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A Cocatalyst that Stabilizes a Hydride Intermediate during Photocatalytic Hydrogen Evolution over a Rhodium‐Doped TiO 2 Nanosheet
Author(s) -
Ida Shintaro,
Sato Kenta,
Nagata Tetsuya,
Hagiwara Hidehisa,
Watanabe Motonori,
Kim Namhoon,
Shiota Yoshihito,
Koinuma Michio,
Takenaka Sakae,
Sakai Takaaki,
Ertekin Elif,
Ishihara Tatsumi
Publication year - 2018
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.201803214
Subject(s) - photocatalysis , hydride , nanosheet , photochemistry , hydrogen , dopant , materials science , density functional theory , hydrogen atom , doping , rhodium , catalysis , chemistry , nanotechnology , computational chemistry , organic chemistry , alkyl , optoelectronics
The hydrogen evolution reaction using semiconductor photocatalysts has been significantly improved by cocatalyst loading. However, there are still many speculations regarding the actual role of the cocatalyst. Now a photocatalytic hydrogen evolution reaction pathway is reported on a cocatalyst site using TiO 2 nanosheets doped with Rh at Ti sites as one‐atom cocatalysts. A hydride species adsorbed on the one‐atom Rh dopant cocatalyst site was confirmed experimentally as the intermediate state for hydrogen evolution, which was consistent with the results of density functional theory (DFT) calculations. In this system, the role of the cocatalyst in photocatalytic hydrogen evolution is related to the withdrawal of photo‐excited electrons and stabilization of the hydride intermediate species; the presence of oxygen vacancies induced by Rh facilitate the withdrawal of electrons and stabilization of the hydride.