Sustainable Semicrystalline/Nanocrystalline UiO-66-Type Zr-MOFs as Photodegraders of Rhodamine B

UiO-type Zr-BDC MOFs have garnered the interest of the scientific community due to their exceptional diversity in composition, structure, and chemical environment, as well as their high thermal and chemical stabilities. This work demonstrates the sustainable synthesis of a series of nanocrystalline/...

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Detalles Bibliográficos
Autores: Yassin, Jemal M., Taddesse, Abi M., Sánchez Sánchez, Manuel
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/391267
Acceso en línea:http://hdl.handle.net/10261/391267
Access Level:acceso abierto
Palabra clave:Sustainable synthesis
UiO-66-type MOFs
RhB degradation
Semicrystalline
Nanocrystalline
Descripción
Sumario:UiO-type Zr-BDC MOFs have garnered the interest of the scientific community due to their exceptional diversity in composition, structure, and chemical environment, as well as their high thermal and chemical stabilities. This work demonstrates the sustainable synthesis of a series of nanocrystalline/semicrystalline UiO-66(Zr) metal–organic frameworks (MOFs) under facile conditions—specifically at room temperature, in water, with high yield, and without the use of modulators or toxic byproducts. The synthesis involves either deprotonating the linker or utilizing various ratios of water and DMF as solvents. The as-prepared materials obtained from both synthesis strategies share key structural features with conventional UiO-66(Zr) in their short- and medium-range physicochemical properties, while exhibiting significant differences in crystallinity and textural properties. Nonetheless, the materials generally lack long-range order (semicrystalline), in particular these synthesized following the deprotonation strategy. However, the materials prepared using mixed solvent strategy seem to exhibit characteristics of nanocrystalline UiO-66(Zr). Overall, both approaches successfully addressed various synthesis challenges related to the highly sought-after Zr-based metal–organic frameworks (MOFs). Some of these MOF materials were tested for the photodegradation of rhodamine B (RhB) under mercury light irradiation, evidencing high photocatalytic efficiency of up to 75 ± 0.078% within 120 min under the pseudo-first-order model. This suggests an interaction between the photocatalyst and the RhB dye, involving electron injection from RhB and the ability for ligand-to-metal charge transfer (LMCT), which enhances the efficient photocatalytic degradation of RhB. The trapping experiments indicated that superoxide radicals (•O2−) and photogenerated holes (h+) are crucial in the photodegradation of RhB. Moreover, the materials showed good recyclability across five tested cycles. A plausible photocatalytic reaction mechanism has been proposed to explain these findings.