A Cocatalyst that Stabilizes a Hydride Intermediate during Photocatalytic Hydrogen Evolution over a Rhodium-Doped TiO2 Nanosheet

Shintaro Ida; Kenta Sato; Tetsuya Nagata; Hidehisa Hagiwara; Motonori Watanabe; Namhoon Kim; Yoshihito Shiota; Michio Koinuma; Sakae Takenaka; Takaaki Sakai; Elif Ertekin; Tatsumi Ishihara

doi:10.1002/anie.201803214

A Cocatalyst that Stabilizes a Hydride Intermediate during Photocatalytic Hydrogen Evolution over a Rhodium-Doped TiO₂ Nanosheet

Shintaro Ida, Kenta Sato, Tetsuya Nagata, Hidehisa Hagiwara, Motonori Watanabe, Namhoon Kim, Yoshihito Shiota, Michio Koinuma, Sakae Takenaka, Takaaki Sakai, Elif Ertekin, Tatsumi Ishihara

Research output: Contribution to journal › Article › peer-review

Abstract

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 TiO₂ 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.

Original language	English (US)
Pages (from-to)	9073-9077
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	29
DOIs	https://doi.org/10.1002/anie.201803214
State	Published - Jul 16 2018

Keywords

cocatalysts
hydrogen evolution
nanosheets
photocatalysis
water splitting

ASJC Scopus subject areas

Catalysis
General Chemistry

Online availability

10.1002/anie.201803214

Library availability

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Cite this

Ida, S., Sato, K., Nagata, T., Hagiwara, H., Watanabe, M., Kim, N., Shiota, Y., Koinuma, M., Takenaka, S., Sakai, T., Ertekin, E., & Ishihara, T. (2018). A Cocatalyst that Stabilizes a Hydride Intermediate during Photocatalytic Hydrogen Evolution over a Rhodium-Doped TiO₂ Nanosheet. Angewandte Chemie - International Edition, 57(29), 9073-9077. https://doi.org/10.1002/anie.201803214

Ida, S, Sato, K, Nagata, T, Hagiwara, H, Watanabe, M, Kim, N, Shiota, Y, Koinuma, M, Takenaka, S, Sakai, T, Ertekin, E & Ishihara, T 2018, 'A Cocatalyst that Stabilizes a Hydride Intermediate during Photocatalytic Hydrogen Evolution over a Rhodium-Doped TiO₂ Nanosheet', Angewandte Chemie - International Edition, vol. 57, no. 29, pp. 9073-9077. https://doi.org/10.1002/anie.201803214

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abstract = "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 TiO2 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.",

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AU - Hagiwara, Hidehisa

AU - Watanabe, Motonori

AU - Kim, Namhoon

AU - Shiota, Yoshihito

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