A Novel Ti12-Based Metal-Organic Framework for Photocatalytic Hydrogen Evolution
[EN] A new microporous titanium-based metal-organic framework (Ti-MOF), labeled as MIP-209(Ti) (MIP: Materials from Institute of Porous Materials of Paris), features nitro terephthalate ligands and Ti12O15 oxo-clusters, as revealed by continuous rotation electron diffraction (cRED). MIP-209(Ti) can...
| Autores: | , , , , , , , , , , , , , , , |
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| Formato: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Recursos: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:dnet:riunet______::2312b854178ddd2cd970eb7a63ac278a |
| Acesso em linha: | https://riunet.upv.es/handle/10251/235303 |
| Access Level: | acceso abierto |
| Palavra-chave: | Titanium-based metal-organic frameworks Photocatalytic hydrogen evolution Water splitting Chromium doping Ti12O15 oxo-clusters Solar photocatalysis |
| Resumo: | [EN] A new microporous titanium-based metal-organic framework (Ti-MOF), labeled as MIP-209(Ti) (MIP: Materials from Institute of Porous Materials of Paris), features nitro terephthalate ligands and Ti12O15 oxo-clusters, as revealed by continuous rotation electron diffraction (cRED). MIP-209(Ti) can be obtained using two different terephthalate (1, 4-BDC2¿) derivatives such as NO2-BDC and 2Cl-BDC in an eco-friendly solvent, suggesting the isostructural versatility of Ti12-MOFs. Alternatively, its Ti-oxo-cluster can be tuned, similarly to MIP-177(Ti)-LT bearing the same Ti12O15 sub-unit. Typically, low percentage Cr3+ doping (¿5 at%) in MIP-209(Ti) favorably enhances the water stability. MIP-209(Ti-Cr)-NO2 shows a significant hydrogen production rate, with good reusability and stability under simulated solar light irradiation. Compared to the benchmark Ti-MOF IEF-11, the hydrogen production of MIP-209(Ti-Cr)-NO2 with 5 at% Cr doping has a fourfold enhancement in photocatalytic hydrogen evolution from water splitting reaction (HER) during 5 h in presence of methanol (5 812 µmol/gcat against 1 391 µmol/gcat), as well as, without any noble metal co-catalyst, a sixfold enhancement in overall water splitting reaction (OWS) (681 and 325 µmol/gcat of H2 and O2, respectively, against 94 and 53 µmol/gcat of H2 and O2, respectively). This work represents a leap forward in the synthesis of Ti-MOFs and their practical photocatalytic applications. |
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