Atomic Layer Deposition-Confined Nonstoichiometric TiO2 Nanocrystals with Tunneling Effects for Solar Driven Hydrogen Evolution

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The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan
Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan
§ PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan
Cite this: J. Phys. Chem. Lett. 2016, 7, 7, 1173–1179
Publication Date (Web):March 10, 2016
Copyright © 2016 American Chemical Society
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Ti3+ self-doped TiO2 nanocrystals (TNCs) confined with controllable atomic layer deposition (ALD) amorphous layers were developed to provide a novel model of metal–insulator–semiconductor (MIS) photocatalysts for hydrogen generation in the ultraviolet to near-infrared region. Photoexcitation of optimized MIS nanostructures consisting of a metal cocatalyst (Pt), electron tunneling layer (ALD TiO2), and photoactive nonstoichiometric core (Ti3+-doped TNC) exhibited efficient hydrogen generation (52 μmol h–1·g–1), good reusability (16 h), and long-term stability (>7 d). The charge-transfer dynamics were examined using transient absorption spectroscopy to clarify the relationship between the photocatalytic activity and the tunneling effect. Our strategies highlight defect engineering in fabricating MIS photocatalysts with improved charge separation and tailored solar energy conversion properties.

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