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Photocatalyst-Mediator Interface Modification by Surface-Metal Cations of a Dye-Sensitized H2 Evolution Photocatalyst
Title: | Photocatalyst-Mediator Interface Modification by Surface-Metal Cations of a Dye-Sensitized H2 Evolution Photocatalyst |
Authors: | Yoshimura, Nobutaka Browse this author | Yoshida, Masaki Browse this author | Kato, Masako Browse this author | Kobayashi, Atsushi Browse this author →KAKEN DB |
Issue Date: | 25-Jul-2022 |
Publisher: | American Chemical Society |
Journal Title: | Inorganic chemistry |
Volume: | 61 |
Issue: | 29 |
Start Page: | 11095 |
End Page: | 11102 |
Publisher DOI: | 10.1021/acs.inorgchem.2c00851 |
Abstract: | To develop highly active H2 evolving dye-sensitized photocatalysts (DSPs) applicable for Z-scheme water splitting, we synthesized a series of Ru(II)-dye-double-layered DSPs, X '- RuCP6-Zr-RuP6@Pt-TiO2 (X '-DSP) with different surface bound metal cations (X ' = Fe2+, Y3+, Zr4+, Hf4+, and Bi3+). In 0.5 M KI aqueous solution, the photocatalytic H2 evolution activity under blue light irradiation (lambda = 460 +/- 15 nm) increased in the following order: nonmetal-modified DSP, H+-DSP (turn over number for 6 h irradiation = 35.2) < Fe2+-DSP (54.9) asymptotic to Bi3+-DSP (55.2) < Hf4+-DSP (65.5)asymptotic to Zr4+-DSP (68.3)asymptotic to Y3+-DSP (71.5), suggesting that the redox-inactive and highly charged metal cations tend to improve the electron donation from the iodide electron mediator. On the other hand, DSPs having heavy metal cations, Hf4+-DSP (18.4) and Bi3+-DSP (16.6), exhibited better activity under green light irradiation (lambda = 530 +/- 15 nm) than Zr4+-DSP (15.7) and H+-DSP (7.80), implying the contribution of a heavy atom effect of the surface-bound metal cation to partially allow the spin-forbidden metal-to-ligand charge-transfer excitation. |
Rights: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-5ZUWXAWTNKYBVGTMXPJD. |
Type: | article (author version) |
URI: | http://hdl.handle.net/2115/90223 |
Appears in Collections: | 理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 小林 厚志
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