Cation Vacancies in Ti-Deficient TiO2 Nanosheets Enable Highly Stable Trapping of Pt Single Atoms for Persistent Photocatalytic Hydrogen Evolution

Jung H, Cha G, Kim H, Will J, Zhou X, Bad'ura Z, Zoppellaro G, Dobrota AS, Skorodumova NV, Pašti IA, Sarma BB, Schmidt J, Spiecker E, Breu J, Schmuki P (2025)

Publication Language: English

Publication Type: Journal article

Publication year: 2025

Journal

Small Wiley-VCH Verlag

Book Volume: 21

Article Number: 2502428

DOI: 10.1002/smll.202502428

Abstract

The stabilization of single-atom catalysts on semiconductor substrates is pivotal for advancing photocatalysis. TiO2, 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 TiO2 nanosheets provide highly stable anchoring sites for Pt single atoms, enabling persistent photocatalytic hydrogen evolution. Ultrathin TiO2 nanosheets with intrinsic Ti4+ 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 Ti4+ 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 Ti4+ 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 with CRIS profile

Hayoon Jung Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) (LKO) Hyesung Kim Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) (LKO) Johannes Will Lehrstuhl für Werkstoffwissenschaften (Mikro- und Nanostrukturforschung) Jochen Schmidt Lehrstuhl für Interfaces und Partikeltechnologie (LFG) Erdmann Spiecker Lehrstuhl für Werkstoffwissenschaften (Mikro- und Nanostrukturforschung) Patrik Schmuki Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) (LKO)

Involved external institutions

Fraunhofer-Institut für Keramische Technologien und Systeme (IKTS) DE Germany (DE) Palacky University Olomouc / Univerzita Palackého v Olomouci CZ Czech Republic (CZ) University of Belgrade / Универзитет у Београду RS Serbia (RS) Luleå University of Technology SE Sweden (SE) Institut National Polytechnique de Toulouse (INP) FR France (FR) Universität Bayreuth DE Germany (DE)

How to cite

APA:

Jung, H., Cha, G., Kim, H., Will, J., Zhou, X., Bad'ura, Z.,... Schmuki, P. (2025). Cation Vacancies in Ti-Deficient TiO2 Nanosheets Enable Highly Stable Trapping of Pt Single Atoms for Persistent Photocatalytic Hydrogen Evolution. Small, 21. https://doi.org/10.1002/smll.202502428

MLA:

Jung, Hayoon, et al. "Cation Vacancies in Ti-Deficient TiO2 Nanosheets Enable Highly Stable Trapping of Pt Single Atoms for Persistent Photocatalytic Hydrogen Evolution." Small 21 (2025).

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