Lucas Santos-Juanes, Noelia Rodriguez-Sanchez, Salvador R. G. Balestra, Nuria O. Núñez, Antonio Arques, A. Rabdel Ruiz-Salvador and Menta Ballesteros
{"title":"A hypervalent metal MOF catalyst as an avenue to go beyond heterogeneous Fenton-like processes for organic contaminant removal in water†","authors":"Lucas Santos-Juanes, Noelia Rodriguez-Sanchez, Salvador R. G. Balestra, Nuria O. Núñez, Antonio Arques, A. Rabdel Ruiz-Salvador and Menta Ballesteros","doi":"10.1039/D4MA01217H","DOIUrl":null,"url":null,"abstract":"<p >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 <em>via</em> 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 <em>via</em> 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.</p>","PeriodicalId":18242,"journal":{"name":"Materials Advances","volume":" 11","pages":" 3612-3621"},"PeriodicalIF":4.7000,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ma/d4ma01217h?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Materials Advances","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/ma/d4ma01217h","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
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.