Post-Synthetic Modification of Zr-based Metal-Organic Frameworks with Imidazole: Variable Optical Behavior and Sensing |
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Authors: | Dibya Prakash Biswal Dipankar Singha Dr Jagannath Panda Dr Malay Kumar Rana |
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Institution: | 1. Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Berhampur, Berhampur, 760010 Odisha, India
Authors contributed equally
Contribution: Conceptualization (equal), Data curation (equal), Writing - original draft (equal);2. Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Berhampur, Berhampur, 760010 Odisha, India
Contribution: Data curation (supporting), Writing - original draft (supporting);3. Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER), Berhampur, Berhampur, 760010 Odisha, India |
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Abstract: | UiO-66-NH2-IM, a fluorescent metal-organic framework (MOF), was synthesized by post-synthetic modification of UiO-66-NH2 with 2-imidazole carboxaldehyde via a Schiff base reaction. It was examined using various characterization techniques (PXRD, FTIR, NMR, SEM, TGA, UV-Vis DRS, and photoluminescence spectroscopy). The emissive feature of UiO-66-NH2-IM was utilized to detect volatile organic compounds (VOCs), metal ions, and anions, such as acetone, Fe3+, and carbonate (CO32?). Acetone turns off the high luminescence of UiO-66-NH2-IM in DMSO, with the limit of detection (LOD) being 3.6 ppm. Similarly, Fe3+ in an aqueous medium is detected at LOD=0.67 μM (0.04 ppm) via quenching. On the contrary, CO32? in an aqueous medium significantly enhances the luminescence of UiO-66-NH2-IM, which is detected with extremely high sensitivity (LOD=1.16 μM, i. e., 0.07 ppm). Large Stern-Volmer constant, Ksv, and low LOD values indicate excellent sensitivity of the post-synthetic MOF. Experimental data supported by density functional theory (DFT) calculations discern photo-induced electron transfer (PET), resonance energy transfer (RET), inner filter effect (IFE), or proton abstraction as putative sensing mechanisms. NMR and computational studies propose a proton abstraction mechanism for luminescence enhancement with CO32?. Moreover, the optical behavior of the post-synthetic material toward analytes is recyclable. |
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Keywords: | metal-organic framework optical sensing post-synthetic modification volatile organic compounds photoluminescence |
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