open access

https://hdl.handle.net/2115/93585

Photoredox Cascade Catalyst for Efficient Hydrogen Production with Biomass Photoreforming

英語

Photoreforming

2023-11-13

Wiley-Blackwell

Angewandte chemie-international edition

62(46)

Biomass photoreforming is a promising method to provide both a clean energy resource in the form of hydrogen (H2) and valuable chemicals as the results of water reduction and biomass oxidation. To overcome the poor contact between heterogeneous photocatalysts and biomass substrates, we fabricated a new photoredox cascade catalyst by combining a homogeneous catalyst, 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), and a heterogeneous dual-dye sensitized photocatalyst (DDSP) composed of two Ru(II)-polypyridine photosensitizers (RuP6 and RuCP6) and Pt-loaded TiO2 nanoparticles. During blue-light irradiation (lambda=460 +/- 15 nm; 80 mW), the DDSP photocatalytically reduced aqueous protons to form H2 and simultaneously oxidized TEMPO center dot radicals to generate catalytically active TEMPO+. It oxidized biomass substrates (water-soluble glycerol and insoluble cellulose) to regenerate TEMPO center dot. In the presence of N-methyl imidazole as a proton transfer mediator, the photocatalytic H2 production activities for glycerol and cellulose reforming reached 2670 and 1590 mu mol H2 (gTiO2)-1 h-1, respectively, which were comparable to those of state-of-the-art heterogeneous photocatalysts. A new photoredox cascade photocatalyst consisting of dual-dye sensitized Pt-TiO2 nanoparticle photocatalyst and 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) molecular catalyst was constructed. The system produced H2 efficiently under blue-light to simultaneously generate one-electron oxidized TEMPO+ that oxidized various biomass substrates ranging from water-soluble glycerol to insoluble cellulose.image

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: Angewandte Chemie International Edition Vol.62(46) , which has been published in final form at https://doi.org/10.1002/anie.202313014. 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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