Oxygen Vacancy Formation at Metal‒TiO₂ Interface Yielding Enhanced Photocatalytic Hydrogen Generation
Strong Metal-Support Interaction (SMSI) is a key concept in heterogeneous catalysis, but it remains underexplored in the context of photon-to-hydrogen conversion, as coupling of metallic nanoparticles with photocatalysts is overlooked and only discussed in terms of Schottky barrier formation. In this study, we provide deep insights into the effect of Au encapsulation with TiO<sub>2</sub> overlayer on enhancing photocatalytic hydrogen generation. Our findings reveal that the construction of a SMSI-like nanostructure induces the formation of oxygen vacancies at the Au‒TiO<sub>2</sub> interface which actively facilitate charge carrier separation through interfacial band reconstruction. The presence of defects is evidenced by Electron Paramagnetic Resonance and X-ray Photoelectron Spectroscopy, unveiling their relationship with photocatalytic activities. Consistent with experimental results, Density Functional Theory (DFT) calculations demonstrate that Au promotes oxygen vacancy formation. These vacancies located at the TiO<sub>2</sub> surface significantly enhances H<sub>2</sub>O and MeOH adsorption during H<sub>2</sub> evolution reactions. The SMSI-like concept was extended to Pt, Pd, and Ag, in which the oxygen vacancy formation energy at the metal-semiconductor interface varied depending on the metal, as computed by DFT. The results suggest that photocatalytic activity is related to the ease of oxygen vacancy formation, which is influenced by the nature of the metals.
Authors
- Jordi Arbiol (ORCID: https://orcid.org/0000-0002-0695-1726)
- Mohamed Nawfal Ghazzal (ORCID: https://orcid.org/0000-0002-2040-995X)
- Vien‐Duong Quach (ORCID: https://orcid.org/0000-0002-1968-9253)
- Tangui Le Bahers (ORCID: https://orcid.org/0000-0003-2166-081X)
- Marc Botifoll (ORCID: https://orcid.org/0000-0002-4876-6393)
- Christophe Colbeau‐Justin (ORCID: https://orcid.org/0000-0003-2343-5878)
- Marija Knezevic (ORCID: https://orcid.org/0009-0002-7498-7138)
- Robert Wojcieszak (ORCID: https://orcid.org/0000-0002-8956-5846)
- María Chiara Spadaro (ORCID: https://orcid.org/0000-0002-6540-0377)
- Carine Michel (ORCID: https://orcid.org/0000-0002-4501-7194)
- Hervé Vezin (ORCID: https://orcid.org/0000-0002-7282-2703)
- Franck Dumeignil (ORCID: https://orcid.org/0000-0001-9727-8196)
- Aparna Harsan
Institutions
- École Normale Supérieure de Lyon (FR)
- Institució Catalana de Recerca i Estudis Avançats (ES)
- Centre National de la Recherche Scientifique (FR)
- Institut Universitaire de France (FR)
- Université de Lille (FR)
- Université Paris-Saclay (FR)
- University of Catania (IT)
- Institut Català de Nanociència i Nanotecnologia (ES)
- Laboratoire de Spectroscopie pour les Interactions, la Réactivité et l'Environnement (FR)
- Institut de Chimie (FR)
- Laboratoire de Chimie (FR)
- Unité de catalyse et de chimie du solide de Lille (FR)
- Institute for Microelectronics and Microsystems (IT)
Publication Details
- Journal
- Advanced Science
- Published
- 2025-06-20
- DOI
- https://doi.org/10.1002/advs.202501835
- Citations
- 24
- Primary Topic
- Advanced Photocatalysis Techniques
- Type
- article
- Field-Weighted Citation Impact
- 8.72
Funders
- Centres de Recerca de Catalunya
- Institut Català de Nanociència i Nanotecnologia
- European Commission
- Agence Nationale de la Recherche
- Generalitat de Catalunya
- Centre National de la Recherche Scientifique
- Université Paris-Saclay
- European Regional Development Fund
- Departament de Salut, Generalitat de Catalunya
- Agencia Estatal de Investigación