Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid

Mori, Kohsuke; Shimada, Yuki; Yoshida, Hideto; Yamashita, Hiromi

doi:https://doi.org/10.1021/acsanm.4c05908

Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid

Mori, Kohsuke; Shimada, Yuki; Yoshida, Hideto et al.

ACS Applied Nano Materials, 2024, 7(24), 28649-28658

アクセス数:586件（2025-09-08 10:46 集計）

固定URL: https://hdl.handle.net/11094/100147

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タイトル	Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid
著者	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
	著者名 Shimada, Yuki
	NRID 1000000452425 1000000452425 ORCID 0000-0002-4195-3225 0000-0002-4195-3225 researchmap permalink read0204918 read0204918 Scopus Author ID 55324307600 55324307600 著者名 Yoshida, Hideto
	NRID 1000040200688 1000040200688 researchmap permalink read0118536 read0118536 Scopus Author ID 7403649198 7403649198 著者名 Yamashita, Hiromi
キーワード等	high-entropy oxides
	palladium
	catalyst
	formic acid
	carbon dioxide
内容	Mori K., Shimada Y., Yoshida H., et al. Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid. ACS Applied Nano Materials 7, 28649 (2024); https://doi.org/10.1021/acsanm.4c05908.
抄録	Active, stable Pd species were incorporated within the matrix of fluorite-based high-entropy oxide (HEO) (YZrLaGdHf)xO2 using an entropy-driven strategy based on a liquid-phase reaction. In situ X-ray absorption fine structure analyses and transmission electron microscopy observations at elevated temperatures under H2 confirmed that partially aggregated Pd oxide species in the as-synthesized Pd@(YZrLaGdHf)xO2 were transformed into an entropy-stabilized isolated form at 600 °C. In contrast, Pd species on the (YZrLaGdHf)xO2 surface were readily reduced with the formation of nanoclusters/nanoparticles even in the temperature range of 100 to 200 °C. This Pd@(YZrLaGdHf)xO2 exhibited enhanced activity during the hydrogenation of CO2 to formic acid with a maximum turnover number of 5000 based on the quantity of surface-exposed Pd atoms. This performance was more than eight times higher than that of the Pd/(YZrLaGdHf)xO2 on the basis of supported Pd. An assessment of the kinetics and theoretical investigations suggested that entropy-stabilized isolated Pd species facilitated both H2 dissociation and the attack of dissociated H atoms on C atoms in HCO3– ions.
出版者	American Chemical Society
収録物名	ACS Applied Nano Materials
巻(号)	7(24)
ページ	28649-28658
刊行年月	2024-12-27
言語	英語
ハンドルURL	https://hdl.handle.net/11094/100147
eISSN	25740970
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1021/acsanm.4c05908
アクセス権	embargoed access
権利情報	This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Nano Materials, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsanm.4c05908.
権利情報	The full-text file will be made open to the public on 27 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
DCTERMS.bibliographicCitation	ACS Applied Nano Materials. 2024, 7(24), p. 28649-28658
DC.title	Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid
DC.creator	Mori, Kohsuke
	Shimada, Yuki
	Yoshida, Hideto
	Yamashita, Hiromi
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	英語
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-12-27
DC.identifier	https://doi.org/10.1021/acsanm.4c05908
DC.subject	high-entropy oxides
	palladium
	catalyst
	formic acid
	carbon dioxide
DC.description	Mori K., Shimada Y., Yoshida H., et al. Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid. ACS Applied Nano Materials 7, 28649 (2024); https://doi.org/10.1021/acsanm.4c05908.
DCTERMS.abstract	Active, stable Pd species were incorporated within the matrix of fluorite-based high-entropy oxide (HEO) (YZrLaGdHf)xO2 using an entropy-driven strategy based on a liquid-phase reaction. In situ X-ray absorption fine structure analyses and transmission electron microscopy observations at elevated temperatures under H2 confirmed that partially aggregated Pd oxide species in the as-synthesized Pd@(YZrLaGdHf)xO2 were transformed into an entropy-stabilized isolated form at 600 °C. In contrast, Pd species on the (YZrLaGdHf)xO2 surface were readily reduced with the formation of nanoclusters/nanoparticles even in the temperature range of 100 to 200 °C. This Pd@(YZrLaGdHf)xO2 exhibited enhanced activity during the hydrogenation of CO2 to formic acid with a maximum turnover number of 5000 based on the quantity of surface-exposed Pd atoms. This performance was more than eight times higher than that of the Pd/(YZrLaGdHf)xO2 on the basis of supported Pd. An assessment of the kinetics and theoretical investigations suggested that entropy-stabilized isolated Pd species facilitated both H2 dissociation and the attack of dissociated H atoms on C atoms in HCO3– ions.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Nano Materials, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsanm.4c05908.
DC.rights	The full-text file will be made open to the public on 27 December 2025 in accordance with the publisher's policy.
DC.format	100147
citation_title	Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid
citation_author	Mori, Kohsuke
	Shimada, Yuki
	Yoshida, Hideto
	Yamashita, Hiromi
citation_publisher	American Chemical Society
citation_language	英語
citation_date	2024-12-27
citation_journal_title	ACS Applied Nano Materials
citation_volume	7
citation_issue	24
citation_firstpage	28649
citation_lastpage	28658
citation_doi	https://doi.org/10.1021/acsanm.4c05908
citation_public_url	https://hdl.handle.net/11094/100147

Entropy-Stabilized Isolated Active Pd Species within a High-Entropy Fluorite Oxide Matrix for CO₂ Hydrogenation to Formic Acid

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