MOFs基材料用于环境污染控制文献整理（2024.10.20-2024.10.26）

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题目：MIL-125-PDI/ZnIn₂S₄ Inorganic-Organic S-Scheme Heterojunction With Hierarchical Hollow Nanodisc Structure for Efficient Hydrogen Evolution from Antibiotic Wastewater Remediation

作者：Weili Yu, Ningjie Fang*, Zhaobing Liu, Yinghao Chu*, Bo Lai

摘要：Efficient photocatalytic production of H₂ from wastewater is expected to address environmental pollution and energy crises effectively. However, the rapid recombination of photoinduced carriers results in low photoconversion efficiency. At present, inorganic-organic S-scheme heterojunction have become a prominent and promising technology. In this study, an organic ligand modified MIL-125-PDI/ZnIn₂S₄ (ZIS) inorganic-organic S-scheme heterojunction catalyst is designed. ZIS nanosheets are grown on the disc-shaped MIL-125-PDI surface to form a distinctive hollow nanodiscs with hierarchical structure, giving the material an abundance of surface active sites, an optimized electronic structure, and a spatially separated redox surface. Consequently, the optimal 100MIL-125-PDI₂₅₀/ZIS exhibited high photocatalytic HER of 508.99 µmol g^-1h^-1 in Tetracycline hydrochloride (TC-HCl) solution. Meanwhile, the catalyst achieved complete TC-HCl removal and mineralization rate of 66.62% in 4 h. Experimental and theoretical calculations corroborate that the staggered band alignment and work function difference between MIL-125-PDI and ZIS induce the formation of a built-in electric field, thus regulating the charge transfer routes and consequently enhancing charge separation efficiency. The possible photocatalytic mechanism is analyzed using liquid chromatography-mass spectrometry (LC-MS), and the toxicities of the degradation products are also evaluated. This work presents a green dual-function strategy for H₂ production and antibiotic wastewater recycling.

期刊信息：Small

DOI：10.1002/smll.202407104

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题目：ZnO@In₂O₃ Core-Shell Heterojunctions Constructed With ZIF-8 and MIL-68 (In) for Improving Photogenerated Carrier Transfer Process

作者：Chonghan Luo, Yuan Liu, Jiatian Yu, Ling Zhou, Rongbin Zhang*, Xuewen Wang*

摘要：The realization of fast carrier transport can effectively enhance photocatalytic performance. A core-shell structure of ZnO and In₂O₃ is successfully constructed by using MIL-68 (In) and ZIF-8 as a substrate, forming a heterojunction. This MOF-derived core-shell heterojunction inherits the advantages of ZIF-8, with pores facilitating carriers transfer to the surface for reactions and a large specific surface area providing more active sites. This Z-scheme heterojunction of ZnO and In₂O₃ can effectively separate and improve the utilization of photogenerated carriers. The well-designed interface of the core-shell structure achieves the rapid transfer of photogenerated carriers. The photocatalytic degradation capability of ZnO@ In₂O₃ is enhanced by the synergistic effect of Z-scheme heterojunction and core-shell structure. This work provides insight into the investigation of constructing core-shell heterojunctions.

期刊信息：Small

DOI：10.1002/smll.202404303

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题目：How the Most Neglected Residual Species in MOF-Based Catalysts Involved in Catalytic Reactions to Form Toxic Byproducts

作者：Fukun Bi, Jiafeng Wei, Bin Gao, Shuting Ma, Ning Liu*, Jingcheng Xu*, Baolin Liu, Yuandong Huang, Xiaodong Zhang*

摘要：In recent years, multifarious new materials have been developed for environmental governance. Thereinto, metal organic framework (MOF)-based catalysts have been widely employed for heterogeneous catalysis because of their high porosity to confine noble metal particles faraway from aggregation. However, the potential reactions between residual species from the material synthesis process and target pollutants, which could form highly toxic byproducts, are often neglected. Herein, we took the widely used Zr-MOF, UiO-66, with highly thermal stability supported Pd catalysts as the example to investigate how the residual species in catalysts are involved in aromatic volatile organic compounds (VOCs) degradation reaction. The results showed that residual Cl species originated from the ZrCl₄ metal precursor participated in the VOC degradation reaction, leading to the production of various chlorine-containing byproducts, even the hypertoxicity dioxin precursor, dichlorobenzene. Meanwhile, the chlorination mechanism for the formation of chlorine-containing byproducts was revealed by density functional theory calculation. Furthermore, the highly efficient residual Cl removal approaches are proposed. Importantly, the migration and transformation of residual Cl during the degradation of five benzene series VOCs are comprehensively studied and elucidated. We anticipate that these findings will raise alarm about the neglected issue of residual species in MOF-based catalysts for heterogeneous catalysis, especially environmentally friendly catalysis.

期刊信息：Environ. Sci. Technol.

DOI：10.1021/acs.est.4c06351

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题目：Trimetallic MOF–derived Fe–Mn–Sn oxide heterostructure enabling exceptional catalytic degradation of organic pollutants

作者：Anqi Li, Yu Yang, Xuening Bai, Hebin Bao, Miao He, Xuzhong Zeng, Yejin Wang, Fang Li, Shijiang Qin*, Wenjing Yang*, Xueming Li

摘要：Developing efficient and environmentally benign heterogeneous catalysts that activate peroxymonosulfate (PMS) for the degradation of persistent organic contaminants remains a challenge. Metal–organic frameworks (MOFs)–derived metal oxide catalysts in advanced oxidation processes (AOPs) have received considerable attention research fraternity. Herein, we report an innovative magnetic trimetallic MOF-derived Fe-Mn-Sn oxide heterostructure (FeMnO@Sn) with adjustable morphology, size and Sn content, prepared through an impregnation–calcination strategy. The formation of a novel magnetic Fe₂O₃/Fe₃O₄/Mn₃O₄ heterostructure induces the generation of abundant Fe²⁺ and Mn²⁺ sites on the FeMnO@Sn surface. Meanwhile, the introduction of SnO₂ into the Fe₂O₃/Fe₃O₄/Mn₃O₄ heterostructure facilitates the cleavage of the O-O bond in adsorbed PMS. The synergy among the different functionalities of each metal oxide plays a vital role in the swift and effective degradation of pollutants. In addition, the uniquely designed catalyst exhibits magnetic properties that facilitate easy recycling and repeated use, thereby meeting environmental protection requirements. Overall, this research highlights the design of heterogeneous catalysts for the effective activation of PMS and provides valuable insights for the advancement of future environmental catalysts.

期刊信息：J. Colloid. Interf. SCI

DOI：10.1016/j.jcis.2024.10.098

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题目：Ultrafast and energy-efficient flowthrough capture of antibiotics through a reusable MOF@wood membrane adsorbent

作者：Yaqin Zhu, Gaigai Duan, Weijie Wu, Yanbo Liu*, Shiyi Zeng, Haoqi Yang, Xiaoshuai Han, Shuijian He, Chunmei Zhang, Jingquan Han, Shaohua Jiang*

摘要：The accumulation of antibiotics in aquatic environments poses escalating risks to both ecosystems and human health. However, current water remediation strategies are hampered by numerous limitations, especially in operating costs and processing efficiency. Herein, the MIL-100(Fe)@wood membrane with high metal-organic frameworks (MOFs) loading is prepared by a simple flow-based fabrication technique. The presented integrated water purification system comprising membrane preparation, antibiotic removal and membrane regeneration allows for the sequential and continuous execution of the individual processes, thereby improving the sustainability, time efficiency and energy efficiency of the system. The highly efficient and flowthrough capturing membranes (MIL-100(Fe)@wood) are reported to remove numerous common antibiotics from water: tetracycline (TC), ciprofloxacin (CIP), amoxicillin (AMX), roxithromycin (RXM), and sulfamethazine (SMT). The stability and excellent long-term performance under different pH environmental conditions of MIL-100(Fe)@wood are demonstrated. Furthermore, the removal mechanisms of the multimolecular interactions occurring between antibiotic and MIL-100(Fe)@wood have also been explored. The unique advantage of MIL-100(Fe)@wood is employed in sustainable, cost-effective, and facile strategies for the removal of antibiotics.

期刊信息：J. Membr. Sci.

DOI：10.1016/j.memsci.2024.123411

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题目：Copper-based photocatalysts with natural organic ligands for efficient removal of tetracycline under visible light

作者：Shouxin Zhu, Can Sun, Zhexiao Zhu, Jingyi Qu, Zijie Fang, Yangben Chen, Jiahui Lin, Xiaolu Xu, Miaoyan Cheng, Min Jiang*, Hui Zheng*

摘要：The excessive use of broad-spectrum antibiotics, such as tetracycline, presents a significant challenge to human survival and development. Oxygen vacancies (OVs) metal-organic framework (MOF) materials were synthesized using natural organic acids (L-malic acid, L-aspartic acid, and L-asparagine) with similar structures but different charge densities, along with copper as the metal linking agent. The presence of oxygen vacancies in the catalyst provides abundant active sites for photocatalytic reactions. The employment of flexible straight-chain organic ligands devoid of rigid polycyclic rings, combined with the incorporation of different substituents to induce variations in charge density, the resulting catalysts exhibit distinct photocatalytic activities under visible light. Density functional theory calculations confirm that L-asparagine exhibits the largest electron density difference, and the Cu-based MOF (Cu-ASU) synthesized as an organic ligand exhibits the highest photocatalytic activity under visible light excitation. The catalyst displayed remarkable photocatalytic activity against tetracycline antibiotics under identical conditions (with removal rates of 93.5 % for tetracycline, 81.4 % for terramycin, and 95.6 % for chloramphenicol hydrochloride). This provides a novel approach for the design and synthesis of photocatalysts for the removal of antibiotics from water.

期刊信息：J. Environ. Manage.

DOI:10.1016/j.jenvman.2024.123052

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题目：Gadolinium doping-induced electronic structure optimization of MIL-101-NH₂: Efficient adsorption of arsenic (V) and phosphorus and electrochemical regeneration

作者：Zhaoneng Wan, Xin Xu, Zhuangzhuang Bi, Du Jiajia, Yudong Li, Muhan Chen*, Zhangjie Huang

摘要：The high concentration of acids/bases used to regenerate MOF adsorbents can compromise their structural integrity and may generate additional environmental pollution. The regeneration challenges of MOF adsorbents limit their use in environmental applications. Here, the electronic structure of the iron-based metal–organic framework MIL-101-NH₂ was optimized by gadolinium (Gd) doping to provide oxygen vacancies and enhance the electrochemical activity for the selective removal of arsenic(V) and phosphorus from water. 0.75GF-MILN, which was prepared using a gadolinium to iron molar ratio of 0.75, showed a maximum arsenic(V) adsorption capacity of 220.7 mg g^-1 and maximum phosphorus adsorption capacity of 112.8 mg P g^-1. Increasing the temperature was conducive to the adsorption of arsenic(V) and phosphorus by 0.75GF-MILN, which also maintained a high uptake capacity for arsenic(V) and phosphorus over the pH range of 4.0–9.0. The electro-assisted desorption of arsenic(V) and phosphorus from 0.75GF-MILN was achieved at −3 V. Moreover, 0.75GF-MILN still maintained 99 % arsenic(V) and phosphorus removal efficiencies from real water samples even after four cycles of electro-assisted adsorption–desorption. Density functional theory calculations and electrochemical tests showed that gadolinium doping optimizes the electron structure of MIL-101-NH₂, leading to improved electron mobility. This is beneficial for electrochemical elution. Unlike other rare earth-doped MOF materials, arsenic can be desorbed from 0.75GF-MILN using a capacitive deionization process, avoiding the destruction of the MOF via exposure to a highly concentrated acid-base desorption solution. This study provides a design strategy for constructing adsorbents suitable for electrochemical elution to co-remove arsenic(V) and phosphorus, demonstrating the practicality of using rare earth-doped MOF materials in the field of watea treatment.

期刊信息：Sep. Purif. Technol.

DOI：10.1016/j.seppur.2024.130133

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题目：Green room-temperature fabrication of phosphotungstic acid functionalized MOF-808 for efficient removal of cationic antibiotics

作者：Kaili Shi , Honghao Su , Keke Liu, Yatao Zhang*, Junyong Zhu*

摘要：Zr^Ⅳ-based metal–organic frameworks (MOFs)–featuring exceptional water stability, large surface area, and structural tunability–hold promise for efficient antibiotics adsorption from water. However, their inherent positive charge in neutral environments and the harsh conditions required for their synthesis hinder their effective removal of cationic antibiotics. To address this challenge, a green one-pot synthesis approach was proposed to fabricate phosphotungstic acid-functionalized MOF-808 (termed as PTA@MOF-808) at room temperature for elevated antibiotic adsorption. This approach not only leverages the strong electronegativity of PTA to improve electrostatic interactions and π-π stacking but also finely tailors the pore size of MOF-808, resulting in enhanced adsorption capacity of PTA@MOF-808. The influence of PTA loading, solution pH, and absorbent dosage on the performance of PTA@MOF-808 were studied in detail. Adsorption experiments demonstrated that PTA@MOF-808 outperformed unmodified MOF-808 in removing various positively charged antibiotics, with 5 % PTA@MOF-808 exhibiting maximum adsorption capacities of 548.1 mg g^-1 and 482.9 mg g^-1, for DOX and TCHC, respectively. The adsorption process followed the Langmuir isothermal model and the pseudo-second-order kinetic equation. Furthermore, the composite PTA@MOF-808 displayed excellent reusability after multiple adsorption–desorption cycles. These findings highlight the potential of PTA@MOF-808 as a promising absorbent for removing specific antibiotics from water, with significant implications for wastewater treatment.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130155

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题目：Novel integration of dual-modified Zr-MOFs and graphene oxide nanocomposites in polyethersulfone membranes: Enhanced permeability, selectivity, and fouling resistance

作者：Elia Gadallah , Mohamed N. Khalil , Sami Karam , Wael Ali , Jinchao Chen , Xiangmin Xu , Yuan Jing , Fang Li*

摘要：Designing and fabricating ultrafiltration membranes that possess relatively high permeability while simultaneously maintaining high rejection and improved antifouling properties continues to be a challenge. In this study, we investigated the integration of novel melamine modified Zr-based metal organic frameworks (Zr-MOFs) with nanosheets of graphene oxide (GO) and sulfonated graphene oxide (SGO). These composite materials were synthesized using the solvothermal process and subsequently coated onto the PES membrane surface using the vacuum-assisted dip-coating method. The stability enhancement of the topmost MOF composite layer adhering to the membrane surface is attributed to hydrogen bonding, π-π stacking, and van der Waals interactions. These effects are augmented by the incorporation of polar functional groups such as hydroxyl, carboxyl, sulfonate, and amine groups. The optimized composite membranes incorporating MOFs exhibit enhanced performance, with a permeability of 80.2  L/m² h bar, achieving a bovine serum albumin (BSA) rejection of ≥97.8 % and a humic acid (HA) rejection of 98.9 %. Moreover, a flux recovery ratio (FRR) of 89.5 %. To investigate the interactions among the incorporated components, molecular dynamics (MD) simulations were employed in a computational study. The simulations validated hydrogen bond formation and reinforced prior studies, demonstrating the potential of Zr-MOF compositions as effective hydrophilic nanoparticles. The overall results indicate a substantial enhancement in membrane performance and underscore the high potential for practical applications.

期刊信息：Sep. Purif. Technol

DOI:10.1016/j.seppur.2024.130137

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本期编辑

李湘雨，女，北京建筑大学资源与环境专业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。

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