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题目：Enhanced photo-Fenton activity and stability for sulfamethoxazole degradation by FeS₂@TiO₂ heterojunction derived from MIL-125

作者：Aofei Du, Huifen Fu*, Peng Wang, Chong-Chen Wang*

摘要：FT-x composites with core-shell structure (FT = FeS₂@TiO₂, x represents the mass ratio of the used FeCl₃·6H₂O to MIL-125) were fabricated by a hydrothermal method using MIL-125(Ti) as a self-sacrificing template. Both the photo-Fenton activity and stability of the FT-1 were improved greatly in comparison with its counterparts due to the unique core-shell structure and synergistic effect between FeS₂ and TiO₂. Especially, the Fe leaching concentration of FT-1 was approximately 1/10 of the individual FeS₂, benefiting from the protection effect of TiO₂ shell. Under dark condition, the formed FeOOH occupied active sites and inhibited iron cycle as well as H₂O₂ decomposition, leading to the inactivation of FT-1. UV light irradiation not only boosted the catalytic activity but also prevented the FT-1 from reactivity decline owning to the regeneration of Fe²⁺ by photogenerated electrons and continuous generation of ·OH. Experimental and DFT calculation results indicated that a type-II heterojunction was formed, in which photogenerated electrons were transferred from FeS₂ core to TiO₂ shell, accelerating charge separation and further boosting sulfamethoxazole (SMX) degradation. FT-1 displayed outstanding photo-Fenton activity in wide pH ranged from 2 to 6 and good anti-interfering ability toward impurities in water matrix. Besides, the reusability of FT-1 was good, in which 90% SMX degradation was maintained even after 5 runs. Noteworthy, the photo-Fenton activity was recovered via a revulcanization process, in which FeOOH was completely transformed into FeS₂. This founding provided insights for the design and construction of heterojunction with both excellent photo-Fenton activity and stability.

期刊信息: Chemosphere

DOI:10.1016/j.chemosphere.2023.138221

论文链接：

题目：Tailoring the Asymmetric Structure of NH₂-UiO-66 Metal–Organic Frameworks for Light-promoted Selective and Efficient Gold Extraction and Separation

作者：Jiazhen Cao, Zhenmin Xu, Yao Chen, Shuangjun Li, Yue Jiang, Lele Bai, Han Yu, Hexing Li, Zhenfeng Bian*

摘要：Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metal-organic framework (MOF) material (NH₂-UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g/g under light irradiation. The selectivity of NH₂-UiO-66 for gold ions is up to 98.8% in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH₂-UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of high-purity gold particles from NH₂-UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89%. Theoretical calculations indicate that -NH₂ functions as a dual donor of electrons and protons, and the asymmetric structure of NH₂-UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.

期刊信息：Angew. Chem. Int. Ed.

DOI：10.1002/anie.202302202

论文链接：

题目：Switching the reaction mechanisms and pollutant degradation routes through active center size-dependent Fenton-like catalysis

作者：Xinhao Wang, Zhaokun Xiong*, Hongle Shi, Zelin Wu, Bingkun Huang, Heng Zhang, Peng Zhou, Zhicheng Pan, Wen Liu, Bo Lai*

摘要：Rationally regulating reaction mechanisms in Fenton-like reactions by tuning the properties of catalysts is of great significance, but still challenging. Herein, we synthesized various active center size-dependent catalysts to realize the switching of reaction mechanisms and pollutant degradation routes in peroxymonosulfate (PMS) activation systems. The results illustrated that the reaction mechanism transformed from radical oxidation (51.64%) to nonradical oxidation (89.92%) with the decrease of active center size from nanoparticle (Co_NP-NC) to single atom (Co_SA-NC). The evolution of reactive species switched the degradation intermediates and pathway of sulfisoxazole (SIZ). The generation of singlet oxygen (¹O₂) in Co_SA-NC tends to selectively attack electron-rich site of SIZ, while reaction between radicals and SIZ prefers non-selective oxidation in Co_NP-NC/PMS system. Besides, the toxicity tests indicated that the conversion from non-selective to selective oxidation resulted in lower toxicity of effluent after reaction, which can further reduce environmental risks of effluent.

期刊信息：Appl. Catal. B: Environ.

DOI:10.1016/j.apcatb.2023.122569

论文链接：

题目：Surface Al and Co coordination for peroxymonosulfate activation: Identification and mechanism

作者：Min-Ping Zhu, Jia-Cheng E. Yang*, Daqin Guan, Baoling Yuan, Xiaoguang Duan, Darren Delai Sun*, Chenghua Sun, Shaobin Wang, Ming-Lai Fu*

摘要：Deciphering the metal-support interaction-oriented catalysis on millimeter-scaled catalysts is highly desirable yet remains scarce in Fenton-like catalysis. Herein, we fine-tune the support-surface reconstruction of Co₂AlO₄ on γ-Al₂O₃ millispheres and reveal the origins of its activity in peroxymonosulfate activation by nuclear magnetic resonance and X-ray photoelectron/adsorption spectroscopy. Calcination of γ-Al₂O₃ supports rearranged their surface octahedral, tetrahedral and pentacoordinate Al³⁺. The reconstructed tetrahedral and pentacoordinate Al³⁺ as binding sites regulated the formation of Co₂AlO₄ with coordinated Co³⁺/Co²⁺ redox centers via strong metal-support interactions. The activities of tailored Co₂AlO₄@Al₂O₃ millispheres in activating peroxymonosulfate follow different binomial models, highly relying on their Co³⁺/Co²⁺ ratio, contents of lattice O and pentacoordinate Al³⁺. The Co-O-Al bonds endow the millimeter-scaled Co₂AlO₄@Al₂O₃ with robust catalytic activity, stability and reusability. The exposed Co₂AlO₄ (200) surface is responsible for the decomposition of PMS into produce SO₄• and ¹O₂ as the dominant oxidants for water detoxification.

期刊信息: Appl. Catal. B: Environ.

DOI: 10.1016/j.apcatb.2023.122570

论文链接：

题目：Cu atoms on UiO-66-NH₂/ZnIn₂S₄ nanosheets enhance photocatalytic performance for recovering hydrogen energy from organic wastewater treatment

作者：Sijia Liu, Xifei Zhou, Changqing Yang, Chaohai Wei, Yun Hu*

摘要：The extensive use of sacrificial agents and the low carrier separation and utilization efficiency remain important factors limiting the development of photocatalytic hydrogen production. We report a three-layered, dual-functional photocatalysts of Cu atomics@UiO-66-NH₂(U6N)/ZnIn₂S₄ nanosheets (ZIS), for the simultaneous production of photocatalytic hydrogen and degradation of organic pollutants. When common and highly toxic organic pollutants (phenolic compounds and antibiotics) were substituted for the sacrificial agents, Cu@U6N/ZIS exhibited superior sustained hydrogen production, approximately 28 times greater than that of pure ZIS. The experimental results suggested that the window size of U6N (< organic pollutants molecular size) separates the reaction sites of organic pollutants oxidation and reduction of hydrogen ions (H⁺), thereby achieving spatial separation of redox sites. Besides, the structure of Cu@U6N/ZIS, which was anchored Cu within U6N and encapsulated by ZIS nanosheets, forming Z-type heterojunctions, achieved the control of the directional transfer of photogenerated electrons. And the coupled system can effectively enhance water quality by reducing the biological toxicity of the wastewater. This study suggests new avenues for environmental restoration and non-fossil fuel production.

期刊信息：Appl. Catal. B: Environ.

DOI：10.1016/j.apcatb.2023.122572

论文链接：

题目：Metal-organic frameworks (MOFs) as efficient catalysts for electro-Fenton (EF) reactions: A critical review

作者：Yixiang Li, Bin Yao*, Yuxin Chen, Yaoyu Zhou*, Xiaoguang Duan

摘要：As a type of coordination polymer, metal-organic frameworks (MOFs) have attracted extensive attention due to their large specific surface area, adjustable pore size and high porosity. Electro-Fenton (EF) technology is an environmentally-friendly and efficient advanced oxidation process (AOPs) degradation technology, which has also received extensive attention. Therefore, the paper systematically reviews the applications of MOFs in EF systems. Firstly, different series of MOFs (i.e., zeolite imidazole framework (ZIF), materials of institute lavoisier frameworks (MIL) and universitetet i oslo (UIO)) were introduced. Secondly, the advantages and disadvantages of homogeneous and heterogeneous EF were generalized, and the influencing factors of EF system (i.e., electrode, pH, current density, conductivity) were summarized. Then, the methods to improve the catalytic activity and water stability of MOFs were also described. Finally, the future application of MOFs in EF systems is prospected, which provides a detailed summary and foreshadowing for future research in this direction.

期刊信息：Chem. Eng. J.

DOI：10.1016/j.cej.2023.142287

论文链接：

题目：An ideal confined catalytic model via MOFs derived yolk-shell nanoreactors: the formation mechanism and catalytic performance for single-core and multi-core

作者：Zhenqing Zhao, Ming Zhang*, Jingqi Ruan, Lianjie Wang, Jing Wang*, Wuxiang Zhang, Weichuan Qiao*

摘要：Yolk-shell nanoreactors with diversified structure has received enormous attention in field of catalytic degradation due to the confined catalytic mechanism. Here, the single-core and multi-core yolk-shell nanoreactors are easily prepared by thermolysis of ZIF-67@SiO₂ precursor, where the controllable single-core and multi-core structures are adjusted by variable pyrolysis process. In order to confirm the effect of structure on catalytic mechanism and performance, tetracycline hydrochloride (TTCH), a common antibiotic, was selected as the model pollutant for degradation. Under the optimal conditions, the reaction rate of single-core yolk-shell nanoreactors (SCYSN) reached 0.067 min^-1, and the degradation efficiency of TTCH reached 85.05% within 25 min. However multi-core yolk-shell nanoreactors (MCYSN) reached 0.079 min^-1, and the degradation efficiency of TTCH reached 93.7% at the same time. The radical mechanism was confirmed by quenching experiments and electron paramagnetic resonance. Degradation pathway was inferred by three-dimensional fluorescence spectrum and liquid chromatography-mass spectrograph. Biotoxicity tests was conducted on the degradation products by culturing Staphylococcus aureus. This work demonstrates an ideal confined catalytic model for yolk-shell nanoreactors in field of environmental remediation.

期刊信息：Appl. Surf. Sci.

DOI: 10.1016/j.apsusc.2023.156958

论文链接：

题目：Bisthiourea immobilized UiO-66-NH₂ supported Fe₂O₃ nanoparticles to accelerate dual centers Fenton-like reaction

作者：Xu Huang, Xiaohu Fan, Aimin Li, Yechao Tian, Dawei Li*

摘要：In this paper, an efficient catalyst UiO-66-BTU/Fe₂O₃ was synthesized by using bisthiourea modified zirconium-based metal organic framework (Zr-MOF). The UiO-66-BTU/Fe₂O₃ system features outstanding Fenton-like activity that is 22.84 times and 12.91 times larger than Fe₂O₃ and conventional UiO-66-NH₂/Fe₂O₃ system. It also exhibits good stability, broad pH range and recycle ability. Through comprehensive mechanistic investigations, we have ascribed the excellent catalytic performance of the UiO-66-BTU/Fe₂O₃ system to ¹O₂ and HO· as the reactive intermediates, cause Zr centers can make complexation with Fe to form dual centers. Meanwhile, the CS on the bisthiourea can form Fe-S-C bonds with Fe₂O₃, reducing the redox potential of Fe(III)/Fe(II) and influencing the decomposing of H₂O₂, which indirectly regulate the interaction between Fe and Zr to accelerate electron transfer during the reaction. This work exhibits the design and understanding of the iron oxides incorporated in modified MOFs with excellent Fenton-like catalytic performance to remove phenoxy acid herbicides.

期刊信息：Sci. Total Environ.

DOI: 10.1016/j.scitotenv.2023.162651

论文链接：

本期编辑

   孙鸣忆，女，北京建筑大学资源与环境专业2022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应用。

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