Cation Vacancies in Ti‐Deficient TiO<sub>2</sub> Nanosheets Enable Highly Stable Trapping of Pt Single Atoms for Persistent Photocatalytic Hydrogen Evolution
The stabilization of single-atom catalysts on semiconductor substrates is pivotal for advancing photocatalysis. TiO<sub>2</sub>, a widely employed photocatalyst, typically stabilizes single atoms at oxygen vacancies-sites that are accessible but prone to agglomeration under illumination. Here, we demonstrate that cation vacancies in Ti-deficient TiO<sub>2</sub> nanosheets provide highly stable anchoring sites for Pt single atoms, enabling persistent photocatalytic hydrogen evolution. Ultrathin TiO<sub>2</sub> nanosheets with intrinsic Ti<sup>4+</sup> vacancies are synthesized via lepidocrocite-type titanate delamination and Pt single atoms are selectively trapped within these vacancies through a simple immersion process. The resulting Pt-decorated nanosheets exhibit superior photocatalytic hydrogen evolution performance, outperforming both Pt nanoparticle-loaded nanosheets and benchmarked Pt single-atom catalysts on P25. Crucially, Pt atoms anchored at Ti<sup>4+</sup> vacancies display remarkable resistance to light-induced agglomeration, a key limitation of conventional single-atom photocatalysts. Density functional theory calculations reveal that Pt incorporation into Ti<sup>4+</sup> vacancies is highly thermodynamically favorable and optimizes hydrogen adsorption energetics for enhanced catalytic activity. This work highlights the critical role of cation defect engineering in stabilizing single-atom co-catalysts and advancing the efficiency and durability of photocatalytic hydrogen evolution.
Authors
- Xin Zhou (ORCID: https://orcid.org/0000-0002-4385-8379)
- Hyesung Kim (ORCID: https://orcid.org/0000-0002-2578-9760)
- Natalia V. Skorodumova (ORCID: https://orcid.org/0000-0001-6417-5844)
- Hayoon Jung
- Giorgio Zoppellaro (ORCID: https://orcid.org/0000-0003-2304-2564)
- Jochen Schmidt (ORCID: https://orcid.org/0000-0002-9056-2749)
- Gihoon Cha
- Erdmann Spiecker (ORCID: https://orcid.org/0000-0002-2723-5227)
- Ana S. Dobrota (ORCID: https://orcid.org/0000-0001-6200-8612)
- Zdeňěk Baďura (ORCID: https://orcid.org/0009-0002-2330-2012)
- Johannes Will (ORCID: https://orcid.org/0000-0003-0326-9913)
- Josef Breu (ORCID: https://orcid.org/0000-0002-2547-3950)
- Patrik Schmuki (ORCID: https://orcid.org/0000-0002-9208-5771)
- Igor A. Pašti (ORCID: https://orcid.org/0000-0002-1000-9784)
- Bidyut Bikash Sarma (ORCID: https://orcid.org/0000-0002-5292-7890)
Institutions
- Centre National de la Recherche Scientifique (FR)
- Serbian Academy of Sciences and Arts (RS)
- VSB - Technical University of Ostrava (CZ)
- Université Fédérale de Toulouse Midi-Pyrénées (FR)
- Friedrich-Alexander-Universität Erlangen-Nürnberg (DE)
- Luleå University of Technology (SE)
- Institut National Polytechnique de Toulouse (FR)
- University of Belgrade (RS)
- Laboratoire de Chimie de Coordination (FR)
- Regional Centre of Advanced Technologies and Materials (CZ)
- Institute of General and Physical Chemistry (RS)
- Fraunhofer Institute for Ceramic Technologies and Systems (DE)
- University of Bayreuth (DE)
- Palacký University Olomouc (CZ)
Publication Details
- Journal
- Small
- Published
- 2025-06-02
- DOI
- https://doi.org/10.1002/smll.202502428
- Citations
- 8
- Primary Topic
- Advanced Photocatalysis Techniques
- Type
- article
- Field-Weighted Citation Impact
- 2.91
Funders
- European Commission
- Deutsche Forschungsgemeinschaft
- Grantová Agentura České Republiky
- National Science Council
- Vetenskapsrådet
- European Regional Development Fund
- HORIZON EUROPE European Research Council