Photoaccumulation of Long‐Lived Reactive Electrons in a Microporous Ti(IV) Oxocluster‐Based Metal–Organic Framework for Light and Dark Photocatalysis
Year: 2025
Type: article
Abstract: The microporous Ti 12 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 2 and UiO‐66(Zr)‐NH 2 . Photogenerated holes oxidize water with an O 2 yield of 335 µmol g −1 h −1 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 2 and methyl viologen. Dark addition of a Pt co‐catalyst to photocharged MIP‐177(Ti)‐LT induces H 2 evolution at ≈300 µmol g −1 (≈58 C g −1 ), 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.
Source: Advanced Materials
Institutions: Imperial College London, Centre National de la Recherche Scientifique, Université Paris Sciences et Lettres, École Normale Supérieure - PSL, Institut des Matériaux Poreux de Paris, ESPCI Paris, Consejo Superior de Investigaciones Científicas, Instituto de Tecnología Química, Universitat Politècnica de València, Université de Versailles Saint-Quentin-en-Yvelines, Université Paris-Saclay, Institut Lavoisier de Versailles, Universitat de València
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $6,070
Awards: G120905174, G1272927172, G139723338, G1482201912, G1530851820, G1620616899, G18271642, G2004761401, G204576392, G2309174360, Metal Organic Frameworks for Hydrogen production by photocatalytic overall water splitting, G2660406951, G2815556424, G3480869486, G348919436, G357246561, G363809202, G3836762566, G434337789, Application Targeted and Integrated Photovoltaics - Enhancing UK Capability in Solar, International cooperation for selective conversion of CO2 into METHAnol under SOLar light, G5080475149, G531036588, G5482073696, Polymer semiconductors toward efficient photocatalytic H2 production from sea water - understanding and exploiting the presence of ions, G6033112984, G6074969379, G7084143925, G726759913, G8546142835
OpenAlex ID: W4416940631