title: Atomic Layer Deposition-Confined Nonstoichiometric TiO2 Nanocrystals with Tunneling Effects for Solar Driven Hydrogen Evolution.
abstract: Ti(3+) 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 (Ti(3+)-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.
authors.affiliation: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Peng
authors.initials: P
authors.lastname: Zhang
authors.affiliation: 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.
authors.forename: Takashi
authors.initials: T
authors.lastname: Tachikawa
authors.affiliation: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.affiliation: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima