open access

https://hdl.handle.net/2115/91151

Importance of Electron Mediator Transparency : Photocatalytic Hydrogen Production from Polyoxometalate using Dye-double-layered Photocatalysts

英語

Surface modification

2023-02-20

Wiley-Blackwell

ChemCatChem

15(4)

e202201386

One-directional electron transfer is crucial for two-step photoexcitation (Z-scheme) water-splitting photocatalysis. We investigated the hydrogen evolution activity of PS-double-layered photocatalysts (X-DSP, X-RuCP6-Zr-RuP6@Pt/KxH4-xNb6O17; X=Zr4+, H+) in the presence of highly charged polyoxometalates-K-6[(SiVW11O40)-W-IV] center dot nH(2)O (V-IV-POM) and K-6[SiW11O39MnII(H2O)] center dot nH(2)O (Mn-II-POM)-as redox-reversible electron donors, to induce effective photocatalyst-donor electrostatic attraction. Surface-phosphonate-comprising H+-DSP completely one-electron oxidized V-IV-POM with 0.39 % apparent quantum yield in the initial hour (iAQY) in both HCl and phosphate buffer aqueous solutions. Conversely, the Zr4+-DSP iAQY decreased to 0.05 % in HCl aq. Considering that the 0.39 % iAQY was retained when replacing V-IV-POM with Mn-II-POM in HCl aq, we supposed that energy transfer deactivation from photoexcited PS* to surface-immobilized V-IV-POM is the plausible origin of the lower iAQY, owing to the stronger visible-light absorptivity of V-IV-POM. This suggests that accumulation of visible-light-transparent electron mediator on the photocatalyst surface is an effective approach for one-directional electron transfer in Z-scheme water-splitting photocatalysis.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: [Yoshimura, N., Tomita, O., Abe, R., Yoshida, M., Kobayashi, A., ChemCatChem 2023, 15, e202201386.], which has been published in final form at https://doi.org/10.1002/cctc.202201386. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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