One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts

Hirayama, Yuma; Miura, Akira; Hirayama, Motoaki; Nakamura, Hiroyuki; Fujita, Koji; Kageyama, Hiroshi; Yamaguchi, Sho; Mizugaki, Tomoo; Mitsudome, Takato

doi:https://doi.org/10.1002/smll.202412217

One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts

Hirayama, Yuma; Miura, Akira; Hirayama, Motoaki et al.

Small, 2025, 2412217

Number of Access:582（2025-08-15 01:09 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/101405

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Title	One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts
Creator	CreatorName Hirayama, Yuma
	CreatorName Miura, Akira
	NRID 1000070761005 1000070761005 CreatorName Hirayama, Motoaki
	CreatorName Nakamura, Hiroyuki
	CreatorName Fujita, Koji
	NRID 1000040302640 1000040302640 CreatorName Kageyama, Hiroshi
	NRID 1000050700150 1000050700150 researchmap permalink 7000018077 7000018077 Scopus Author ID 56424690000 56424690000 CreatorName Yamaguchi, Sho
	NRID 1000050314406 1000050314406 ORCID 0000-0001-5701-7530 0000-0001-5701-7530 researchmap permalink read0054694 read0054694 Scopus Author ID 7003481890 7003481890 CreatorName Mizugaki, Tomoo
	NRID 1000000437360 1000000437360 ORCID 0000-0003-3071-8243 0000-0003-3071-8243 researchmap permalink read0107411 read0107411 Scopus Author ID 11240122700 11240122700 CreatorName Mitsudome, Takato
Subject	amination
	heterogeneous catalyst
	metastable
	ε-iron carbide
Description	Hirayama Y., Miura A., Hirayama M., et al. One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts. Small (2025); https://doi.org/10.1002/smll.202412217.
Abstract	ε-Iron carbide has garnered increasing interest for its superior magnetic characteristics and catalytic performance compared to other iron carbides. However, its metastable nature has posed significant challenges for synthesis, often requiring ultrahigh pressure, multistep processes, complex reaction condition control, and highly toxic reagents. Consequently, the properties of ε-iron carbide remain largely unexplored. A simplified synthesis method for ε-iron carbide can accelerate the exploration of new functionalities. In this study, a novel one-step selective synthesis method for ε-iron carbide nanoparticles under mild conditions via a wet-chemical approach is presented. In this method, Fe3(CO)₁₂, cetyltrimethylammonium bromide (CTAB), and bis(pinacolato)diboron (B₂pin₂) are added to hexadecylamine and reacted at 220 °C—a simple process that eliminates the need for extreme pressures and toxic substances. Detailed investigations elucidate the crucial roles of CTAB and B₂pin₂ in facilitating the selective formation of ε-iron carbide. This accessible and efficient synthesis process for ε-iron carbide can further enable the discovery of unprecedented catalytic properties in the reductive amination of benzaldehyde, distinct from those of conventional iron nanoparticle catalysts. Density functional theory calculations reveal insights into the electronic states responsible for the distinct activity of the ε-iron carbide nanoparticles.
Publisher	John Wiley and Sons Inc
Source Title	Small
Page	2412217
Date of Issued	2025-04-24
Language	English
Handle URL	https://hdl.handle.net/11094/101405
PISSN	16136810
eISSN	16136829
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1002/smll.202412217
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution 4.0 International License.
oaire:version	Version of Record
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	Small. 2025, p. 2412217
DC.title	One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts
DC.creator	Hirayama, Yuma
	Miura, Akira
	Hirayama, Motoaki
	Nakamura, Hiroyuki
	Fujita, Koji
	Kageyama, Hiroshi
	Yamaguchi, Sho
	Mizugaki, Tomoo
	Mitsudome, Takato
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-04-24
DC.identifier	https://doi.org/10.1002/smll.202412217
DC.subject	amination
	heterogeneous catalyst
	metastable
	ε-iron carbide
DC.description	Hirayama Y., Miura A., Hirayama M., et al. One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts. Small (2025); https://doi.org/10.1002/smll.202412217.
DCTERMS.abstract	ε-Iron carbide has garnered increasing interest for its superior magnetic characteristics and catalytic performance compared to other iron carbides. However, its metastable nature has posed significant challenges for synthesis, often requiring ultrahigh pressure, multistep processes, complex reaction condition control, and highly toxic reagents. Consequently, the properties of ε-iron carbide remain largely unexplored. A simplified synthesis method for ε-iron carbide can accelerate the exploration of new functionalities. In this study, a novel one-step selective synthesis method for ε-iron carbide nanoparticles under mild conditions via a wet-chemical approach is presented. In this method, Fe3(CO)₁₂, cetyltrimethylammonium bromide (CTAB), and bis(pinacolato)diboron (B₂pin₂) are added to hexadecylamine and reacted at 220 °C—a simple process that eliminates the need for extreme pressures and toxic substances. Detailed investigations elucidate the crucial roles of CTAB and B₂pin₂ in facilitating the selective formation of ε-iron carbide. This accessible and efficient synthesis process for ε-iron carbide can further enable the discovery of unprecedented catalytic properties in the reductive amination of benzaldehyde, distinct from those of conventional iron nanoparticle catalysts. Density functional theory calculations reveal insights into the electronic states responsible for the distinct activity of the ε-iron carbide nanoparticles.
DC.rights	This article is licensed under a Creative Commons Attribution 4.0 International License.
DC.format	101405
citation_title	One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts
citation_author	Hirayama, Yuma
	Miura, Akira
	Hirayama, Motoaki
	Nakamura, Hiroyuki
	Fujita, Koji
	Kageyama, Hiroshi
	Yamaguchi, Sho
	Mizugaki, Tomoo
	Mitsudome, Takato
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2025-04-24
citation_journal_title	Small
citation_firstpage	2412217
citation_doi	https://doi.org/10.1002/smll.202412217
citation_public_url	https://hdl.handle.net/11094/101405

One-Step Low-Temperature Synthesis of Metastable ε-Iron Carbide Nanoparticles with Unique Catalytic Properties Beyond Conventional Iron Catalysts

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