title: Pt-Enhanced Mesoporous Ti3+/TiO2with Rapid Bulk to Surface Electron Transfer for Photocatalytic Hydrogen Evolution.
abstract: Pt-doped mesoporous Ti3+self-doped TiO2(Pt-Ti3+/TiO2) is in situ synthesized via an ionothermal route, by treating metallic Ti in an ionic liquid containing LiOAc, HOAc, and a H2PtCl6aqueous solution under mild ionothermal conditions. Such Ti3+-enriched environment, as well as oxygen vacancies, is proven to be effective for allowing the in situ reduction of Pt4+ions uniformly located in the framework of the TiO2bulk. The photocatalytic H2evolution of Pt-Ti3+/TiO2is significantly higher than that of the photoreduced Pt loaded on the original TiO2and commercial P25. Such greatly enhanced activity is due to the various valence states of Pt (Ptn+, n = 0, 2, or 3), forming Pt-O bonds embedded in the framework of TiO2and ultrafine Pt metal nanoparticles on the surface of TiO2. Such Ptn+-O bonds could act as the bridges for facilitating the photogenerated electron transfer from the bulk to the surface of TiO2with a higher electron carrier density (3.11 × 1020cm-3), about 2.5 times that (1.25 × 1020cm-3) of the photoreduced Pt-Ti3+/TiO2sample. Thus, more photogenerated electrons could reach the Pt metal for reducing protons to H2.
authors.affiliation: Chinese Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University , Shanghai 200234, China.
authors.forename: Zichao
authors.identifier: http://orcid.org/0000-0003-2528-3572
authors.initials: Z
authors.lastname: Lian
authors.affiliation: Chinese Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University , Shanghai 200234, China.
authors.forename: Wenchao
authors.initials: W
authors.lastname: Wang
authors.affiliation: Chinese Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University , Shanghai 200234, China.|Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
authors.forename: Guisheng
authors.initials: G
authors.lastname: Li
authors.affiliation: Institute of Computational Science and Engineering, Qingdao University , Qingdao 266071, China.
authors.forename: Fenghui
authors.initials: F
authors.lastname: Tian
authors.affiliation: Department of Chemistry, University of Florida , Gainesville, Florida 32611, United States.
authors.forename: Kirk S
authors.initials: KS
authors.lastname: Schanze
authors.affiliation: Chinese Education Ministry Key Laboratory of Resource Chemistry, Shanghai Normal University , Shanghai 200234, China.
authors.forename: Hexing
authors.initials: H
authors.lastname: Li
keywords: H2 evolution; Pt doping; Ti3+; TiO2; oxygen vacancies