Photoaccumulation of Long‐Lived Reactive Electrons in a Microporous Ti(IV) Oxocluster‐Based Metal–Organic Framework for Light and Dark Photocatalysis
Abstract
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.
Article Details
Authors (16)
Shilin Yao
Department of Chemistry Molecular Science Research Hub Imperial College London White City London W12 0BZ UK
Katrin Heinzerling
Institut des Matériaux Poreux de Paris ESPCI Paris Ecole Normale Supérieure CNRS PSL University Paris 75005 France
Sam A. J. Hillman
Department of Chemistry Molecular Science Research Hub Imperial College London White City London W12 0BZ UK
Filip Podjaski
Department of Chemistry Molecular Science Research Hub Imperial College London White City London W12 0BZ UK
Tianhao He
Department of Chemistry, Centre for Processable Electronics
Alberto García‐Baldoví
Instituto de Tecnología Química (CSIC‐UPV) Agencia Estatal Consejo Superior de Investigaciones Científicas Universitat Politècnica de València Av. de los Naranjos s/n Valencia 46022 Spain
Yasmine Baghdadi
Department of Chemical Engineering and Center for Processable Electronics Imperial College London London SW7 2AZ UK
Khaled Dassouki
Institut Lavoisier de Versailles Université de Versailles St Quentin en Yvelines Université Paris Saclay 45 Avenue des Etats Unis Versailles 78035 France
Hermenegildo García
Instituto Universitario de Tecnología Química, CSIC-UPV
Salvador Eslava
Department of Chemical Engineering and Centre for Processable Electronics
Nathalie Steunou
Institut Lavoisier de Versailles Université de Versailles St Quentin en Yvelines Université Paris Saclay 45 Avenue des Etats Unis Versailles 78035 France
Soranyel Gonzalez‐Carrero
Department of Chemistry Molecular Science Research Hub Imperial College London White City London W12 0BZ UK
Sergio Navalón
Departamento de Química, Universitat Politècnica de València, C/Camino de Vera, s/n, Valencia 46022, Spain
Georges Mouchaham
Institut des Matériaux Poreux de Paris, Ecole Normale Supérieure, ESPCI Paris, CNRS
Christian Serre
Institut des Matériaux Poreux de Paris, Ecole Normale Supérieure, ESPCI Paris, CNRS
James R. Durrant
Chemistry Research Laboratory