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Lanthanide-Functionalized Metal−Organic Framework as Ratiometric Probe for Selective Detection of 4-NA and Fe3+

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Abstract

Luminescent MOFs with dual or multiple emission centers can act as multi-target and self-calibrating probes to selectively detect environment pollutants with high precision. In this paper, we synthesized Ln3+@Zn-MOF (Ln3+ = Eu3+ and Tb3+) with dual emission characteristics by post-encapsulation Ln3+ ions into Zn-MOF. The fluorescence sensing experiments show that Eu3+@Zn-MOF can be used as a multi-functional and self-calibrating probe to selectively detect 4-nitroaniline (4-NA) and Fe3+ ions with high sensitivity, good anti-interference and repeatability. The LOD is 6.01 μM and 60.99 μM for 4-NA and Fe3+ ions, respectively. Compared to the pristine Zn-MOF, Eu3+@Zn-MOF exhibits the higher sensitivity and accuracy in detection application. Further studies on UV–vis adsorption spectra show that the possible fluorescence quenching mechanism are the competitive absorption of excitation light between MOF and the analytes. And this work presents a promising strategy to prepare dual emissions probes for effective detection of environment pollutants.

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References

  1. A.J. Lan, K.H. Li, H.H. Wu et al., A luminescent microporous metal-organic framework for the fast and reversible detection of high explosives. Angew Chem Int Edit 48(13), 2334–2338 (2010)

    Article  CAS  Google Scholar 

  2. L.H. Shi, N. Li, D.M. Wang et al., Environmental pollution analysis based on the luminescent metal organic frameworks: a review. TrAC Trend Anal Chem 134, 116131 (2021)

    Article  CAS  Google Scholar 

  3. G.Q. Tang, S.Y. Chen, P.E. Shaw et al., Fluorescent carbazole dendrimers for the detection of explosives. Polym Chem 2(10), 2360–2368 (2011)

    Article  CAS  Google Scholar 

  4. W.L. Fan, S.W. Yang, Y.Z. Zhang et al., Multifunctional flexible SERS sensor on a fixate gel pad: capturing, derivation, and selective picogram indirect detection of explosive 2,2’,4,4’,6,6’-hexanitrostilbene. ACS Sens 5(11), 3599–3606 (2020)

    Article  CAS  Google Scholar 

  5. Z.C. Hu, B.J. Deibert, J. Li, Luminescent metal-organic frameworks for chemical sensing and explosive detection. Chem Soc Rev 43(16), 5815–5840 (2014)

    Article  CAS  Google Scholar 

  6. X.C. Sun, Y. Wang, Y. Lei, Fluorescence based explosive detection: from mechanisms to sensory materials. Chem Soc Rev 44(22), 8019–8061 (2015)

    Article  CAS  Google Scholar 

  7. J. Li, J.F. Xia, F.F. Zhang et al., An electrochemical sensor based on copper-based metal-organic frameworks-graphene compositesfor determination of dihydroxy-benzene isomers in water. Talanta 181, 80–86 (2018)

    Article  CAS  Google Scholar 

  8. Z. Alexieva, M. Gerginova, P. Zlateva et al., Monitoring of aromatic pollutants biodegradation. Biochem Eng J 40(2), 233–240 (2008)

    Article  CAS  Google Scholar 

  9. Z.Q. Xu, X.L. He, Y.L. He et al., A luminescent terbium coordination complex as multifunctional sensing platform. Talanta 208, 120363 (2020)

    Article  CAS  Google Scholar 

  10. R.M. Wen, S.D. Han, G.J. Ren et al., A flexible zwitterion ligand based lanthanide metal–organic framework for luminescence sensing of metal ions and small molecules. Dalton Trans 44(24), 10914–10917 (2015)

    Article  CAS  Google Scholar 

  11. H.H. Yu, M.Y. Fan, Q. Liu et al., Two highly water-stable imidazole-based Ln-MOFs for sensing Fe3+, Cr2O72–/CrO42–in a water environment. Inorg Chem 59(3), 2005–2010 (2020)

    Article  CAS  Google Scholar 

  12. H. Li, Y. Han, Z. Shao et al., Water-stable Eu-MOF fluorescent sensors for trivalent metal ions and nitrobenzene. Dalton Trans 46(36), 12201–12208 (2017)

    Article  CAS  Google Scholar 

  13. L. Zhang, J.S. Hu, J.X. Li et al., A thermal and pH stable fluorescent coordination polymer for sensing nitro explosives or metal ions with high selectivity and sensitivity in aqueous solution. J Lumin 234, 117958 (2021)

    Article  CAS  Google Scholar 

  14. X. Luo, X. Zhang, Y.L. Duan et al., A novel luminescent Pb(II)-organic framework exhibiting a rapid and selective detection of trace amounts of NACs and Fe3+ with excellent recyclability. Dalton Trans 46(19), 6303–6311 (2017)

    Article  CAS  Google Scholar 

  15. J. Li, B. Yu, L. Fan et al., A novel multifunctional Tb-MOF fluorescent probe displaying excellent abilities for highly selective detection of Fe3+, Cr2O72− and acetylacetone. J Solid State Chem 306, 122782 (2022)

    Article  CAS  Google Scholar 

  16. Y. Zhou, H.H. Chen, B. Yan, An Eu3+ post-functionalized nanosized metal-organic framework for cation exchange-based Fe3+-sensing in an aqueous environment. J Mater Chem A 2(33), 13691–13697 (2014)

    Article  CAS  Google Scholar 

  17. T.K. Das, S. Ganguly, S. Remanan et al., Mussel-inspired Ag/poly (norepinephrine)/ MnO2 heterogeneous nanocatalyst for efficient reduction of 4-nitrophenol and 4-nitroaniline: an alternative approach. Res Chem Intermediat 46(7), 3629–3650 (2020)

    Article  CAS  Google Scholar 

  18. T.K. Das, A. Poater, Review on the use of heavy metal deposits from water treatment waste towards catalytic chemical syntheses. Int J Mol Sci 22(24), 13383 (2021)

    Article  CAS  Google Scholar 

  19. B.L. Chen, L.B. Wang, Y.Q. Xiao et al., A luminescent metal-organic framework with Lewis basic pyridyl sites for the sensing of metal ions. Angew. Chem. 121(3), 508–511 (2009)

    Article  Google Scholar 

  20. Z. Chen, Y.W. Sun, L.L. Zhang et al., A tubular europium-organic framework exhibiting selective sensing of Fe3+ and Al3+ over mixed metal ions. Chem Commun 49(98), 11557–11559 (2013)

    Article  CAS  Google Scholar 

  21. X.F. Wang, C.X. Chu, Y.W. Wu, Y.Y. Deng, J. Zhou, M. Yang et al., Synthesis of yttrium(III)-based rare-earth metal-organic framework nanoplates and its applications for sensing of fluoride ions and pH. Sensor Actuat B Chem 321, 128455 (2020)

    Article  CAS  Google Scholar 

  22. M.L. Hu, S.A.A. Razavi, M. Piroozzadeh, A. Morsali, Sensing organic analytes by metal-organic frameworks: a new way of considering the topic. Inorg Chem Front 7(7), 1598–1632 (2020)

    Article  CAS  Google Scholar 

  23. W. Raza, D. Kukkar, H. Saulat, N. Raza, M. Azam, A. Mehmood et al., Metal-organic frameworks as an emerging tool for sensing various targets in aqueous and biological media. TrAC-Trend Anal Chem 120, 115654 (2019)

    Article  CAS  Google Scholar 

  24. L. Zhang, J.S. Hu, J.X. Li, J. Zhang, A thermal and pH stable fluorescent coordination polymer for sensing nitro explosives or metal ions with high selectivity and sensitivity in aqueous solution. J Lumin 234, 117958 (2021)

    Article  CAS  Google Scholar 

  25. N.N. Ji, Z.Q. Shi, H.L. Hu, H.G. Zheng, A triphenylamine-functionalized luminescent sensor for efficient p-nitroaniline detection. Dalton Trans 47(21), 7222–7228 (2018)

    Article  CAS  Google Scholar 

  26. G. Chakraborty, S.K. Mandal, Neutral luminescent metal-organic frameworks: structural diversification, photophysical properties, and sensing applications. Inorg Chem 56(23), 14556–14566 (2017)

    Article  CAS  Google Scholar 

  27. Z.H. Wei, D.S. Chen, Z.F. Guo et al., Eosin Y-embedded zirconium-based metal-organic framework as a dual-emitting built-in self-calibrating platform for pesticide detection. Inorg Chem 59(8), 5386–5393 (2020)

    Article  CAS  Google Scholar 

  28. W. Xie, W.W. He, S.L. Li et al., An anionic interpenetrated zeolite-like metal-organic framework composite as a tunable dual-emission luminescent switch for detecting volatile organic molecules. Chem-Eur J 22, 17298–17304 (2016)

    Article  CAS  Google Scholar 

  29. H.J. Yu, Q. Liu, M.Y. Fan et al., Novel Eu-MOF-based mixed matrix membranes and 1D Eu-MOF-based ratiometric fluorescent sensor for the detection of metronidazole and PA in water. Dyes Pigments 197, 109812 (2022)

    Article  CAS  Google Scholar 

  30. Y.J. Li, J.Y. Wang, Z.J. Huang et al., An Eu-doped Zr-metal-organic framework for simultaneous detection and removal of antibiotic tetracycline. J Environ Chem Eng 9(5), 106012 (2021)

    Article  CAS  Google Scholar 

  31. L. Zhao, X. Song, X. Ren et al., Rare self-luminous mixed-valence Eu-MOF with a self-enhanced characteristic as a near-infrared fluorescent ECL probe for nondestructive immunodetection. Anal Chem 93(24), 8613–8621 (2021)

    Article  CAS  Google Scholar 

  32. A. Helal, M. Naeem, M.E. Arafat et al., Europium doped Ni(BTC) metal-organic framework for detection of heteroaromatic compounds in mixed aqueous media. Mater Res Bull 146, 111604 (2022)

    Article  CAS  Google Scholar 

  33. M. Jurcic, W.J. Peveler, C.N. Savory et al., The vapour phase detection of explosive markers and derivatives using two fluorescent metal-organic frameworks. J Mater Chem A 3(12), 6351–6359 (2015)

    Article  CAS  Google Scholar 

  34. Y.J. Yang, M.J. Wang, K.L. Zhang, A novel photoluminescent Cd (II)-organic framework exhibiting rapid and efficient multi-responsive fluorescence sensing for trace amounts of Fe3+ ions and some NACs, especially for 4-nitroaniline and 2-methyl-4-nitroaniline. J Mater Chem C 4(48), 11404–11418 (2016)

    Article  CAS  Google Scholar 

  35. C. Liu, X. Bo, L. Guo, A novel electrochemical sensing platform of JUC-62 metal-organic framework/platelet ordered mesoporous carbon for high selective detection of nitro-aromatic compounds. Sensor Actuat B-Chem 297, 126741 (2019)

    Article  CAS  Google Scholar 

  36. Q.Q. Tu, L.L. Ren, A.L. Cheng et al., Fabrication of a dual-emitting RhB@Zn-1 composite as a recyclable luminescent sensor for sensitive detection of nitrofuran antibiotics. CrystEngComm 23(3), 629–637 (2021)

    Article  CAS  Google Scholar 

  37. Q.T. Xu, Z.H. Chen, H. Min et al., Water stable heterometallic Zn-Tb coordination polymer for rapid detection of the ultraviolet filter benzophenone. Inorg Chem 59(10), 6729–6735 (2020)

    Article  CAS  Google Scholar 

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Acknowledgements

This project is supported by NSF of Tianjin (No. 18JCYBJC89100).

Funding

Funding was provided by Natural Science Foundation of Tianjin City (Grant No.: 18JCYBJC89100)

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Authors and Affiliations

  1. School of Chemistry & State Key Lab Separate Membranes & Membrane Process, Tiangong University, Tianjin, 300387, China

    Zhenyu Sun, Zhongrui Zhao & Fengqin Wang

  2. School of Chemical Engineering and Technology, Tiangong University, Tianjin, 300387, China

    Jianbo Liu & Xiaoqing Wang

  3. School of Materials Science and Engineering, Tiangong University, Tianjin, 300387, China

    Yang Li

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  1. Zhenyu Sun
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  3. Jianbo Liu
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Correspondence to Fengqin Wang or Xiaoqing Wang.

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Supplementary Information

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10904_2022_2323_MOESM1_ESM.docx

Supplementary file1 FT-IR spectra and PXRD patterns of Ln3+@Zn-MOF and Zn-MOF (Fig. S1); SEMimages and corresponding element contents (Fig. S2); Emission spectra in differentorganic solvents (Fig. S3); Fluorescence titration with the addition of different volumesof 4-NA (Fig. S4); IR spectra and PXRD patterns before and after cycle of Eu3+@Zn-MOF (Fig. S5); Fluorescence titration of with the addition of different volumes of Fe3+(Fig. S6); The UV-vis absorption spectra and different kind of nitroaromatic compoundsand cations (Fig. S7). (DOCX 7564 kb)

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Sun, Z., Li, Y., Liu, J. et al. Lanthanide-Functionalized Metal−Organic Framework as Ratiometric Probe for Selective Detection of 4-NA and Fe3+. J Inorg Organomet Polym 32, 2953–2960 (2022). https://doi.org/10.1007/s10904-022-02323-y

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  • DOI: https://doi.org/10.1007/s10904-022-02323-y

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