active neutral structure, Fe-MOFs exhibit excellent performance in activating hydrogen peroxide (H₂O₂) and peroxymonosulfate (PMS) for the degradation of antibiotics. Moreover, the two adjacent nitrogen atoms in pyrazole strengthen the interaction with active neutral Fe, thereby enhancing the efficiency and selectivity of the catalytic sites. In the presence Fe-MOF/H₂O₂, a free radical process involving hydroxyl radicals (radical ·OH) is activated to achieve a degradation rate of 98.36 % for tetracycline (TC) within 10 min. In a Fe-MOF/PMS system, 97.01 % of TC can be degraded within 10 min through a non-free radical process with singlet oxygen (¹O₂) as the primary active species. The high degradation efficiency of Fe-MOF is primarily attributed to its highly catalytically active structure, which exerts a van der Waals force effect on the pollutants, thereby facilitating electron transfer between the pollutants and active centers. This shortens the distance between the pollutants and Fe catalytic center, enhances electron transfer, and promotes the chemical adsorption of H₂O₂ and PMS to form FeN₄-H₂O₂ and FeN₄-PMS, respectively. Additionally, the strong coordination within the Fe-N₄ pyrazole structure significantly suppresses Fe leaching, facilitating a stable adsorption configuration.

期刊信息：J. Colloid. Interf. 

DOI:10.1016/j.jcis.2024.11.004

论文链接:

题目：Investigation of efficient adsorption-electrochemical degradation performance of ZIF-8/MWCNTs nanocomposites toward 2,4-dichlorophenol

作者：Xinyue Liang , Xiaolong Yao*, Sijie Chen , Wei Wang , Hong Zhu , Qingwei Bu , Zheng Liu

摘要：The highly toxic and recalcitrant organic pollutant, 2,4-dichlorophenol (2,4-DCP), is commonly found in wastewater. Therefore, it is critical to investigate novel techniques for the efficient removal of 2,4-DCP from wastewater. The present study employed a one-step synthesis method to fabricate ZIF-8/multi-walled carbon nanotubes (ZIF-8/MWCNTs) nanocomposites with well-defined mesoporous structures, which were subsequently coated onto carbon cloth (CC) to form the anode ZIF-8/MWCNTs/CC. Subsequently, the adsorption performance of ZIF-8/MWCNTs toward 2,4-DCP and the adsorption-electrochemical degradation performance of ZIF-8/MWCNTs/CC toward 2,4-DCP were investigated. ZIF-8/MWCNTs exhibit exceptional adsorption capacity and rate toward the 2,4-DCP. At 303 K, it achieved a saturated adsorption amount as high as 1056.78 mg·g^-1 within only 30 min of reaching equilibrium. Moreover, when coated on CC substrates, the internal pore structure of ZIF-8/MWCNTs is effectively exploited during the adsorption. In addition, the incorporation of MWCNTs enhances the conductivity of the ZIF-8/MWCNTs/CC electrodes, leading to reduced resistance and improved electron transfer rate. Notably, ZIF-8/MWCNTs/CC enabled complete removal of a 25 mg·L^-1 solution of 2,4-DCP within only 90 min and a 50 mg·L^-1 solution within 120 min. Furthermore, the degradation mechanism of 2,4-DCP was analyzed by means of DFT modeling theoretical calculations and intermediate product determination analysis, while evaluating the toxicity of the generated material was evaluated. This study provides improved solutions and strategies for the treatment of chlorophenolic compound pollution in wastewater.

期刊信息：Sep. Purif. Technol.

DOI:10.1016/j.seppur.2024.130385

论文链接:

题目：Wood meet MOFs: Facile, green, and highly selective adsorbent for textile wastewater

作者：Hanmeng Yuan , Zonghang Liu, Zhimin Zhao , Hongshuai Gao*, 

Yi Nie*

摘要：Owing to their unique physicochemical features, ionic liquids (ILs) are extensively utilized to dissolve cellulose for the preparation of regenerated cellulose fibers (RCFs) in the textile industry. However, Cu²⁺ is introduced during the cellulose dissolution process and gradually accumulates, seriously affecting the RCF performance and IL recovery. Herein, to achieve an efficient and selective adsorption of Cu²⁺ from ILs aqueous solutions, a facile and green method based on the in situ growth of zeolitic imidazolate framework-67 in wood hydrogels (ZIF-67@WH) is presented. The morphology, functional groups, crystallinity, thermal stability, and pore structure of the resulting ZIF-67@WH were investigated using various characterization techniques, and the adsorption selectivity, adsorption thermodynamics, adsorption kinetics, and recoverability were examined in depth by performing batch experiments. The ZIF-67@WH exhibits high adsorption selectivity for Cu²⁺ and ILs with adsorption ratios of 92.8 % and 2.2%, respectively. The selective adsorption mechanism was elucidated by means of FT-IR, XPS, DFT, and MD. As the key for the selective adsorption, the N site in ZIF-67 dramatically promotes the coordination with Cu²⁺, while the adsorption for ILs mainly occurs via hydrogen bonding and van der Waals interactions with adsorption energies of –80.61 and –35.33 kcal mol⁻¹, respectively. The results demonstrate that this approach constitutes a feasible technique for the efficient separation of Cu²⁺ and ILs in the textile industry.

期刊信息：Sep. Purif. Technol.

DOI:10.1016/j.seppur.2024.130384

论文链接:

本期编辑

张子石，男，北京建筑大学环境工程专业2023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。

扫描下方二维码|关注我们

新型环境修复材料与技术课题组

课题组网站链接：http://nmter.bucea.edu.cn

★北建大/北大深研院/华理Nat. Commun.：多酸MOF电子海绵效应实现多通道电子定向传递强化类芬顿反应