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The serious problems derived from the presence and accumulation of organic pollutants in waters has led in recent years to the use of new porous materials for their detection and capture [1]. Metal-Organic Frameworks (MOFs) have emerged as ideal candidates for such purposes due to their high permanent porosity, stability and great chemical versatility, including the potential for post-synthetic modifications [2]. In this work [3], zirconium(IV) and hafnium(IV) analogues of the MOF families MOF-808 and MIP-206 were synthesized and post-synthetically functionalized with europium(III) ions. The resulting materials combine the MOFs’ inherent stability and porosity with the exceptional luminescent properties provided by the Eu(III) ions [4], leading to dual-functional MOFs suitable for the simultaneous capture and optical sensing of organic molecules in water. Namely, the ability of these MOFs to capture and detect amoxicillin and chloramphenicol antibiotics in water was evaluated, demonstrating promising potential for water remediation applications.
The local structure of the post-synthetic Eu(III)-modified materials was also studied employing advanced synchrotron techniques, elucidating the exact coordination environment of the Eu (III) ions. These techniques included X-ray pair distribution function (xPDF) [5] and XAS analysis (Zr K-edge and Eu L3-edge measurements) performed at BL-16 NOTOS beamline in ALBA [6]. Additional in situ XAS spectra, recorded during pollutant capture in water, allowed monitoring of the pollutant∙∙∙MOF´s cluster interactions taking place during the process [7].
This work demonstrates how the synchrotron techniques employed can also serve as indispensable structural study tools for understanding specific host-guest interactions in MOFs, providing insights into the mechanistic aspects and the nature of the chemical processes involved.
[FIGURE 1]:Representation of the inorganic M6O8 (M=Zr or Hf) clusters in MIP-206 and MOF-808 and the chemical formula of chloramphenicol and the amoxicillin, and the k2-weighted Zr K-edge EXAFS for Zr-MOF-808 and Zr-MIP-206 series.
References:
1. Homem, V.; Santos, L. J. Environ. Manage. 2011, 92, 2304–2347.
2. Howarth, A. J.; Liu, Y.; Hupp, J. T.; Farha, O. K. CrystEngComm 2015, 17, 7245–7253.
3. Roselló-González, M.; Loukopoulos, E.; Marini, C.; Gil-San-Millan; R.; Platero-Prats, A. Chemrxiv, 2026, doi.org/10.26434/chemrxiv.15005663/v1
4. DeCoste, J. B.; Peterson, G. W.; Jasuja, H.; Glover, T. G. ; Huang, Y.; Walton, K. S. J. Mater. Chem. A 2013, 1, 5642.
5. Romero-Muñiz, I.; Loukopoulos, E.; Xiong, Y.; Li, F.; Ab, Z.; Platero-Prats, A. E. Chem. Soc. Rev. 2024, 53, 24, 11772–11803.
6. Castillo-Blas, C.; Romero-Muñiz, I.; Mavrandonakis, A.; Simonelli, L.; Platero-Prats, A. E. Chem. Commun. 2020, 56, 100, 15615–15618.
7. Marugán-Benito, S.; Vlachos, M.; Ahrens, L.; Roselló-González, M.; Marini, C.; Prat Albert, J.; Mavrandonakis, A.; Loukopoulos, E.; Platero-Prats, A. E. J. Am. Chem. Soc. 2026, 148, 19, 19672–19683.