MOFs基材料用于环境污染控制文献整理（2024.12.22-2024.12.28）

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：Cerium-based metal-organic frameworks: Synthesis, properties, and applications

作者：Hossein Molavi*

摘要：Within the great variety of metal-organic frameworks (MOFs), Cerium-based MOFs (Ce-MOFs) have achieved significant interest in the recent years and different studies have reported their great potential in different applications. Ce-MOFs with diverse valence states (Ce(III) and Ce(IV)) are first classified and discussed in view of distinct topologies, inorganic building units (IBUs), connectivity, and organic linkers. Then, concisely summarized their structural properties with emphasize on exploring their structure-property relationships. Subsequently, the latest progress in the synthesis strategies of Ce-MOFs were summarized with highlighting the green strategies under ambient conditions that are applicable for scale-up production of Ce-MOFs. Moreover, their applications in different fields including; corrosion inhibitors, biomedical applications, energy storage and conversion, gas adsorption, separation, and conversion, catalysis/photocatalysis, chemical sensing, and water/wastewater treatment are highlighted. Representative examples are reviewed with a focus on elucidating the relationship between their structures, properties, and applications. Finally, the future challenges and outlooks of Ce-MOFs in practical applications are also discussed. It is hope that the present review provide inspiration for researchers in this field and be a valuable reference for extending their knowledge about MOFs.

期刊信息：Coord. Chem. Rev.

DOI：10.1016/j.ccr.2024.216405

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题目：Metal-organic framework membranes and their advanced oxidation processes in water treatment: From material regulation to stability evaluation

作者：Xiaoyu Zhao, Mei Long, Xia Huang, Zhenghua Zhang*

摘要：The integration of membrane technology with heterogeneous advanced oxidation processes (AOPs) has shown great potential as a promising strategy to deal with contemporary water crisis. In order to overcome the intrinsic problems of membrane-based AOP systems, including the membrane selectivity-permeability trade-off, membrane fouling, limited reaction interface area and catalyst deactivation, metal–organic frameworks (MOFs) can be adopted as AOP membrane modifiers. However, among the research related to MOF-based membranes for water treatment, the discussion on their aqueous stability and evaluation of their AOP performances are generally deficient. Therefore, this work conducts a radical review on the MOF membranes specializing in AOPs for water treatment by summarizing the studies published within the last decade with keywords of stable MOF, MOF catalysts, and MOF-based membranes. Specifically, the most fundamental factors and principles that dominate the stability of MOFs are profoundly discussed, and the unique influences on MOF stability from oxidative environments are taken into consideration for the first time. Various strategies to fabricate MOF membranes, and their performances in various AOP systems are comprehensively summarized. More importantly, extensive discussions are made on the challenges and perspectives of MOF membranes for AOPs, which include the stability improvement approaches, mechanism illustration methods, and their application potentials in more advanced catalysis processes (e.g. nanoconfinement catalysis, high-entropy alloy catalysis, large-scale catalytic AOP reactions).

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158523

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题目：Rapid one-pot synthesis of multifunctional UiO-66(Zr/Ce)-NH₂ for detection and photocatalytic degradation of tetracycline

作者：Chaoting Shi, Ninghan Tang, Shan Pu, Hui Xin^*, Lan Wu^*, Xiandeng Hou

摘要：Metal-Organic Frameworks (MOFs) have been widely used for the antibiotic pollution control. However, it remains a challenge to simple design and synthesis of multifunctional MOFs for sensing and degradation antibiotics. Herein, a multifunctional UiO-66(Zr/Ce)-NH₂ ratiometric fluorescence sensing and photocatalytic degradation platform was rapidly and simply constructed at room temperature by a one-pot method using a dielectric barrier discharge device. The mixed-metal centers and mixed-ligands of this platform enabled effective ratiometric fluorescence sensing of tetracycline (TC), along with a visual fluorescence shift from blue to yellow-green color. The platform demonstrated a detection of TC ranged from 200 nM to 15 μM, with a detection limit of 43 nM. Moreover, the UiO-66(Zr/Ce)-NH₂ exhibited strong light absorption and efficient photogenerated carrier separation, thus offering excellent degradation performance of TC compared with that of MOFs with single metal center, mixed ligands or mixed metal centers. The mechanism of fluorescence detection and potential charge transfer pathways by the UiO-66(Zr/Ce)-NH₂ were analyzed. This work provided a new approach for the simple design and synthesis of multifunctional MOFs platforms.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158621

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题目：Difunctional MOF-EDTA modified wood membrane for efficient water purification

作者：Bo Yue, Zhongwei Pang, Yang Yu, Jianfei Wu, Jiafu Qu, Jundie Hu, Dan Tian, Jianzhang Li, Yahui Cai*

摘要：The environmental pollution caused by the discharge of oily wastewater and printing and dyeing wastewater is becoming more and more serious. Therefore, it is necessary to find an efficient method to separate oil/water emulsions and remove organic dyes from water simultaneously. However, the traditional separation membranes are usually very expensive and easy polluting the environment. Therefore, how to prepare high-efficiency separation membrane from low-cost, green renewable materials remains a huge challenge. In this study, ethylenediaminetetraacetic acid (EDTA) modified metal–organic framework (MOF-808) nanoparticles were introduced into the wood substrate to construct a 3D wood/MOF-808-EDTA membrane with efficient water purification performance (oil/water emulsion separation and organic dye removal). Due to the introduction of hydrophilic MOF-808-EDTA nanoparticles, this novel membrane can effectively separate stable oil-in-water emulsions and remove organic dyes from water. The prepared wood/MOF-808-EDTA membrane has a high separation efficiency (more than 99.9 %) and permeation flux (1698 ± 15.85 L·m⁻²·h⁻¹). The removal efficiency of organic dyes is more than 94 % with the permeation flux 1360 ± 2.54 L·m⁻²·h⁻¹. More importantly, the separation efficiency (oil/water emulsion) remained above 99.9 % and the dye removal efficiency was still above 90 % after 10 cycles. Additionally, the wood/MOF-808-EDTA membrane also has good mechanical/chemical stability and anti-fouling properties. This work opens a new approach for the development of functional biomass material membranes for sewage purification.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158896

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题目：Synergistic pyrolysis of Cellulose/Fe-MOF Composite: A Combined experimental and DFT study on dye removal

作者：Sherif Hegazy, Hanan H. Ibrahim, Timo Weckman, Tao Hu, Sari Tuomikoski, Ulla Lassi, Karoliina Honkala*, Varsha Srivastava*

摘要：We propose the development of an innovative composite material formed through the pyrolysis of oxidized cellulose derived from sawdust, utilizing iron-based MOF as a precursor. This novel material incorporates multiple iron-based components (Fe₃O₄, Fe₃C and Fe⁰) within a biochar matrix. We employed the composite to adsorb a cationic dye from aqueous solution. Batch adsorption studies explored the effects of pH, contact time, and initial dye concentration. The experimental data fitted well with the pseudo-second-order kinetic model, suggesting chemisorption as the primary mechanism, while equilibrium adsorption results fitted to the Langmuir isotherm model, described monolayer adsorption displaying the highest adsorption capacity (106 mg/g). A fixed-bed column experiment further demonstrated effective removal of methylene blue (MB) dye, achieving an initial breakthrough time of approximately 12 h, and exhibiting an adsorption capacity (q_e = 71.14 mg/g) surpassing batch adsorption capacity at the same concentration (q_e batch = 52.53 mg/g), signifying the practical utility of the materials. In addition, pyrolysis-derived biochar samples displayed improved total organic carbon (TOC) removal efficiency, with P-Cell-MOF achieving 93 % TOC removal. Density functional theory (DFT) calculations were employed to investigate the binding of MB on the various materials derived from the pyrolysis of cellulose with MOF. The calculations show that MB chemisorbs on both Fe (110) and Fe₃C (001) surfaces while only physisorption was observed on Fe₃O₄(111) and graphene. These computational findings align well with the experimental data and provide an explanation for the enhanced TOC removal observed with the P-Cell-MOF.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158654

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题目：The lead-free halide perovskite/UiO-66 with dual Lewis acid sites for efficient photocatalytic NO removal

作者：Zhijian Xiao, Wenda Yang, Jing Wang, Shuang Cao*, Jingling Yang*, Mingshan Zhu

摘要：Photocatalysis is a promising technology for removing low concentrations of nitric oxide (NO) from the atmosphere. However, the unsatisfactory photocatalytic NO removal efficiency and the high selectivity for NO₂ in catalysts limit the development of this technology. In this work, we used an in-situ synthesis method to incorporate Cs₃Bi₂Br₉ into UiO-66 for efficient and robust photocatalytic NO removal. The Cs₃Bi₂Br₉/UiO-66 catalyst exhibits a 77.6 % NO removal efficiency and low NO₂ selectivity under visible light irradiation at a WHSV of 1,650,000 mL h⁻¹ g⁻¹, exceeding the efficiencies of Cs₃Bi₂Br₉ (36.4 %) and UiO-66 (2.3 %), as well as those of most reported MOF-based photocatalysts. The synergy of weak Lewis acid sites from Cs₃Bi₂Br₉ in Cs₃Bi₂Br₉/UiO-66 and the strong Lewis acid sites from UiO-66 promotes the enrichment of NO on the catalyst surface and act as electron traps to induce carrier separation, thereby promoting the generation of ·O₂⁻ to achieve high efficiency. This work provides a new idea for the development of catalysts in NO elimination.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.159022

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题目：Combination of adsorption and oxidation over Fe-doped Cu-1,3,5-benzenetricarboxylate to boost room temperature H₂S removal

作者：Yeshuang Wang , Mingxian Duan , Zhelin Su , Chao Yang* , Yuxiao Wang , Tian Kou , Jiawei Kou , Huiling Fan*

摘要：Cu–1,3,5-benzenetricarboxylate (Cu–BTC) exhibited potential for hydrogen sulfide (H₂S) removal, however, its sulfur capacity is limited due to it relies only on the adsorption reaction path. Herein, a series of Fe-doped Cu–BTC materials (denoted as xFe–Cu–BTC) were synthesized to enhance H₂S removal capacity via a adsorption–oxidation bifunctional synergism mechanism. The prepared materials were characterized using various techniques, and their H2S removal performance was measured under dry and ambient conditions. The experimental results demonstrated that the 18%Fe–Cu–BTC shown the optimal breakthrough sulfur capacity of 122.8 mg S/g, marking a 2.1-fold and 10.3-fold improvement over pure Cu–BTC and Fe–BTC, respectively. The characterization analyses revealed that the Cu²⁺ active sites initially react with H2S to form CuS, while the incorporated Fe³⁺ sites trigger the oxidation of CuS, yielding elemental sulfur, Cu²⁺ and Fe²⁺. The resultant Cu²⁺ and Fe²⁺ further engage in reactions with H₂S to form CuS and FeS, thereby enhancing the H₂S removal capacity via dual reaction pathways of adsorption and oxidation. Additionally, appropriate Fe doping increased the specific surface area and pore volume of Cu–BTC, which exposed more active sites and improved molecular diffusion. Based on the obtained findings, a plausible desulfurization mechanism involving adsorption and oxidation synergism for remove H₂S was proposed.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131044

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题目：Excellent low-temperature catalytic performance on toluene oxidation over spinel Ce_aMn_3-aO₄ catalyst derived from pyrolysis of metal organic framework

作者：Bilal Ahmad, Ahmed Ismail, Yushi Li, Zixiang Sun, Yujun Zhu*

摘要：The pursuit is to boost the low temperature oxidation efficacy of catalyst through element doing, is attractive and complex in its challenges. Herein, spinel Mn₃O₄ and Ce_aMn_3-aO₄, catalysts were synthesized via pyrolysis of Mn and MnCe-MOF-74 with calcination temperatures of 350 °C and were evaluated for toluene oxidation. Different characterization techniques were used to comprehensively elucidate the physicochemical characteristic of the catalysts. The Ce-modified Ce_0.03Mn_2.97O₄ catalyst featuring a 2D rod morphology, exhibited superior low-temperature catalytic oxidation performance with enhanced activity stability and resistance to humidity, achieving 90 % toluene conversion (T₉₀₎ at 214 °C, 21 °C lower than spinel Mn₃O₄. Various characterization results revealed that surface oxygen species (O_ads) can directly oxidize toluene while oxygen vacancies facilitated the conversion of gaseous oxygen into surface active oxygen species for deep oxidation. This is resulting from the vigorous interaction between Ce and Mn facilitated by redox coupling reactions (Ce⁴⁺ + Mn³⁺ ↔ Ce³⁺ + Mn⁴⁺), promote the emergence of additional oxygen vacancies on Ce_0.03Mn_2.97O₄.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131130

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题目：Improving the performance of imprinted MOFs catalyst for targeted degradation of refractory organic pollutants in water: Functional design and recognition mechanism

作者：Jianxin Yi, Jinquan Wan* , Yang Liu , José Alemán , Yan Wang , Wenhui Yuan

摘要：In this study, molecular theoretical calculation was successfully applied to the preparation of high-performance imprinted MOFs catalyst to achieve efficient targeted degradation of refractory organic pollutants (ROPs) in water. The binding energies and weak interactions of imprinted systems were analyzed in depth. Moreover, the solvent effect of the porogenic agent on the prepolymers was also simulated. The imprinting recognition sites containing amide groups have the best targeted adsorption performance. Complex hydrogen bonding is the key to selective adsorption. Based on the functional design, the best adsorption performance of imprinted MOFs on sulfamethoxazole (SMX) was 4.63 times higher than that of MIL100. Under the synergistic effect of adsorption and catalysis, the removal of SMX reached 82 mg/g. The targeted adsorption mechanism of imprinted MOFs on SMX and their catalytic mechanism in advanced oxidation processes were investigated. This study is significant for the rapid development of highly efficient imprinted MOFs and their application in the deep elimination of refractory organic pollutants in water.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131197

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题目：In situ growth of ZIF-67 on silanization-modified cellulose fibers with enhanced toluene adsorption property and hydrophobicity

作者：Bing Yu*, Ping Wang*, Li Wang*, Fan Yang*, Gang Zhang*, Zhengchun Cai*, Muhua Chen, Xinbao Zhu*, Bo Fu*

摘要：The selection of adsorption materials is a key factor affecting the adsorption of toluene. The zeolite imidazolium ester skeleton (ZIF-67) was grown in situ onto the surface of biomass fibers and deposited with methyltrichlorosilane (MTCS) to construct a hydrophobic adsorption material for volatile organic compounds (VOCs). The specific surface area of the prepared adsorbent was as high as 350.05 m²·g⁻¹, which decreased after the deposition of MTCS. The water contact angle of the material increased from 0° to 119.8°. The static adsorption of toluene on the composite paper was 92–120 mg·g⁻¹, and the dynamic adsorption of toluene was 52–69 mg·g⁻¹, and the hydrophobically modified samples had better adsorption effects in humid environments. The interactions between ZIF-67 and toluene were analyzed by electrostatic potential (ESP) and independent gradient model (IGM) based on density flooding theory (DFT), which provided some theoretical support for this study.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.131222

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本期编辑

于伟建，男，北京建筑大学市政工程2024级硕士研究生。主要研究方向为金属有机框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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