Santos Juanes, LucasRodríguez Sánchez, NoeliaBalestra, Salvador R. G.O. Núñez, NuriaArques, AntonioRuiz-Salvador, A. RabdelBallesteros, María de la Menta2025-05-052025-05-052025-05-0110.1039/d4ma01217hhttps://hdl.handle.net/10433/23838This work was supported by Spanish Ministerio de Ciencia e Innovación (PID2021-126400OB-C31, AquaEnAgri Project) and the European Commission (HORIZON.1.2 – Marie Skłodowska-Curie Actions VALZEO Project 101086354). Salvador R. G. Balestra also thanks Consejería de Universidades, Investigación e Innovación, Junta de Andalucía (grant number: POSTDOC_21_00069). We are grateful to C3UPO for providing high performance computing facilities.Metal–organic frameworks (MOFs) have recently been proposed as a plausible solution to the pressing issue of water scarcity and as a means of remediating contaminated water bodies. In light-assisted water treatment, they have so far only been exploited via the hydroxyl radical route, through Fenton-like processes. A new avenue is introduced here by the biomimetic conceptual design of MOF bearing hypervalent metal atoms for photocatalytic water treatment. We report a zeolitic imidazole framework (ZIF) material doped with iron (Fe-ZIF-7-III; UPO-4) synthesized via a novel mild treatment to stabilize photoactive hypervalent ferryl ions for the first time in a MOF for water treatment. The successful synthesis of the 2D material and the adequate incorporation of iron into the structure were demonstrated using X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). A simulation study analyzed the structure and stability of the Fe-ZIF-7-III material as well as the involvement of ferryl ions in the photo-Fenton-type process. Furthermore, the calculated band gap of this material shows its viability for use in photocatalysis using sunlight. This was confirmed by evaluating the photodegradation of caffeine, a model pollutant in water, without the assistance of hydroxyl radicals as indicated by a scavenger test. The recyclability test revealed that Fe-ZIF-7-III could be used continuously with effective catalytic activity, thus opening the door to the field of studying hypervalent metal MOFs not yet explored in water treatment.application/pdfenAttribution-NonCommercial 4.0 Internationalhttp://creativecommons.org/licenses/by-nc/4.0/Metal–organic frameworksOrganic contaminantjournal articleopen access