MOFs基材料用于环境污染控制文献整理（2024.10.24-2024.11.30）

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：Confined pyrolysis to transfer MXene-like MOF into 2D carbon nanosheet boosting the ozone oxidation of antibiotic: Degradation behavior and intrinsic mechanism

作者：Wenhui Li, Xiufang Shen, Zhonglin Chen, Tian Tian, Chenyong Liu, Cheng Gu, Weichuan Qiao, Ming Zhang*

摘要：Ozone oxidation as a means of water treatment has received great attention in recent years, but ozone has low solubility and utilization, which hinders their efficient treatment of refractory pollutants. Herein, a dopamine-encapsulated 2D MOF strategy is proposed, where different metal salts including (acetylacetone iron, manganese, copper, etc.) are doped in it as active site precursors. After pyrolysis, 2D hollow porous carbon nanosheet catalysts such as Mn-HCNSs, Fe-HCNSs, Cu-HCNSs and Co-HCNSs are formed due to the rigid interface-induction of dopamine. Mn-doped Mn-HCNSs exhibits the best catalytic degradation performance when the antibiotic tetracycline is used as the target pollutant, and the degradation efficiency reached 90 % within 25 min (k = 0.213 min⁻¹). This excellent catalytic performance can be attributed to several advantages: (i) the hollow porous 2D structure facilitates mass transfer and enhances the reaction kinetic constants; (ii) the confinement effect of dopamine wrapping facilitates the generation of more dispersed active sites and accelerates its ozone decomposition efficiency. This study expands the application of 2D MOF-derived porous carbon materials in ozone oxidation.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158109

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题目：Fabricated S-scheme CoS/CeO₂ heterojunction photocatalyst efficiently activates peroxymonosulfate for polyethylene terephthalate plastic degradation: Insight into radicals and electron transfer

作者：Yang Wan, Huijie Wang, Jiejing Liu, Yuhe Lei, Wei Ma*, Xianghai Song, Weiqiang Zhou, Xin Liu, Jisheng Zhang, Binrong Li*, Pengwei Huo*

摘要：Polyethylene terephthalate (PET) plastics are widely utilized, yet they also give rise to significant environmental contamination. In this study, a CoS/CeO₂ material with an S-scheme heterojunction was constructed using CoS with CeO₂ derived from MOFs and employed for the photocatalytic activation of peroxomonosulfate (PMS) for the degradation of PET. The CoS/CeO₂/vis/PMS system demonstrated a degradation rate of up to 95.75 % (weight loss rate) for PET plastic. The performance of this system is much better than that of simple photocatalytic or PMS systems. Photogenerated carriers generated by heterojunctions upon illumination accelerate the fast electron cycling of Co²⁺/Co³⁺ through the S-scheme transfer pathway driven by a directional interfacial electric field. This promoted efficient mass transfer in the inhomogeneous phase system (such as SO₄^•−, e⁻) and acted as an adsorption activation site for PMS. In-situ X-ray photoelectron spectroscopy (In-situ XPS) and ESR test proved that the electron flow in the heterojunction conforms to the S-scheme mechanism. Density functional theory (DFT) calculations revealed the material of the CoS/CeO₂ interface and the successful construction of the modulated electronic structure led to the accumulation of holes on CeO₂ and electrons on CoS. Bader analysis on charge density distribution further demonstrated that the formation of the heterojunction decreased the adsorption energy of the PMS on the Co sites, which in turn lowered the energy barrier for the generation of SO₄^•−. This work would provide a novel solution to the problem of removing plastic pollutants from water, as well as new insight into the construction of S-scheme heterojunctions and the mechanism of photocatalytic PMS activation.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158124

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题目：Flexible electrochemical sensors based on nanomaterials: Constructions, applications and prospects

作者：Xiuying Li, Zheng Yong Zhang*, Fengyu Li*

摘要：With the widespread application of flexible electrochemical sensors in environmental monitoring, medical diagnosis, food quality and safety analysis, and the other related fields, many functional nanomaterials have been developed for the construction of flexible electrodes. Here, we review the recent advances in the construction of flexible electrochemical sensors, with special attention to the functional nanomaterials. Firstly, the working principle of such electrochemical sensors with functional materials are introduced. The functional materials are mainly including metal nanomaterials, carbon-based materials, metal organic framework-based materials, single-atom materials, conductive polymers, MXene-based materials, and others. These materials are employed in the construction of flexible electrochemical sensors based on their excellent electrochemical activity, large specific surface area, and good biocompatibility. Then, the review explores the different application of flexible electrochemical sensors in fields of sports monitoring, environmental monitoring, medical diagnosis, and food quality and safety. Finally, the challenges and future directions of flexible electrochemical sensing are further discussed.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2024.158101

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题目：Defective NH₂-MIL-53(Fe) with highly exposed metal active centers for enhanced synergistic adsorption and photocatalysis of ibuprofen

作者：Yanyu Song ,Xianbo Sun , Long D. Nghiem , Jun Duan , Wen Liu , Yongdi Liu*, Zhengqing Cai*

摘要：Since adsorption is a prerequisite for photocatalytic surface reactions, it is attractive to study adsorption and photocatalysis as a synergistic technique to achieve efficient decontamination. In this study, defective NH₂-MIL-53(Fe) with highly exposed metal active centers was prepared through ligand modification and defect engineering, which exhibits dramatically enhanced adsorption and photocatalysis activity compared with the original MIL-53(Fe). With ibuprofen (IBP) as the target pollutant, the adsorption capacity increases from 11.4 to 25.0 mg/g within 60 min, and the photocatalysis rate under simulated solar light increases from 0.0044 to 0.056 min⁻¹. For adsorption, -NH₂ groups improves the adsorption affinity of the catalyst through additional hydrogen bonding effect and acid-base interaction. With HCl as modulator, defect construction ensures full exposure of metal active centers, and the exposed metal clusters become new adsorption sites for IBP through hydrogen bonding interaction. Moreover, by inducing increased free pore volume, defect engineering enhances the specific surface area of the material, thus allowing sufficient contact between the material and IBP to improve the adsorption capacity. For photocatalysis, -NH₂ groups provide lone pair nitrogen to increase the electron density of benzene rings, thus promoting the electron transfer from ligands to metal clusters. Simultaneously, -NH₂ substitution narrows the bandgap of catalyst by regulating the electronic structure, and narrower bandgap improves the visible light response of the material. As active sites for photocatalysis, highly exposed Fe-O clusters become more accessible due to defect construction, which can be directly excited by visible light to produce photoinduced carriers. The quenching experiments demonstrate that h⁺ and •O₂⁻ play the dominant role for photolysis, and the ecological toxicity of IBP is significantly reduced through the photocatalysis process. This work provides valuable reference for the research of bifunctional catalysts with synergistic adsorption and photocatalytic oxidation ability.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130754

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题目：Effective adsorption of Congo red by an innovative biochar/LDH-derived MIL-100(Al): Investigation of coexisting pollutants and mechanism revelation

作者：Weikun Sun , Chuanfu Liu , Shengqin Liu , Jian Zhang*, Hongbin Chen , Zumin Qiu*

摘要：Herein, the innovative use of 2-aminoterephthalic acid on biochar/LDH(Mg/Al) derivatization succeeded in obtaining BL@MIL-100(Al), which was applied as an excellent adsorbent for the efficient removal of Congo red (CR). The adsorption capacity of BL@MIL-100(Al) was 5 times that of biochar and 2.5 times that of LDH(Mg/Al), respectively. The experimental results showed that the maximum adsorption capacity of BL@MIL-100(Al) reached 1672.34 mg/g at 303 K, which was much higher than that of the reported adsorbents. The Langmuir model and Elovich model described the adsorption process of BL@MIL-100(Al) better. In addition, the thermodynamic results indicated that the higher temperature favored the adsorption process of CR. Besides, BL@MIL-100(Al) showed strong immunity to chloride and sodium salts, and the presence of microplastics facilitated the adsorption of CR onto BL@MIL-100(Al). Meanwhile, BL@MIL-100(Al) still achieved ∼ 81 % removal efficiency after 6 cycles and showed long-term water purification in fixed-bed column experiment, indicating its outstanding stability. Additionally, the excellent adsorption performance in different kinds of natural water environments and binary systems demonstrated its wide applicability. Moreover, the adsorption mechanism of BL@MIL-100(Al) was systematically explored based on XRD, FT-IR, and XPS characterizations, in which amino protonation contributed prominently to the adsorption process. Thus, an innovative and facile approach to synthesize BL@MIL-100(Al) as an adsorbent for the removal of CR from wastewater is feasible.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130670

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题目：CN vacancy engineering in Quasi-PBA heterojunction enhances photo-synergistic peroxymonosulfate activation efficiency

作者：Xiai Zhang , Yongren Liang , Xinwei Zhang , Huanran Miao, Qikui Fan , Jun Li , Tong Wang , Jingquan Wang , Zhimao Yang , Chuncai Kong*

摘要：The development of traditional photocatalysis and peroxymonosulfate activation is limited due to the stable removal and mineralization of mobile phase VOC, and the synergistic mechanism of the two processes is ignored. Quasi-CoFe PBA/g-C₃N₄ (H-CF PBA/g-C₃N₄) heterojunction was first designed and synthesized for the photocatalytic-enhanced PMS activation to degrade toluene. The construction of Quasi-Fe PBA with abundant CN vacancy increases the active metal site and enhances the light absorption and electron transport, promoting the synergistic effect. The built-in electric field between H-CoFe PBA and g-C₃N₄ further promotes efficient separation and transfer of photogenerated charge carriers. This synergy significantly boosts PMS activation, producing more reactive oxygen species and achieving efficient toluene mineralization. The H-CoFe PBA/g-C₃N₄ heterojunction achieved 91 % toluene degradation rate and 77 % mineralization rate, maintaining stability after five cycles, outperforming individual photocatalysis or PMS activation. Continuous-flow experiments revealed the feasibility of engineering applications. Thus, it is reasonable to believe that the synergistic catalytic system of heterojunction functional materials provides a new perspective for the removal of flowing-phase VOCs under low-temperature conditions.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130594

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题目：Exploiting the nodes of metal-organic framework by grafting functional organic molecules for synergistic uranium extraction

作者：Zixuan Ma, Chang Sun , Danyan Lin , Wen Yao*, Hairui Hou , Dedong Wu , Xinrong Guo , Xin Yu* , Xiangxue Wang*

摘要：High-efficiency elimination of uranium was a research hotspot from the aspect of nuclear energy development. Metal chelators and porous materials were two cutting-edge technologies for the recovery and separation of uranium from wastewater. However, there was only limited success in transferring the metal coordination function of metal chelators to chemically stable host materials. Herein, oxamic acid (OxA) and glycine (Gly) functionalized MOF-808 were prepared by a simple solvent-assisted ligand incorporation method and used for uranium removal. The ordered porous structure of MOFs provided rapid diffusion channels, and the introduction of amino acids on Zr₆ nodes endowed MOF-808 channels more functional groups with strong binding ability and high hydrophily. The MOF-808@OxA exhibited higher elimination ability (q_max = 370.76 mg·g^-1), rapider elimination rate (∼40 min), and higher selectivity than those of MOF-808@Gly and original MOF-808 at pH = 5. Particularly, density functional theory calculations revealed that MOF-808@OxA had a stronger affinity for uranium compared to MOF-808@Gly due to the synergistic effect of C = O and -NH₂ groups. Thus, this study provided a feasible strategy for modifying MOFs and a promising prospect for MOF-based materials to eliminate uranium from wastewater.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130607

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题目：Ultrathin metal-organic framework synergizes with carbon quantum dots improving photoelectrochemical water oxidation and tetracycline hydrochloride degradation performance

作者：Ruyi Wang* , Xingzhi Li , Yuxin Kan , Wenjun Fang , Caiyun Chen , Yongyan Chen ,Lingling Wang , Yong Jia*

摘要：Finding clean dual functional materials which can simultaneously alleviate energy and environmental issues is currently a research hotspot. In our work, TiO₂/CQDs/NH₂-MIL-125 photoanode system was constructed to explore the application of metal–organic frameworks (MOFs) materials in water splitting and biomedical wastewater treatment. The photocurrent density of the optimal TiO₂/CQDs/NH₂-MIL-125 photoanode reaches 1.7 mA/cm² at 1.23 V vs. RHE, which is about 1.8 times that of pristine TiO₂. More importantly, optimized photoanode displays an excellent remove ratio toward tetracycline hydrochloride of 74 % within 60 min. Through mechanism exploration, the excellent performance is attributed to the narrow band gap of NH₂-MIL-125 widens the light absorption range to the visible region. Additionally, the specific electron conduction behavior of CQDs and the type Ⅱ heterojunction between TiO₂/NH₂-MIL-125 inhibited the photogenerated electron-hole recombination. This work explores the application of photoelectrochemical (PEC) materials in environmental catalytic clean production.

期刊信息：Sep. Purif. Technol

DOI：10.1016/j.seppur.2024.130589

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本期编辑

  吕星霖，女，北京建筑大学资源与环境专业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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