随着工业化进程的加速与农业生产活动的扩大,废气废水的排放以及化学物质的滥用日益严重,对人类健康和动植物栖息地构成严峻挑战。因此,研发高效、精准、便捷、可重复且能实现可视化、快速准确检测的环境污染物监测技术显得尤为重要。金属有机框架(MOFs)材料作为一类新型的多孔晶体材料,在环境污染物检测领域展现出了卓越的性能。其中,稀土元素掺杂的MOFs(REMOFs),凭借其独特而优异的光学性质在环境污染监测领域具有巨大应用潜力。深入探讨了REMOFs的发光原理及其荧光检测机制。一系列具有代表性的研究成果表明,REMOFs能够巧妙地利用荧光传感技术,实现对环境中各类金属阳离子、阴离子以及有机污染物的精准检测。REMOFs的这些创新应用,为环境污染物监测技术的发展注入了新的活力,也为环境保护与人类健康保障提供了强有力的技术支持。
The acceleration of industrialization and the expansion of agricultural activities have led to a surge in waste gas and wastewater emissions,coupled with the misuse of chemical substances,posing significant threats to human health and the natural habitats of flora and fauna.In light of these challenges,the development of efficient,precise,convenient,repeatable,and visualizable technologies for monitoring environmental pollutants is of utmost importance.Metal-organic frameworks (MOFs),as emerging porous crystalline materials,have demonstrated remarkable capabilities in detecting environmental pollutants.Notably,rare earth element-doped MOFs (REMOFs),with their unique and exceptional optical properties,hold tremendous potential for application in environmental pollution monitoring.This paper delved into the luminescence principles and fluorescence detection mechanisms of REMOFs.Representative research findings revealed that REMOFs materials could adeptly utilize fluorescence sensing technology to achieve precise detection of various metal cations,anions,and organic pollutants in the environment.These innovative applications of REMOFs had infused new energy into the development of environmental pollutant monitoring technologies and provided robust technical support for safeguarding the environment and human health.
[1] Daniel E B,Ricardo E R.Standard dilution analysis (SDA) using high-resolution continuum source flame atomic absorption spectroscopy for the determination of Li,Cr,and Ni in complex matrices[J].Microchemical Journal,2025,212:113470.
[2] Almeida T D,Nicolau A S,Schirru R,et al.Development of a deep neural network and a PSO algorithm to predict ore hardness using X-ray diffraction and atomic emission spectroscopy[J].Minerals Engineering,2024,213:108760.
[3] Jasmine M W,Sean C T.Laser-ablation vs.bulk tissue ICP-MS for conifer tissue elemental analysis[J].Chemosphere,2025,374:144200.
[4] Robert W,Markus M.B,Martina B,et al.LAMAS 4 IC-Laboratory approved metadata acquisition schemas for ion chromatography[J].Journal of Chromatography B,2025,1256:124556.
[5] Lorenzo C,Elisa I,Francesca C,et al.Nitrogen and hydrogen as alternatives to helium using wide-bore columns in preparative multidimensional gas chromatography[J].Green Analytical Chemistry,2025,13:100255.
[6] Mateusz M,Andrzej P,Grzegorz B.First truly deep eutectic solvent (DES) based stationary phase for high-performance liquid chromatography (HPLC)[J].Talanta,2025,292:127963.
[7] Liu Y Y,Liu M L,Xiao J Y,et al.A ratiometric fluorescence biosensor based on enzyme-cascade signal amplification technology for the detection of lincomycin[J].Food Control,2025,175:111344.
[8] Wei Q S,Di Y M,You M H,et al.Metal-organic framework radiochromic materials:recent advances and applications[J].Coordination Chemistry Reviews,2025,534:216616.
[9] Yuan T X,Qi S T,Ye L Z,et al.Metal-organic frameworks-based materials:a feasible path for redox flow battery[J].Coordination Chemistry Reviews,2025,531:216503.
[10] Wang Y,Huang R,Zhang J J,et al.Lanthanide(Tb3+,Eu3+)-functionalized a new one dimensional Zn-MOF composite as luminescent probe for highly selectively sensing Fe3+[J].Polyhedron,2018,148:178-183.
[11] Zhou Z,Shang M C,Yao Z H,et al.Eu-MOF fluorescent fiber detector based on polyacrylonitrile:a highly selective and sensitive luminescence sensor for trace amounts of Fe3+[J].Dyes and Pigments,2022,198:110016.
[12] Peng L P,Guo H,Wu N,et al.A novel dual emission ratiometric fluorescence sensor Eu3+/CDs@UiO-66 to achieve Cu2+ detection in water environment[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2023,664:131205.
[13] Li Z H,Chen L,Deng J X,et al.Eu-MOF based fluorescence probe for ratiometric and visualization detection of Cu2+[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2024,304:123367.
[14] Liu W,Dai X,Bai Z L,et al.Highly sensitive and selective uranium detection in natural water systems using a luminescent mesoporous metal-organic framework equipped with abundant Lewis basic sites:a combined batch,X-ray absorption spectroscopy,and first pinciples simulation investigation[J].Environmental Science & Technology Journal,2017,51(7):3911-3921.
[15] Deng Y Q,Jiang S,Yan Z F,et al.Fluorescent Eu-MOF@nanocellulose-based nanopaper for rapid and sensitive detection of uranium(Ⅵ)[J].Analytica Chimica Acta,2024,1292:342211.
[16] Liu W,Dai X,Wang Y L,et al.Ratiometric monitoring of thorium contamination in natural water using a dual-emission luminescent europium organic framework[J].Environmental Science & Technology Journal,2019,53(1):332-341.
[17] Cui Y Y,Lu H J,Hou H L,et al.Dissolution-recrystallization:a novel mechanism for fluorochromic detection of Th4+ using color-tunable luminescent metal-organic frameworks[J].Angewandte Chemie International Edition,2024,136(46):e202410453.
[18] Ge X Y,Chen J B,Guo S X,et al.Facile synthesis of dual-ligand Eu-MOF for ratiometric fluorescence and smartphone-assisted visual detection of Al3+[J].Dyes and Pigments,2025,239:112812.
[19] Wang X Y,Liu H J,Liu Y J,et al.Selective and visual detection of UO2+2 and Al3+ in real water by a luminescent Tb(Ⅲ) metal-organic framework sensor[J].Microchemical Journal,2024,207:111812.
[20] Wu C M,Feng Z H,Zhou H Q,et al.Metal-organic frameworks constructed from trivalent lanthanide nodes (Eu3+,Tb3+,and Dy3+) and thiophenethio-functionalized linker with photoluminescent response selective towards Ag+ ions[J].Dyes and Pigments,2022,198:109999.
[21] Luo J,Liu B S,Zhang X R,et al.A new fluorescent sensor constructed by Eu3+ post-functionalized metal-organic framework for sensing Ag+ with high selectivity and sensitivity in aqueous solution[J].Journal of Molecular Structure,2021,1227:129518.
[22] Yan D F,Yuan F,Chen Z,et al.Eu-doped carbon dots-MOF based turn-on fluorescent probe for trace Hg2+ and Pb2+ and construction of the simultaneous detection model[J].Chemical Engineering Journal,2024,499:156102.
[23] Syed A.A novel strategy for the synthesis of samarium/europium-metal organic frameworks,and their utilization for detection of Cr3+,Pb2+,and acetone as a luminescent sensor with superior selectivity and sensitivity properties[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2024,316:124345.
[24] Li Y,Cai D G,Zhu Z H,et al.Solvothermal synthesis and device fabrication of a Eu3+-based metal-organic framework as a turn-on and blue-shift fluorescence sensor toward Cr3+,Al3+ and Ga3+[J].Dalton Transactions,2023,52(13):4167-4175.
[25] Shi W,Zhang S Q,Wang Y,et al.Preparation of dual-ligands Eu-MOF nanorods with dual fluorescence emissions for highly sensitive and selective ratiometric/visual fluorescence sensing phosphate[J].Sensors and Actuators B:Chemical,2022,367:132008.
[26] Zhao J R,Zhang J Y,Yang W X,et al.Rational design of core-shell Ln-MOF hierarchitecture for ratiometric fluorescent sensing and bioimaging for phosphate or ATP[J].Sensors and Actuators B:Chemical,2023,389:133907.
[27] Wang Z G,Zhai W L,Wu Z Q,et al.Eu3+ and Tb3+ anchoring a 2D Zr-MOF for highly efficient fluorescence sensing detection towards Cr2O2-7 ions with high sensitivity,selectivity and anti-interference performances[J].Journal of Molecular Structure,2025,1321:139809.
[28] Zhao B B,Liu X F,Cheng Z,et al.A portable Eu-MOF-loaded paper-based probe integrated with smartphone for the visual and on-site detection of Cr2O2-7 in aqueous media[J].Talanta,2024,278:126462.
[29] Li J Y,Liu M,Li J X,et al.A MOF-on-MOF composite encapsulating sensitized Tb(Ⅲ) as a built-in self-calibrating fluorescent platform for selective sensing of F ions[J].Talanta,2023,259:124521.
[30] Che H C,Li Y,Zhang S Y,et al.A portable logic detector based on Eu-MOF for multi-target,on-site,visual detection of Eu3+ and fluoride in groundwater[J].Sensors and Actuators B:Chemical,2020,324:128641.
[31] Li Y P,Zhao Y J,Zhang W,et al.A fluorescent probe of nitrite based on Eu3+ functionalized metal-organic frameworks[J].Zeitschrift Für Anorganische und Allgemeine Chemie,2021,647(10):1091-1095.
[32] Min H,Han Z,Wang M,et al.A water-stable terbium metal-organic framework as a highly sensitive fluorescent sensor for nitrite[J].Inorganic Chemistry Frontiers,2020,7(18):3379-3385.
[33] Fan L H,Zhang J Y,Zhao Y,et al.A robust Eu-MOF as a multi-functional fluorescence sensor for detection of benzaldehyde,Hg2+,and Cr2O2-7/CrO2-4[J].Microchemical Journal,2024,196:109712.
[34] Xia Y F,Yuan H Q,Qiao C,et al.Multifunctional Eu3+-MOF for simultaneous quantification of malachite green and leuco-malachite green and efficient adsorption of malachite green[J].Journal of Hazardous Materials,2024,465:133386.
[35] Song J Y,Zhao B B,Wang Y R,et al.A portable smartphone-assisted Tb-MOF-based agar-slice probe for the rapid and on-site fluorescence assay of malachite green in aquatic products[J].Food Chemistry,2024,437:137883.
[36] Liu X F,Ma Q Q,Feng X,et al.A recycled Tb-MOF fluorescent sensing material for highly sensitive and selective detection of tetracycline in milk[J].Microchemical Journal,2021,170:106714.
[37] Kabak B.Synthesis and application of Tb-MOF for efficient fluorescence detection and removal of tetracycline from aqueous environments[J].Journal of Molecular Structure,2025,1322:140348.
[38] Chen X Z,Xu J,Li Y X,et al.A novel intelligently integrated MOF-based ratio fluorescence sensor for ultra-sensitive monitoring of TC in water and food samples[J].Food Chemistry,2023,405:134899.
[39] Zhao Y,Wang C A,Li J K,et al.A Eu(Ⅲ) metal-organic framework based on anthracenyl and alkynyl conjugation as a fluorescence probe for the selective monitoring of Fe3+ and TNP[J].RSC Advances,2022,12(41):26945-26952.
[40] Hanif S,Bhat Z U H,Abbasi A,et al.Hydrolyticallystabilized 5-hydroxyisophthalateappended Tb-MOF as a twofold chemosensor for discerning detection of 2,4,6-trinitrophenol and ferric ion:structural,topological and mechanistic sensing exploration via experimental and computational studies[J].Inorganica Chimica Acta,2023,552:121488.
[41] Bai W Q,Li C Y,Zhao Z J,et al.Eu3+ doped ethylenediamine functionalized UiO-66 probe for fluorescence sensing of formaldehyde[J].Spectrochim Acta A,2024,310:123937.
[42] Che H C,Li Y,Tian X K,et al.A versatile logic detector and fluorescent film based on Eu-based MOF for swift detection of formaldehyde in solutions and gas phase[J].Journal of Hazardous Materials,2021,410:124624.
[43] Zhang C Y,Lu K R,Li L R,et al.A water-stabilized Tb-MOF can be used as a sensitive and selective fluorescence sensor for the detection of oxytetracycline hydrochloride[J].Spectrochim Acta A,2024,304:123379.
[44] Liu L,Chen X L,Shang L,et al.Eu3+-postdoped MOFs are used for fluorescence sensing of TNP,TC and pesticides and for anti-counterfeiting ink application[J].Dyes and Pigments,2022,202:110253.
[45] Chi J,Song Y Y,Feng L.A ratiometric fluorescence sensor with different responsive modes based on carbon dots-embedded Tb-MOFs for the determination of norfloxacin and levofloxacin[J].Talanta,2024,280:126763.
基金资助
国家自然科学基金面上项目(52171089);辽宁省重点研发项目(民生科技类)(2024JH2/102500080);辽宁省教育厅基本科研(面上)项目(LJKMZ20220514);沈阳工业大学研究生教学改革研究项目(SYJG20222036)
PDF
