PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor

Hayashida, Naoyuki; Kim, Hyo Jin; Shun, Kazuki; Yoshida, Hideto; Nakano, Takayoshi; Mori, Kohsuke

doi:https://doi.org/10.1021/acsaem.6c00086

PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor

Hayashida, Naoyuki; Kim, Hyo Jin; Shun, Kazuki et al.

ACS Applied Energy Materials, 2026, 9(8), 4887-4896

Number of Access:100（2026-07-16 10:11 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/104911

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Title	PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor
Creator	CreatorName Hayashida, Naoyuki
	CreatorName Kim, Hyo Jin
	ORCID 0009-0005-3669-8513 0009-0005-3669-8513 researchmap permalink 87364816 87364816 Scopus Author ID 57216689610 57216689610 CreatorName Shun, Kazuki
	NRID 1000000452425 1000000452425 ORCID 0000-0002-4195-3225 0000-0002-4195-3225 researchmap permalink read0204918 read0204918 Scopus Author ID 55324307600 55324307600 CreatorName Yoshida, Hideto
	NRID 1000030243182 1000030243182 ORCID 0000-0001-8052-1698 0000-0001-8052-1698 researchmap permalink read0013987 read0013987 Scopus Author ID 7403896013 7403896013 CreatorName Nakano, Takayoshi
	NRID 1000090423087 1000090423087 ORCID 0000-0003-3915-4528 0000-0003-3915-4528 researchmap permalink 7000018582 7000018582 Scopus Author ID 35426128700 35426128700 CreatorName Mori, Kohsuke
Subject	catalytic reactor
	formic acid
	metal 3D-printing
	Na₂Ti₃O₇
	PdAg alloy nanoparticles
Description	Hayashida N., Kim H.J., Shun K., et al. PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor. ACS Applied Energy Materials 9(8), 4887–4896 (2026); https://doi.org/10.1021/acsaem.6c00086.
Abstract	Formic acid (FA: HCOOH) has emerged as a promising hydrogen storage material because of its high hydrogen storage density and ease of handling. Thus, a practical and rational heterogeneous catalyst for FA synthesis via liquid-phase CO₂ hydrogenation is highly expected. In this study, we first prepared PdAg alloy nanoparticles (NPs) supported on Na₂Ti₃O₇ via simple ion-exchange followed by chemical reduction. These powdered specimens promote the efficient selective hydrogenation of CO₂ to give FA even under mild reaction conditions. The attack of the dissociated H atom on the HCO₃– intermediate was found to be the rate-determining step, which is facilitated by PdAg alloy NPs with a low Pd/Ag ratio. The insights obtained from the powdered specimens were subsequently applied to the design of a self-catalytic reactor fabricated using metal three-dimensional (3D)-printing technology. Oxidation and hydrothermal treatment under alkaline conditions of cylindrical-shaped Ti-based catalytic reactors produced Na₂Ti₃O₇ nanofibers on their surface, which further enabled the deposition of PdAg NPs via ion-exchange followed by chemical reduction, and facilitated the liquid-phase CO₂ hydrogenation into FA. We also investigated the influence of 3D-printing scan strategies on the microstructure and catalytic performance by changing the laser scan direction.
Publisher	American Chemical Society
Source Title	ACS Applied Energy Materials
Volume (Issue)	9(8)
Page	4887-4896
Date of Issued	2026-03-28
Language	English
Handle URL	https://hdl.handle.net/11094/104911
eISSN	25740962
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/acsaem.6c00086
Access Rights	embargoed access
CopyRight	This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Appl. Energy Mater., © 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/acsaem.6c00086.
CopyRight	The full-text file will be made open to the public on 28 March 2027 in accordance with the publisher's policy.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	ACS Applied Energy Materials. 2026, 9(8), p. 4887-4896
DC.title	PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor
DC.creator	Hayashida, Naoyuki
	Kim, Hyo Jin
	Shun, Kazuki
	Yoshida, Hideto
	Nakano, Takayoshi
	Mori, Kohsuke
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2026-03-28
DC.identifier	https://doi.org/10.1021/acsaem.6c00086
DC.subject	catalytic reactor
	formic acid
	metal 3D-printing
	Na₂Ti₃O₇
	PdAg alloy nanoparticles
DC.description	Hayashida N., Kim H.J., Shun K., et al. PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor. ACS Applied Energy Materials 9(8), 4887–4896 (2026); https://doi.org/10.1021/acsaem.6c00086.
DCTERMS.abstract	Formic acid (FA: HCOOH) has emerged as a promising hydrogen storage material because of its high hydrogen storage density and ease of handling. Thus, a practical and rational heterogeneous catalyst for FA synthesis via liquid-phase CO₂ hydrogenation is highly expected. In this study, we first prepared PdAg alloy nanoparticles (NPs) supported on Na₂Ti₃O₇ via simple ion-exchange followed by chemical reduction. These powdered specimens promote the efficient selective hydrogenation of CO₂ to give FA even under mild reaction conditions. The attack of the dissociated H atom on the HCO₃– intermediate was found to be the rate-determining step, which is facilitated by PdAg alloy NPs with a low Pd/Ag ratio. The insights obtained from the powdered specimens were subsequently applied to the design of a self-catalytic reactor fabricated using metal three-dimensional (3D)-printing technology. Oxidation and hydrothermal treatment under alkaline conditions of cylindrical-shaped Ti-based catalytic reactors produced Na₂Ti₃O₇ nanofibers on their surface, which further enabled the deposition of PdAg NPs via ion-exchange followed by chemical reduction, and facilitated the liquid-phase CO₂ hydrogenation into FA. We also investigated the influence of 3D-printing scan strategies on the microstructure and catalytic performance by changing the laser scan direction.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Appl. Energy Mater., © 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/acsaem.6c00086.
DC.rights	The full-text file will be made open to the public on 28 March 2027 in accordance with the publisher's policy.
DC.format	104911
citation_title	PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor
citation_author	Hayashida, Naoyuki
	Kim, Hyo Jin
	Shun, Kazuki
	Yoshida, Hideto
	Nakano, Takayoshi
	Mori, Kohsuke
citation_publisher	American Chemical Society
citation_language	English
citation_date	2026-03-28
citation_journal_title	ACS Applied Energy Materials
citation_volume	9
citation_issue	8
citation_firstpage	4887
citation_lastpage	4896
citation_doi	https://doi.org/10.1021/acsaem.6c00086
citation_public_url	https://hdl.handle.net/11094/104911

PdAg Nanoparticles Supported on Na₂Ti₃O₇ for CO₂ Hydrogenation into Formic Acid: Expanding Catalyst Design from Powder to a Metal 3D-Printed Self-Catalytic Reactor

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