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Site Sensitivity of Interfacial Charge Transfer and Photocatalytic Efficiency in Photocatalysis: Methanol Oxidation on Anatase TiO 2 Nanocrystals
Author(s) -
Fu Cong,
Li Fei,
Zhang Jiachen,
Li Dan,
Qian Kun,
Liu Yong,
Tang Junwang,
Fan Fengtao,
Zhang Qun,
Gong XueQing,
Huang Weixin
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202014037
Subject(s) - photocatalysis , anatase , materials science , nanocrystal , valence (chemistry) , band bending , surface states , methanol , chemical engineering , nanotechnology , chemical physics , photochemistry , catalysis , chemistry , surface (topology) , geometry , mathematics , optoelectronics , organic chemistry , engineering , biochemistry
Photocatalytic oxidation of methanol on various anatase TiO 2 nanocrystals was studied by in situ and time‐resolved characterizations and DFT calculations. Surface site and resulting surface adsorbates affect the surface band bending/bulk‐to‐surface charge migration processes and interfacial electronic structure/interfacial charge transfer processes. TiO 2 nanocrystals predominantly enclosed by the {001} facets expose a high density of reactive fourfold‐coordinated Ti sites (Ti 4c ) at which CH 3 OH molecules dissociate to form the CH 3 O adsorbate (CH 3 O(a) Ti4c ). CH 3 O(a) Ti4c localized density of states are almost at the valence band maximum of TiO 2 surface, facilitating the interfacial hole transfer process; CH 3 O(a) Ti4c with a high coverage promotes upward surface band bending, facilitating bulk‐to‐surface hole migration. CH 3 O(a) Ti4c exhibits the highest photocatalytic oxidation rate constant. TiO 2 nanocrystals enclosed by the {001} facets are most active in photocatalytic methanol oxidation.