Photoaccumulation of Long‐Lived Reactive Electrons in a Microporous Ti(IV) Oxocluster‐Based Metal–Organic Framework for Light and Dark Photocatalysis
The microporous Ti<sub>12</sub> oxocluster-based metal-organic framework (MOF) MIP-177(Ti)-LT exhibits excellent stability and photoactivity, making it highly promising for photocatalysis. Using transient and photoinduced absorption spectroscopies, the behavior of reactive electrons in MIP-177(Ti)-LT across femtosecond-to-second timescales is investigated. The framework shows efficient charge separation and slow decay kinetics, with photogenerated charges persisting into the microsecond-second (µs-s) range and displaying higher yields and slower recombination than benchmark MOFs MIL-125(Ti)-NH<sub>2</sub> and UiO-66(Zr)-NH<sub>2</sub>. Photogenerated holes oxidize water with an O<sub>2</sub> yield of 335 µmol g<sup>-1</sup> h<sup>-1</sup> in the presence of electron scavengers. Under continuous irradiation, long-lived electrons accumulate, further enhanced by a hole scavenger (methanol). Remarkably, these electrons persist over 48 h post-excitation under argon, accompanied by a reversible white-to-black color change. The stored electrons remain redox-active, efficiently reducing added O<sub>2</sub> and methyl viologen. Dark addition of a Pt co-catalyst to photocharged MIP-177(Ti)-LT induces H<sub>2</sub> evolution at ≈300 µmol g<sup>-1</sup> (≈58 C g<sup>-1</sup>), corresponding to an accumulated electron density of one electron per 12 Ti atoms. These results highlight the photocharging properties of MIP-177(Ti)-LT and its potential for sustainable photocatalytic applications.
Authors
- Salvador Eslava (ORCID: https://orcid.org/0000-0002-2416-3205)
- Filip Podjaski (ORCID: https://orcid.org/0000-0002-5428-4526)
- Sam A. J. Hillman (ORCID: https://orcid.org/0000-0003-2619-2859)
- Sergio Navalón (ORCID: https://orcid.org/0000-0001-8423-0759)
- Alberto García‐Baldoví
- Georges Mouchaham (ORCID: https://orcid.org/0000-0001-8696-9733)
- Hermenegildo García (ORCID: https://orcid.org/0000-0003-4768-094X)
- Soranyel González‐Carrero (ORCID: https://orcid.org/0000-0003-2430-4458)
- Khaled Dassouki (ORCID: https://orcid.org/0009-0003-0710-6895)
- Christian Serre (ORCID: https://orcid.org/0000-0003-3040-2564)
- Yasmine Baghdadi
- Nathalie Steunou (ORCID: https://orcid.org/0000-0002-7049-7388)
- James Robert Durrant (ORCID: https://orcid.org/0000-0001-8353-7345)
- Shilin Yao (ORCID: https://orcid.org/0009-0005-5498-8135)
- Tianhao He (ORCID: https://orcid.org/0009-0003-1164-7782)
- Katrin Heinzerling
Institutions
- Centre National de la Recherche Scientifique (FR)
- Université de Versailles Saint-Quentin-en-Yvelines (FR)
- Université Paris Sciences et Lettres (FR)
- Université Paris-Saclay (FR)
- Parc Científic de la Universitat de València (ES)
- London Biofoundry (GB)
- Instituto de Tecnología Química (ES)
- Institut Lavoisier de Versailles (FR)
- Imperial College London (GB)
- Universitat Politècnica de València (ES)
- ESPCI Paris (FR)
Publication Details
- Journal
- Advanced Materials
- Published
- 2025-12-03
- DOI
- https://doi.org/10.1002/adma.202517595
- Citations
- 2
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 1.07
Funders
- UK Research and Innovation
- European Commission
- Generalitat Valenciana
- China Scholarship Council
- Ministerio de Ciencia e Innovación
- Engineering and Physical Sciences Research Council
- European Regional Development Fund
- Agencia Estatal de Investigación