Abstract
In this research, Zn- or Cd-based metal–organic frameworks (coded ZnMOF-1 and CdMOF-1) containing benzene-1,4-dicarboxylic acid (H2bdc) and pyridyl-based Schiff base (4-pyridylcarboxaldehydeisonicotinoylhydrazone (L)) dual ligands were successfully assembled via a conventional solvothermal method. The photoluminescence quenching response of ZnMOF-1 and CdMOF-1 and their sensing sensitivity and selectivity towards various inorganic anions were evaluated in aqueous media. Crystallographic and thermogravimetric studies confirm the formation of both MOFs with good crystallinity and thermal stability. Photoluminescence studies also verify the selectivity of ZnMOF-1 and CdMOF-1 for efficient sensing of inorganic oxyanions (like chromate/dichromate: CrO42− and Cr2O72−). Further, it was noted that only chromate/dichromate (CrO42−/Cr2O72−) anions showed a significant turn-off quenching effect while other anions (like F−, Br−, I−, Cl−, ClO4−, SCN−, SO42−, NO3−, and NO2−) have a low/negligible effect on the photoluminescence intensity of both MOFs. The limit of detection (LOD) of chromate/dichromate by ZnMOF-1 and CdMOF-1 was 9.79/10.94 µM and 2.68/1.48 µM, respectively. A probable mechanism for turn-off quenching response towards chromate and dichromate anions could be attributed to the spectral overlap of both excitation and emission spectra of ZnMOF-1/CdMOF-1 with the absorption spectra of chromate/dichromate anions. As a result, the energy transfer from ZnMOF-1 or CdMOF-1 to the target chromate and dichromate anions decreased fluorescence intensity (i.e., fluorescence quenching effect).
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Acknowledgements
The authors are thankful to the Chemistry Department, Punjabi University, Patiala, for providing lab and instrument facilities. One of the author Manpreet kaur is highly obliged to the UGC, New Delhi, India, for UGC-SRF fellowship.
Funding
One of the authors, Manpreet kaur is grateful to University Grants Commission (UGC), New Delhi, India, for providing senior research fellowship.
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Manpreet Kaur: Performed the experimentation. Ashok Kumar Malik and Mohamad Yusuf: Writing and checking the paper.
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Highlights
• Two metal–organic frameworks (ZnMOF-1 and CdMOF-1) associated with pyridyl Schiff-base ligand were successfully synthesized.
• Both MOFs displayed a good photoluminescent recognition ability for oxyanions (like chromate and dichromate) in the aqueous phase.
• Competetive energy absorption and FRET mechanisms explained the fluorescence quenching effect of both MOFs.
• The prepared Zn or Cd-MOFs exhibited excellent sensing recyclability for at least three cycles.
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10895_2022_3036_MOESM1_ESM.docx
Supplementary file1 (DOCX 906 KB) FT-IR, PL spectra, SV plots, quenching percentage graph, UV−vis spectra, LOD calculations, comparison table for chromate and dichromate anions.
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Kaur, M., Yusuf, M. & Malik, A.K. Schiff Base-functionalized Metal–organic Frameworks for Selective Sensing of Chromate and Dichromate in Water. J Fluoresc 33, 61–75 (2023). https://doi.org/10.1007/s10895-022-03036-8
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DOI: https://doi.org/10.1007/s10895-022-03036-8