MOFs基材料用于环境污染控制文献整理（2024.12.01-2024.12.07）

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：Tubular nanofiber membranes combined with Z-scheme CuS@Co₃S₄ heterojunction catalyst for high-efficient removal of polyvinyl alcohol from waste water with high COD

作者：Hongwei Piao, Jian Zhao*, Yifei Tang, Linpeng Fan, Xupin Zhuang,  Shujie Zhang, Qinglin Huang, Yong Liu, Changfa Xiao, Changwei Zhao,  Shaomin Liu

摘要：Polyvinyl alcohol (PVA), a typical water-soluble polymer with huge global production, is becoming one of the most ubiquitous pollutants and indeed the villain of the piece contributing high chemical oxygen demand (COD) in wastewater. Membrane technology is an effective method for wastewater purification, in particular, with the combination of peroxymonosulfate (PMS)-assisted advanced oxidation or photocatalytic process, is capable of maintaining high water flux and anti-fouling. Herein, a ZIF-67 derived Z-scheme CuS@Co₃S₄ heterojunction catalyst immobilized by poly (m-phenylene isophthalamide) (PMIA) tubular nanofiber membrane (CuS@Co₃S₄/PMIA-TNM) is designed using a polyester braided tube as interior reinforcement. The resultant membrane features with outstanding superhydrophilicity and commendable porosity (82.1 %), leading to a significantly enhanced permeability (water flux > 82.3 L·m⁻²·h⁻¹). Meanwhile, the membrane shows promising PVA removal efficiency (> 99.9 %) with a high COD removal efficiency (~ 83.4 %) and enhanced antifouling capacity (flux recovery ratio > 99.7 %) with the assistance of PMS driven by an ultra low-power LED lamp. The universal applicability and environmental adaptability are also verified in various reaction conditions. In terms of ecotoxicological impacts of the PVA wastewater before and after treatment on aquatic organisms, Zebrafish embryonic development dynamically demonstrated that the treated PVA waste water by the developed hybrid membrane is healthy for fish to grow. Our study definitely opens up a new avenue to develop high-performance catalytic membranes for PVA-based wastewater treatment.

期刊信息：J. Hazard. Mater.

DOI：10.1016/j.jhazmat.2024.136354

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题目：A novel trimesoyl chloride/hyper branched polyethyleneimine /MOF (MIL-303)/P84 co-polyimide nanocomposite mixed matrix membranes with an ultra-thin surface cross linking layer for removing toxic heavy metal ions from wastewater

作者：Netsanet Kebede Hundessa, Chien-Chieh Hu*, Dun-Yen Kang*, Eyasu Gebrie Ajebe, Biadglign Ayalneh Habet, Wei-Song Hung, Kueir-Rarn Lee, Juin-Yih Lai

摘要：In this study, a positively charged nanofiltration (NF) nanocomposite mixed matrix membrane (MMM) was developed by incorporating metal-organic frameworks (MOFs) (MIL-303) into P84 co-polyimide and cross-linking with hyperbranched polyethyleneimine (HPEI). A very thin selective layer was subsequently formed on the cross-linked membrane surface using trimesoyl chloride (TMC). The incorporation of MIL-303 introduced specific water channels, enhancing the permeance of the nanocomposite MMMs. Additionally, it improved hydrophilicity and influenced the diffusion of the TMC monomer through the channels. The cross-linker HPEI resulted in NF membranes with increased electro-positivity and a reduced mean pore diameter. The very thin crosslinked TMC layer further improved permeance and heavy metal ions rejection of the membrane. This optimized membrane exhibited excellent rejection for both bivalent and monovalent ions, as well as heavy metal ions, effectively overcoming the common trade-off between permeance and rejection in NF membranes. The membrane demonstrated a remarkable permeance of 13.0 LMH/bar, coupled with exceptional rejection for heavy metal ions (96.8 % for Zn²⁺, 95.2 % for Ni²⁺, 95.7 % for Cu²⁺, 93.2 % for Pb²⁺, and 92.9 % for Cd²⁺). The TMC/HPEI/MIL-303/P84 system presented in this study holds significant promise for customizing high-performance positively charged NF membranes for the removal of heavy metal ions from wastewater.

期刊信息：J. Hazard. Mater.

DOI：10.1016/j.jhazmat.2024.136221

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题目：Performance of Ti/TiO₂-ZIF-67 photoanode under LED irradiation applied to the photoelectrodegradation of the antidepressant venlafaxine (VEN) in municipal wastewater effluent

作者：Kallyni Irikura, Hernán Dário Rojas-Mantilla, Saidy Cristina Ayala-Durán, João Carlos de Souza, Eduardo Luiz Rossini, Ricardo Salazar-González , Maria Valnice Boldrin Zanoni

摘要：This work describes the direct deposition of ZIF-67 metal-organic framework (MOF) onto Ti/TiO₂ nanotubes forming a photoanode for the degradation of the antidepressant Venlafaxine (VEN). This material combines the excellent characteristics of ZIF-67 MOF in enhancing photocatalytic reduction and oxidation reactions induced by UV LED irradiation, as well as the storage of VEN molecules in its pores. Ti/TiO₂-ZIF-67 features an eco-friendly technology for degradation of pharmaceutical micropollutants such as antidepressants. The photoanode was prepared, characterized and applied in the degradation of VEN by photocatalysis (PC), electrocatalysis (EC), photolysis (PL) and PEC processes. PEC process presented the best performance when compared to the others processes in both simulated solutions and real wastewater, achieving 100% and 89% degradation of VEN after 60 and 90 min, with TOC removal rates of 50% and 4%, respectively. The lower mineralization rate suggests that the degradation of VEN in complex matrices such as that of real wastewater produced recalcitrant by-products that are difficult to convert into CO₂ and H₂O. Zeta potential measurement showed that at pH 6 and 8 there is an effect of attraction of opposite electrostatic charges between the surface of ZIF-67 (positive) and VEN (negative), favoring the degradation of VEN in this pH range. The good performance of the Ti/TiO₂-ZIF-67 can be attributed to the formation of the Z-scheme heterojunction between the TiO₂ nanotubes and the ZIF-67 MOF which contributed to a lower rate of electron-hole (e⁻/h⁺) pairs recombination, favoring VEN degradation mainly to higher generation of ^•OH radical and less contribution of O₂^•- superoxide produced by UV irradiation forming some degradation by-products through demethylation and oxidation reactions.

期刊信息：J. Environ. Manage.

DOI：10.1016/j.jenvman.2024.123460

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题目：Schottky junctions integrated with S-scheme heterojunctions in recyclable loaded ZnIn₂S₄/UiO-66/calcined graphite felt photocatalysts with enhanced carrier separation for photocatalytic degradation

作者：Jiajun An, Jinqiao Wang, Yanan Li, Lei Wang*, Bo Gao, Xudong Wang, Rui Miao, Miaolu He

摘要：Photocatalytic technology holds significant potential in the purification of antibiotic wastewater. However, efficient carrier separation and convenient recyclability are crucial for the practical application of photocatalysts. Herein, a loaded ZnIn₂S₄/UiO-66/calcined graphite felt (ZU/C-GF) composite photocatalyst was demonstrated to achieve efficient and stable removal of tetracycline hydrochloride (TCH) from water. Detailed characterization and theoretical calculations suggested that ZnIn₂S₄ could form a Schottky junction with C-GF and an S-scheme heterojunction with UiO-66. The internal electric field (IEF) at the interface could promote the migration of photoelectrons, while the Schottky barrier could inhibit electron backflow. This synergistic strategy maximized the separation of photogenerated electrons and holes, thereby enhancing the photocatalytic performance. The optimal composite material exhibited the highest removal efficiency (97.0 %) and reaction rate (0.02312 min⁻¹) while maintaining comparable degradation performance under solar irradiation. Additionally, this C-GF-based immobilization scheme allowed for rapid recovery and reuse of the photocatalyst, effectively addressing the challenge of recycling. ZU-10/C-CF demonstrated stable reusability after five consecutive cycles, revealing its significant potential for practical applications. This work presents novel insights for coupling Schottky junctions and S-scheme heterojunctions, and describes a more convenient approach for the continuous and stable treatment of antibiotic wastewater.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130814

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题目：Constructing exchangeable dual-sites in DUT-67 framework for efficient removal of selenite ions

作者：Jiaqian Wang , Min Yang , Zhengjie Li*, Xudong Zhao*

摘要：Efficient removal of toxic selenite ions (SeO₃²⁻) from aqueous media is highly significant while still faces challenges. In this work, we prepared a series of DUT-67-AA (DUT, Dresden University of Technology; AA, acetic acid) samples in water solvent, via controlling the addition amount of AA. It is demonstrated that the introduction of AA induces the formation of active open metal sites (i.e. Zr-AA and Zr-H₂O), both serving as potential adsorption sites for SeO₃²⁻. AA usage is found to well tailor the porosity, oxygen vacancy (or open metal sites), and particle morphology, and accordingly, to regulate the adsorption capacity of SeO₃²⁻. As an optimal selection, DUT-67-AA-6 shows a high adsorption capacity of 261.1 mg/g for Se(IV) and rapid adsorption rate (1 min for ∼90 % of saturated capacity) at 303 K. Neutral and weakly alkaline pH were found to benefit for the adsorption, and common cations and anions except for PO₄³⁻ have negligible interferences on the adsorption. The combination of characterization results and theoretical calculations together prove the chemical interactions of the Zr-AA and Zr-H₂O sites with SeO₃²⁻, i.e. the AA and H₂O molecules can be exchanged by SeO₃²⁻ to achieve the adsorption. Thus, our work provides an efficient adsorbent for toxic SeO₃²⁻, and proposes a feasible strategy to construct MOFs with abundant exchangeable sites.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130843

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题目：Efficient and selective adsorption of Ni(II) and Mo(VI) utilizing novel materials derived from in situ aminated Co/Zn-ZIF-Modified biochar

作者：Feiyu Gao , Chaowen Tan , Yang You , Yong Hou* , Hongyan Yan* , Xuewei Lv , Jie Dang*

摘要：The imperative need for efficient and selective adsorption of Ni(II) and Mo(VI) is crucial for resource utilization and environmental protection. However, this process faces a challenge due to the scarcity of adsorbents that can adeptly adsorb both metal ions simultaneously. To address this, this study introduces a novel composite adsorbent material, denoted as BECZN, achieved through composite cross-linking of waste orange peel biochar with in situ aminated cobalt/zinc-zeolitic imidazolate frameworks (Co/Zn-ZIF-NH₂). The incorporation of Co/Zn-ZIF-NH₂ enhances the availability of active groups within BECZN. The aerogel structure of BECZN prevents ZIF material collapse and agglomeration, thereby improving active site exposure. BECZN exhibits notable adsorption capacities, reaching 151.84 mg/g for Ni(II) at pH = 7 and 842.54 mg/g for Mo(VI) at pH = 3. Further investigations indicated that the adsorption of Ni(II) and Mo(VI) obeys the Langmuir isotherm model, while exhibiting pseudo-second-order kinetics and intraparticle diffusion characteristics. Notably, BECZN selectively adsorbs Ni(II) and Mo(VI) efficiently under acidic and neutral conditions, respectively. It can maintain high capacity under the interference of various cations and anions. Meanwhile, this excellent selective adsorption of Ni(II) and Mo(VI) by Co/Zn-ZIF-NH₂ is revealed at the atomic level using density functional theory (DFT) calculations. This study offers a theoretical basis and experimental reference for the design and synthesis of ZIF and biomass-based composite adsorbents.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130669

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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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本期编辑

 闫燕娇，女，北京建筑大学环境工程专业2024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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