Skip to main content
SpringerLink
Log in

Amine-decorated Zirconium Based Metal Organic Framework for Ultrafast Detection of 2,4,6-Trinitrophenol in Aqueous Samples

  • Research
  • Published:
Journal of Fluorescence Aims and scope Submit manuscript

Abstract

An amine-decorated zirconium based metal organic framework (MOF) UiO-66-NH2 with rod shape morphology was synthesized by solvothermal process using 2-aminoterephthalic acid as an organic linker. Crystallinity of synthesized MOF material was confirmed with PXRD technique. MOF was employed as selective and sensitive sensor for ultra-trace detection of 2,4,6-trinitrophenol (TNP) in aqueous matrix, even in coexistence with other competitive nitroaromatic analytes. High value of Stern-Volmer quenching constant Ksv (1.106 × 105 M− 1), plausible photoluminescent quenching efficiency (97.8%) and lower detection limit (0.95 µM/217ng mL− 1) ascertained extraordinary sensitivity of developed MOF for TNP. Density functional theory calculations and electrostatic interactions (i.e. ionic interaction, H-bonding and π-π interaction) indicated that electron and energy transfer processes play a key role in turn-off quenching response of UiO-66-NH2 sensor. Spiked real samples were analysed to validate the developed method, which satisfactorily established the developed MOF sensor as an efficient tool for analysis.

Graphical Abstract

Highlights

An amine-decorated zirconium based metal organic framework (UiO-66-NH2) was synthesised.

Developed sensor detected 2,4,6-trinitrophenol (TNP) in water samples.

Detection of TNP was done in presence of other potentially competitive nitroaromatic analytes.

Lower detection limit (0.95 µM/217ng mL− 1) ascertained extraordinary sensitivity of developed UiO-66-NH2 for TNP.

Electron and energy transfer processes justify the sensitivity of UiO-66-NH2 sensor for TNP.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

Data Availability

All the data associated with this research has been presented in this paper.

Code Availability

Not applicable.

References

  1. Bhatt DR, Maheria KC, Parikh JK (2015) Highly efficient micellar extraction of toxic picric acid into novel ionic liquid: effect of parameters, solubilization isotherm, evaluation of thermodynamics and design parameters. J Hazard Mater 300:338–346

    Article  CAS  PubMed  Google Scholar 

  2. Han Y, Chen Y, Feng J et al (2017) One-pot synthesis of fluorescent silicon nanoparticles for sensitive and selective determination of 2, 4, 6-trinitrophenol in aqueous solution. Anal Chem 89:3001–3008

    Article  CAS  PubMed  Google Scholar 

  3. Chen X, Sun C, Liu Y et al (2020) All-inorganic perovskite quantum dots CsPbX3 (Br/I) for highly sensitive and selective detection of explosive picric acid. Chem Eng J 379:122360

    Article  CAS  Google Scholar 

  4. Shen J, Zhang J, Zuo Y et al (2009) Biodegradation of 2, 4, 6-trinitrophenol by Rhodococcus sp. isolated from a picric acid-contaminated soil. J Hazard Mater 163:1199–1206

    Article  CAS  PubMed  Google Scholar 

  5. Takahashi M, Ogata H, Izumi H et al (2004) Comparative toxicity study of 2, 4, 6-trinitrophenol (picric acid) in newborn and young rats. Congenit Anom (Kyoto) 44:204–214

    Article  CAS  PubMed  Google Scholar 

  6. Barron L, Gilchrist E (2014) Ion chromatography-mass spectrometry: a review of recent technologies and applications in forensic and environmental explosives analysis. Anal Chim Acta 806:27–54

    Article  CAS  PubMed  Google Scholar 

  7. Lopez-Lopez M, Garcia-Ruiz C (2014) Infrared and Raman spectroscopy techniques applied to identification of explosives. TrAC Trends Anal Chem 54:36–44

    Article  CAS  Google Scholar 

  8. Rahimi-Nasrabadi M, Zahedi MM, Pourmortazavi SM et al (2012) Simultaneous determination of carbazole-based explosives in environmental waters by dispersive liquid—liquid microextraction coupled to HPLC with UV-Vis detection. Microchim Acta 177:145–152

    Article  CAS  Google Scholar 

  9. Yan F, He Y, Ding L, Su B (2015) Highly ordered binary assembly of silica mesochannels and surfactant micelles for extraction and electrochemical analysis of trace nitroaromatic explosives and pesticides. Anal Chem 87:4436–4441

    Article  CAS  PubMed  Google Scholar 

  10. Majumder S, Pramanik A, Mandal S, Mohanta S (2019) Experimental and theoretical exploration of sensing and magnetic properties of a triply bridged dicopper (II) complex: the first discrete metal complex to sense picric acid in pure water. J Photochem Photobiol A Chem 383:111987

    Article  CAS  Google Scholar 

  11. Rong M, Lin L, Song X et al (2015) A label-free fluorescence sensing approach for selective and sensitive detection of 2, 4, 6-trinitrophenol (TNP) in aqueous solution using graphitic carbon nitride nanosheets. Anal Chem 87:1288–1296

    Article  CAS  PubMed  Google Scholar 

  12. Ju B, Wang Y, Zhang Y-M et al (2018) Photostable and low-toxic yellow-green carbon dots for highly selective detection of explosive 2, 4, 6-trinitrophenol based on the dual electron transfer mechanism. ACS Appl Mater Interfaces 10:13040–13047

    Article  CAS  PubMed  Google Scholar 

  13. Jiang S, Meng L, Ma W et al (2021) Morphology controllable conjugated network polymers based on AIE-active building block for TNP detection. Chin Chem Lett 32:1037–1040

    Article  CAS  Google Scholar 

  14. Shellaiah M, Sun K-W (2021) Progress in metal-organic frameworks facilitated mercury detection and removal. Chemosensors 9:101

    Article  CAS  Google Scholar 

  15. Olorunyomi JF, Geh ST, Caruso RA, Doherty CM (2021) Metal–organic frameworks for chemical sensing devices. Mater Horizons 8:2387–2419

    Article  CAS  Google Scholar 

  16. Qiu Q, Chen H, Wang Y, Ying Y (2019) Recent advances in the rational synthesis and sensing applications of metal-organic framework biocomposites. Coord Chem Rev 387:60–78

    Article  CAS  Google Scholar 

  17. Wang B, Lv X-L, Feng D et al (2016) Highly stable zr (IV)-based metal–organic frameworks for the detection and removal of antibiotics and organic explosives in water. J Am Chem Soc 138:6204–6216

    Article  CAS  PubMed  Google Scholar 

  18. Yu F, Du T, Wang Y et al (2022) Ratiometric fluorescence sensing of UiO-66-NH2 toward hypochlorite with novel dual emission in vitro and in vivo. Sens Actuators B Chem 353:131032

    Article  CAS  Google Scholar 

  19. Peterson GW, Mcentee M, Harris CR et al (2016) Detection of an explosive simulant via electrical impedance spectroscopy utilizing the UiO-66-NH 2 metal–organic framework. Dalt Trans 45:17113–17116

    Article  CAS  Google Scholar 

  20. Zhang N, Jin R, Mao G et al (2022) Nickle-Schiff base covalently grafted to UiO-66-NH2 as heterogeneous catalyst for ethylene oligomerization. Inorganica Chim Acta 531:120674

    Article  CAS  Google Scholar 

  21. Liang Y, He J, Huang Z et al (2020) An amino-functionalized zirconium-based metal-organic framework of type UiO-66-NH2 covered with a molecularly imprinted polymer as a sorbent for the extraction of aflatoxins AFB1, AFB2, AFG1 and AFG2 from grain. Microchim Acta 187:1–8

    Article  Google Scholar 

  22. Tambat SN, Sane PK, Suresh S et al (2018) Hydrothermal synthesis of NH2-UiO-66 and its application for adsorptive removal of dye. Adv Powder Technol 29:2626–2632

    Article  CAS  Google Scholar 

  23. Pramanik S, Zheng C, Zhang X et al (2011) New microporous metal – organic framework demonstrating unique selectivity for detection of high explosives and aromatic compounds. J Am Chem Soc 133:4153–4155

    Article  CAS  PubMed  Google Scholar 

  24. Ma Y, Zhang Y, Kong L, Yang J (2019) Rational molecular design: functional quinoline derivatives for PA detection, gaseous acid/base switching and anion-controlled fluorescence. CrystEngComm 21:94–101

    Article  CAS  Google Scholar 

  25. Ahmed R, Ali A, Ahmad M et al (2020) Phenanthroimidazole derivatives as a chemosensor for picric acid: a first realistic approach. New J Chem 44:20092–20100

    Article  CAS  Google Scholar 

  26. Kumar V, Kumar A, Chini MK, Satapathi S (2021) Fluorescent Fe2O3-CdSe nanocomposite probe for selective detection and removal of picric acid. Mater Chem Phys 260:124130

    Article  CAS  Google Scholar 

  27. Li Y, Wang D, Li S et al (2020) Magnetically separable Fe3O4@ Au@ Tb-MOF fluorescent probe with well‐designed Sandwich structure and metal‐enhanced fluorescence. ChemistrySelect 5:4028–4033

    Article  CAS  Google Scholar 

  28. Singh R, Mitra K, Singh S et al (2019) Highly selective fluorescence ‘turn off’sensing of picric acid and efficient cell labelling by water-soluble luminescent anthracene-bridged poly (N-vinyl pyrrolidone). Analyst 144:3620–3634

    Article  CAS  PubMed  Google Scholar 

  29. Srivastava S, Gupta BK, Gupta R (2017) Lanthanide-based coordination polymers for the size-selective detection of nitroaromatics. Cryst Growth Des 17:3907–3916

    Article  CAS  Google Scholar 

  30. Khatua S, Goswami S, Biswas S et al (2015) Stable multiresponsive luminescent MOF for colorimetric detection of small molecules in selective and reversible manner. Chem Mater 27:5349–5360

    Article  CAS  Google Scholar 

  31. Dong S, Hu J, Wu K, Zheng M (2018) A mg (II)-MOF as recyclable luminescent sensor for detecting TNP with high selectivity and sensitivity. Inorg Chem Commun 95:111–116

    Article  CAS  Google Scholar 

  32. Jin J-C, Wu J, He Y-X et al (2017) A 3D luminescent zn (II) MOF for the detection of high explosives and the degradation of organic dyes: an experimental and computational study. CrystEngComm 19:6464–6472

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful to the Chemistry Department, Punjabi University, Patiala, for providing lab and instrument facilities.

Funding

Not applicable.

Author information

Authors and Affiliations

  1. Department of chemistry, Punjabi university, Patiala, 147002, Punjab, India

    Rajpal Verma, Manpreet Kaur, Deepika Garg & Ashok Kumar Malik

  2. Punjabi university constituent college, Ghanaur, Patiala, 140702, Punjab, India

    Gaurav Dhingra

  3. Department of Chemistry, Panjab University, Sector 14, Chandigarh, 160014, India

    Irshad Mohiuddin

  4. Presently associated with Dr. B. R. Ambedkar Govt. college Dabwali, Sirsa, Haryana, India

    Rajpal Verma

Authors
  1. Rajpal Verma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Gaurav Dhingra
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Manpreet Kaur
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Deepika Garg
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Irshad Mohiuddin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ashok Kumar Malik
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Rajpal Verma and Gaurav Dhingra: Conceptualization, Methodology, Data curation, Writing - original draft, Visualization, Validation. Manpreet Kaur, Deepika Garg and Irshad Mohiuddin: Project administration, Investigation, Writing - original draft, reviewing and editing. Ashok Kumar Malik: Investigation, Project administration, Supervision, Formal analysis, Writing - review and editing.

Corresponding author

Correspondence to Ashok Kumar Malik.

Ethics declarations

Ethics Approval

Not applicable.

Consent to Participate

Not applicable.

Consent for publication

Not applicable.

Conflict of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Verma, R., Dhingra, G., Kaur, M. et al. Amine-decorated Zirconium Based Metal Organic Framework for Ultrafast Detection of 2,4,6-Trinitrophenol in Aqueous Samples. J Fluoresc 33, 2085–2098 (2023). https://doi.org/10.1007/s10895-023-03216-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10895-023-03216-0

Keywords

Search

Navigation