Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst

Mori, Kohsuke; Shinogi, Jun; Shimada, Yuki; Yamashita, Hiromi

doi:https://doi.org/10.1021/acscatal.4c05484

Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst

Mori, Kohsuke; Shinogi, Jun; Shimada, Yuki et al.

ACS Catalysis, 2024, 14(24), 18861-18871

Number of Access:389（2025-08-15 01:10 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100148

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Title	Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst
Creator	NRID 1000090423087 1000090423087 ORCID 0000-0003-3915-4528 0000-0003-3915-4528 researchmap permalink 7000018582 7000018582 Scopus Author ID 35426128700 35426128700 CreatorName Mori, Kohsuke
	CreatorName Shinogi, Jun
	CreatorName Shimada, Yuki
	NRID 1000040200688 1000040200688 researchmap permalink read0118536 read0118536 Scopus Author ID 7403649198 7403649198 CreatorName Yamashita, Hiromi
Subject	carbon dioxide
	cobalt oxide
	formic acid
	hydrogenation
	tandem catalysis
Description	Mori K., Shinogi J., Shimada Y., et al. Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst. ACS Catalysis 14, 18861 (2024); https://doi.org/10.1021/acscatal.4c05484.
Abstract	The transformation of carbon dioxide (CO2) into formic acid (FA; HCOOH) in an aqueous phase is a promising method of realizing an environmentally friendly FA/CO2-mediated chemical hydrogen storage/supply cycle. Despite progress in the design of catalysts that operate under basic conditions, the development of efficient catalysts that operate under additive-free conditions lags behind owing to the difficulty in activating CO2 and the low solubility of CO2 in pure water. In the present study, we present a heterogeneous tandem catalysis strategy in which Co3O4 is used as a CO2 hydration cocatalyst to produce a HCO3- intermediate, in combination with our previously reported PdAg/TiO2 as a catalyst for the hydrogenation of HCO3- to afford FA. The turnover number based on Pd improved by a factor of more than 8 in the presence of the Co3O4 cocatalyst with a cubic particle morphology enclosed by (100) facets. A series of morphology-controlled Co3O4 cocatalysts was investigated to elucidate the effect of the exposed crystal facets (i.e., (100), (111), or (112)) on their physicochemical properties and catalytic activity in FA synthesis. A systematic comparison based on experimental and density functional theory calculations demonstrated that the substantial enhancement effect of the Co3O4 cubes is attributable to the in situ generation of the largest amount of surface Co-OH groups with strong basicity originating from the exposed (100) facets. In addition, the present tandem catalytic system displayed high recyclability without exhibiting a structural change or a significant loss of activity. These findings will allow the rational design of an environmentally benign catalytic system for the hydrogenation of CO2 to FA.
Publisher	American Chemical Society
Source Title	ACS Catalysis
Volume (Issue)	14(24)
Page	18861-18871
Date of Issued	2024-12-20
Language	English
Handle URL	https://hdl.handle.net/11094/100148
eISSN	21555435
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/acscatal.4c05484
Access Rights	embargoed access
CopyRight	This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, © 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/acscatal.4c05484.
CopyRight	The full-text file will be made open to the public on 20 December 2025 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
DCTERMS.bibliographicCitation	ACS Catalysis. 2024, 14(24), p. 18861-18871
DC.title	Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst
DC.creator	Mori, Kohsuke
	Shinogi, Jun
	Shimada, Yuki
	Yamashita, Hiromi
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-12-20
DC.identifier	https://doi.org/10.1021/acscatal.4c05484
DC.subject	carbon dioxide
	cobalt oxide
	formic acid
	hydrogenation
	tandem catalysis
DC.description	Mori K., Shinogi J., Shimada Y., et al. Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst. ACS Catalysis 14, 18861 (2024); https://doi.org/10.1021/acscatal.4c05484.
DCTERMS.abstract	The transformation of carbon dioxide (CO2) into formic acid (FA; HCOOH) in an aqueous phase is a promising method of realizing an environmentally friendly FA/CO2-mediated chemical hydrogen storage/supply cycle. Despite progress in the design of catalysts that operate under basic conditions, the development of efficient catalysts that operate under additive-free conditions lags behind owing to the difficulty in activating CO2 and the low solubility of CO2 in pure water. In the present study, we present a heterogeneous tandem catalysis strategy in which Co3O4 is used as a CO2 hydration cocatalyst to produce a HCO3- intermediate, in combination with our previously reported PdAg/TiO2 as a catalyst for the hydrogenation of HCO3- to afford FA. The turnover number based on Pd improved by a factor of more than 8 in the presence of the Co3O4 cocatalyst with a cubic particle morphology enclosed by (100) facets. A series of morphology-controlled Co3O4 cocatalysts was investigated to elucidate the effect of the exposed crystal facets (i.e., (100), (111), or (112)) on their physicochemical properties and catalytic activity in FA synthesis. A systematic comparison based on experimental and density functional theory calculations demonstrated that the substantial enhancement effect of the Co3O4 cubes is attributable to the in situ generation of the largest amount of surface Co-OH groups with strong basicity originating from the exposed (100) facets. In addition, the present tandem catalytic system displayed high recyclability without exhibiting a structural change or a significant loss of activity. These findings will allow the rational design of an environmentally benign catalytic system for the hydrogenation of CO2 to FA.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, © 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/acscatal.4c05484.
DC.rights	The full-text file will be made open to the public on 20 December 2025 in accordance with the publisher's policy.
DC.format	100148
citation_title	Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst
citation_author	Mori, Kohsuke
	Shinogi, Jun
	Shimada, Yuki
	Yamashita, Hiromi
citation_publisher	American Chemical Society
citation_language	English
citation_date	2024-12-20
citation_journal_title	ACS Catalysis
citation_volume	14
citation_issue	24
citation_firstpage	18861
citation_lastpage	18871
citation_doi	https://doi.org/10.1021/acscatal.4c05484
citation_public_url	https://hdl.handle.net/11094/100148

Heterogeneous Tandem Catalysis Strategy for Additive-Free CO₂ Hydrogenation into Formic Acid in Water: Crystal Plane Effect of Co₃O₄ Cocatalyst

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