Perfluoroalkyl-functionalization of zirconium-based metal–organic framework nanosheets for photosynthesis of hydrogen peroxide from dioxygen and water

Kondo, Yoshifumi; Mizutani, Shiori; Kuwahara, Yasutaka; Mori, Kohsuke; Sekino, Tohru; Yamashita, Hiromi

doi:https://doi.org/10.1039/D4TA07808J

Perfluoroalkyl-functionalization of zirconium-based metal–organic framework nanosheets for photosynthesis of hydrogen peroxide from dioxygen and water

Kondo, Yoshifumi; Mizutani, Shiori; Kuwahara, Yasutaka et al.

Journal of Materials Chemistry A, 2024, 13(5), 3701-3710

アクセス数:46件（2025-09-08 10:46 集計）

固定URL: https://hdl.handle.net/11094/102071

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タイトル	Perfluoroalkyl-functionalization of zirconium-based metal–organic framework nanosheets for photosynthesis of hydrogen peroxide from dioxygen and water
著者	NRID 1000010982118 1000010982118 ORCID 0000-0001-7189-2649 0000-0001-7189-2649 researchmap permalink 10982118 10982118 Scopus Author ID 57203531351 57203531351 著者名 Kondo, Yoshifumi
	著者名 Mizutani, Shiori
	NRID 1000040635330 1000040635330 ORCID 0000-0002-5867-6463 0000-0002-5867-6463 researchmap permalink yasutakakuwahara yasutakakuwahara Scopus Author ID 16052495300 16052495300 著者名 Kuwahara, Yasutaka
	NRID 1000090423087 1000090423087 ORCID 0000-0003-3915-4528 0000-0003-3915-4528 researchmap permalink 7000018582 7000018582 Scopus Author ID 35426128700 35426128700 著者名 Mori, Kohsuke
	NRID 1000020226658 1000020226658 ORCID 0000-0002-6605-9166 0000-0002-6605-9166 researchmap permalink tohrusekino tohrusekino Scopus Author ID 7006706950 7006706950 著者名 Sekino, Tohru
	NRID 1000040200688 1000040200688 ORCID 0000-0003-1796-5776 0000-0003-1796-5776 researchmap permalink read0118536 read0118536 Scopus Author ID 7403649198 7403649198 著者名 Yamashita, Hiromi
内容	Reproduced from J. Mater. Chem. A, 2025, 13, 3701-3710 with permission from the Royal Society of Chemistry.
抄録	Solar-light-driven photosynthesis of hydrogen peroxide (H₂O₂) from dioxygen (O₂) and water (H₂O) is a sustainable process. Metal–organic frameworks (MOFs) are promising candidates for the photosynthesis of H₂O₂ because of their unlimited design flexibility. However, MOF-driven H₂O₂ production from O₂ and H₂O remains a challenge because MOF photocatalysts need to exhibit high structural stability in aqueous reaction systems while suppressing H₂O₂ decomposition. In addition, the efficiency of H₂O₂ production in pure water has suffered from low O₂ solubility in aqueous solution and difficult-to-inhibit side reactions. In the present study, we demonstrate that hydrophobic Zr-based MOF (Zr-MOF) nanosheets modified with perfluoroalkyl carboxylates substantially accelerate the photocatalytic production of H₂O₂ from O₂ and H₂O under visible-light (λ > 420 nm) irradiation without any additives. Perfluoroalkyl-functionalization improves the hydrophobicity of the MOF, leading to suppression of H₂O₂ decomposition on Zr–oxo clusters. The high hydrophobicity enhances the enrichment of O₂ on the photocatalyst surface and the selectivity of two-electron oxidation of H₂O to generate H₂O₂, which promotes photocatalytic H₂O₂ synthesis. The length of the perfluoroalkyl chain plays a critical role in the enhancement of photocatalytic H₂O₂ production, and optimization of the chain length led to a 7.2-fold increase in activity compared with that of the pristine hydrophilic Zr-MOF. This study provides a noble design strategy for achieving highly selective photocatalytic H₂O₂ production via O₂ reduction and H₂O oxidation.
出版者	Royal Society of Chemistry (RSC)
収録物名	Journal of Materials Chemistry A
巻(号)	13(5)
ページ	3701-3710
刊行年月	2024-12-18
言語	英語
ハンドルURL	https://hdl.handle.net/11094/102071
PISSN	20507488
eISSN	20507496
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1039/D4TA07808J
アクセス権	embargoed access
権利情報	The full-text file will be made open to the public on 18 December 2025 in accordance with the publisher's policy.
出版タイプ	Accepted Manuscript
カテゴリ	学術雑誌論文 Journal Article

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
DCMI資源タイプ	text
DCTERMS.bibliographicCitation	Journal of Materials Chemistry A. 2024, 13(5), p. 3701-3710
DC.title	Perfluoroalkyl-functionalization of zirconium-based metal–organic framework nanosheets for photosynthesis of hydrogen peroxide from dioxygen and water
DC.creator	Kondo, Yoshifumi
	Mizutani, Shiori
	Kuwahara, Yasutaka
	Mori, Kohsuke
	Sekino, Tohru
	Yamashita, Hiromi
DC.publisher	Royal Society of Chemistry (RSC)
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-12-18
DC.identifier	https://doi.org/10.1039/D4TA07808J
DC.description	Reproduced from J. Mater. Chem. A, 2025, 13, 3701-3710 with permission from the Royal Society of Chemistry.
DCTERMS.abstract	Solar-light-driven photosynthesis of hydrogen peroxide (H₂O₂) from dioxygen (O₂) and water (H₂O) is a sustainable process. Metal–organic frameworks (MOFs) are promising candidates for the photosynthesis of H₂O₂ because of their unlimited design flexibility. However, MOF-driven H₂O₂ production from O₂ and H₂O remains a challenge because MOF photocatalysts need to exhibit high structural stability in aqueous reaction systems while suppressing H₂O₂ decomposition. In addition, the efficiency of H₂O₂ production in pure water has suffered from low O₂ solubility in aqueous solution and difficult-to-inhibit side reactions. In the present study, we demonstrate that hydrophobic Zr-based MOF (Zr-MOF) nanosheets modified with perfluoroalkyl carboxylates substantially accelerate the photocatalytic production of H₂O₂ from O₂ and H₂O under visible-light (λ > 420 nm) irradiation without any additives. Perfluoroalkyl-functionalization improves the hydrophobicity of the MOF, leading to suppression of H₂O₂ decomposition on Zr–oxo clusters. The high hydrophobicity enhances the enrichment of O₂ on the photocatalyst surface and the selectivity of two-electron oxidation of H₂O to generate H₂O₂, which promotes photocatalytic H₂O₂ synthesis. The length of the perfluoroalkyl chain plays a critical role in the enhancement of photocatalytic H₂O₂ production, and optimization of the chain length led to a 7.2-fold increase in activity compared with that of the pristine hydrophilic Zr-MOF. This study provides a noble design strategy for achieving highly selective photocatalytic H₂O₂ production via O₂ reduction and H₂O oxidation.
DC.rights	The full-text file will be made open to the public on 18 December 2025 in accordance with the publisher's policy.
DC.format	102071
citation_title	Perfluoroalkyl-functionalization of zirconium-based metal–organic framework nanosheets for photosynthesis of hydrogen peroxide from dioxygen and water
citation_author	Kondo, Yoshifumi
	Mizutani, Shiori
	Kuwahara, Yasutaka
	Mori, Kohsuke
	Sekino, Tohru
	Yamashita, Hiromi
citation_publisher	Royal Society of Chemistry (RSC)
citation_language	英語
citation_date	2024-12-18
citation_journal_title	Journal of Materials Chemistry A
citation_volume	13
citation_issue	5
citation_firstpage	3701
citation_lastpage	3710
citation_doi	https://doi.org/10.1039/D4TA07808J
citation_public_url	https://hdl.handle.net/11094/102071

Perfluoroalkyl-functionalization of zirconium-based metal–organic framework nanosheets for photosynthesis of hydrogen peroxide from dioxygen and water

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