A Novel Ti <sub>12</sub> ‐Based Metal‐Organic Framework for Photocatalytic Hydrogen Evolution
Abstract 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 Ti 12 O 15 oxo‐clusters, as revealed by continuous rotation electron diffraction (cRED). MIP‐209(Ti) can be obtained using two different terephthalate (1, 4‐BDC 2− ) derivatives such as NO 2 ‐BDC and 2Cl‐BDC in an eco‐friendly solvent, suggesting the isostructural versatility of Ti 12 ‐MOFs. Alternatively, its Ti‐oxo‐cluster can be tuned, similarly to MIP‐177(Ti)‐LT bearing the same Ti 12 O 15 sub‐unit. Typically, low percentage Cr 3+ doping (≤5 at%) in MIP‐209(Ti) favorably enhances the water stability. MIP‐209(Ti‐Cr)‐NO 2 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)‐NO 2 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 µ mol/g cat against 1 391 µ mol/g cat ), as well as, without any noble metal co‐catalyst, a sixfold enhancement in overall water splitting reaction (OWS) (681 and 325 µ mol/g cat of H 2 and O 2 , respectively, against 94 and 53 µ mol/g cat of H 2 and O 2 , respectively). This work represents a leap forward in the synthesis of Ti‐MOFs and their practical photocatalytic applications.
Authors
- Arianna Melillo (ORCID: https://orcid.org/0000-0002-6932-9192)
- Beibei Xiao (ORCID: https://orcid.org/0000-0001-9637-7512)
- Sergio Navalón (ORCID: https://orcid.org/0000-0001-8423-0759)
- Philippe Boullay (ORCID: https://orcid.org/0000-0002-2867-8986)
- Bingbing Chen (ORCID: https://orcid.org/0000-0001-5995-4464)
- Celia M. Rueda‐Navarro (ORCID: https://orcid.org/0000-0002-9569-7722)
- Georges Mouchaham (ORCID: https://orcid.org/0000-0001-8696-9733)
- Iurii Dovgaliuk (ORCID: https://orcid.org/0000-0003-1997-4748)
- G. Patriarche (ORCID: https://orcid.org/0000-0002-3917-2470)
- Pierre Florian (ORCID: https://orcid.org/0000-0003-4306-0815)
- Christian Serre (ORCID: https://orcid.org/0000-0003-3040-2564)
- Asma Mansouri (ORCID: https://orcid.org/0000-0003-1392-634X)
- Guillaume Maurin (ORCID: https://orcid.org/0000-0002-2096-0450)
- Ieuan Cornu (ORCID: https://orcid.org/0009-0004-5185-920X)
- Fan Dong (ORCID: https://orcid.org/0000-0001-6730-0612)
- Lokuge Aravindani Fernando
- Hermenegildo Garcia
- Juan José Ramírez‐Hernández
Institutions
- École Nationale Supérieure de Chimie de Montpellier (FR)
- Université d'Orléans (FR)
- Centre National de la Recherche Scientifique (FR)
- École Nationale Supérieure d'Ingénieurs de Caen (FR)
- Université de Montpellier (FR)
- Université Paris Sciences et Lettres (FR)
- Jiangsu University of Science and Technology (CN)
- Centre de Nanosciences et de Nanotechnologies (FR)
- Conditions Extrêmes et Matériaux Haute Température et Irradiation (FR)
- Universitat Politècnica de València (ES)
- Université de Caen Normandie (FR)
- ESPCI Paris (FR)
Publication Details
- Journal
- Advanced Energy Materials
- Published
- 2025-04-01
- DOI
- https://doi.org/10.1002/aenm.202500211
- Citations
- 11
- Primary Topic
- Advanced Photocatalysis Techniques
- Type
- article
- Field-Weighted Citation Impact
- 4.00
Funders
- European Commission
- Generalitat Valenciana
- Ministério da Ciência, Tecnologia e Inovação
- Centre National de la Recherche Scientifique
- Ministerio de Ciencia e Innovación
- Grand Équipement National De Calcul Intensif
- European Regional Development Fund
- Agencia Estatal de Investigación
- HORIZON EUROPE European Research Council