Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction

Ohashi, Keitaro; Nishimura, Kosei; Nagita, Kaito; Hashimoto, Takuya; Nakahata, Shoko; Harada, Takashi; Ina, Toshiaki; Nakanishi, Shuji; Kamiya, Kazuhide

doi:https://doi.org/10.1002/cssc.202402576

Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction

Ohashi, Keitaro; Nishimura, Kosei; Nagita, Kaito et al.

ChemSusChem, 2025, e202402576

Number of Access:1,078（2025-08-28 21:08 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100543

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Title	Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction
Creator	CreatorName Ohashi, Keitaro
	CreatorName Nishimura, Kosei
	CreatorName Nagita, Kaito
	CreatorName Hashimoto, Takuya
	CreatorName Nakahata, Shoko
	NRID 1000000379314 1000000379314 researchmap permalink rcsecharada rcsecharada CreatorName Harada, Takashi
	CreatorName Ina, Toshiaki
	NRID 1000040333447 1000040333447 ORCID 0000-0002-3313-2689 0000-0002-3313-2689 researchmap permalink read0191166 read0191166 Scopus Author ID 7402706228 7402706228 CreatorName Nakanishi, Shuji
	NRID 1000050716016 1000050716016 ORCID 0000-0002-6018-9277 0000-0002-6018-9277 researchmap permalink kamiya0908 kamiya0908 Scopus Author ID 24178005800 24178005800 CreatorName Kamiya, Kazuhide
Subject	C₂₊products, Cu nanoclusters derived from single-atom catalysts
	CO reduction reaction
	DFT calculations
	OperandoXAFS
	UniProt
Description	Ohashi K., Nishimura K., Nagita K., et al. Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction. ChemSusChem, (2025); https://doi.org/10.1002/cssc.202402576.
Abstract	Electrochemically grown copper nanoclusters (CuNCs: <3 nm) from single-atom catalysts have recently attracted intensive attention as electrocatalysts for CO2 and CO reduction reaction (CO2RR/CORR) because they exhibit distinct product selectivity compared with conventional Cu nanoparticles (typically larger than 10nm). Herein, we conducted a detailed investigation into the size dependence of CuNCs on selectivity for multicarbon (C2+) production in CORR. These nanoclusters were electrochemically grown from single Cu atoms dispersed on covalent triazine frameworks (Cu-CTFs). Operando X-ray absorption fine structure analysis revealed that Cu-CTFs containing 1.21 wt % and 0.41 wt % Cu (Cu(h)-CTFs and Cu(l)-CTFs, respectively) formed CuNCs of 2.0 and 1.1 nm, respectively, at −1.0 V vs. RHE. The selectivity for CORR products was particularly dependent on the size of CuNCs, with the Faraday efficiencies of C2+ products being 52.3 % and 32.7 % at −1.0 V vs. RHE with Cu(h)-CTFs and Cu(l)-CTFs, respectively. Spherical CuNCs modeling revealed that larger cluster sizes led to a greater proportion of a surface coordination number (SCN) of 8 or 9. Density functional calculations revealed that the CO dimerization reaction was more likely to proceed at SCNs of 8 or 9 compared to SCN of 7 because of the stability of the *OCCO intermediate.
Publisher	John Wiley and Sons Inc
Source Title	ChemSusChem
Page	e202402576
Date of Issued	2025-02-14
Language	English
Handle URL	https://hdl.handle.net/11094/100543
PISSN	18645631
eISSN	1864564X
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1002/cssc.202402576
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 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
DCTERMS.bibliographicCitation	ChemSusChem. 2025, p. e202402576
DC.title	Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction
DC.creator	Ohashi, Keitaro
	Nishimura, Kosei
	Nagita, Kaito
	Hashimoto, Takuya
	Nakahata, Shoko
	Harada, Takashi
	Ina, Toshiaki
	Nakanishi, Shuji
	Kamiya, Kazuhide
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-02-14
DC.identifier	https://doi.org/10.1002/cssc.202402576
DC.subject	C₂₊products, Cu nanoclusters derived from single-atom catalysts
	CO reduction reaction
	DFT calculations
	OperandoXAFS
	UniProt
DC.description	Ohashi K., Nishimura K., Nagita K., et al. Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction. ChemSusChem, (2025); https://doi.org/10.1002/cssc.202402576.
DCTERMS.abstract	Electrochemically grown copper nanoclusters (CuNCs: <3 nm) from single-atom catalysts have recently attracted intensive attention as electrocatalysts for CO2 and CO reduction reaction (CO2RR/CORR) because they exhibit distinct product selectivity compared with conventional Cu nanoparticles (typically larger than 10nm). Herein, we conducted a detailed investigation into the size dependence of CuNCs on selectivity for multicarbon (C2+) production in CORR. These nanoclusters were electrochemically grown from single Cu atoms dispersed on covalent triazine frameworks (Cu-CTFs). Operando X-ray absorption fine structure analysis revealed that Cu-CTFs containing 1.21 wt % and 0.41 wt % Cu (Cu(h)-CTFs and Cu(l)-CTFs, respectively) formed CuNCs of 2.0 and 1.1 nm, respectively, at −1.0 V vs. RHE. The selectivity for CORR products was particularly dependent on the size of CuNCs, with the Faraday efficiencies of C2+ products being 52.3 % and 32.7 % at −1.0 V vs. RHE with Cu(h)-CTFs and Cu(l)-CTFs, respectively. Spherical CuNCs modeling revealed that larger cluster sizes led to a greater proportion of a surface coordination number (SCN) of 8 or 9. Density functional calculations revealed that the CO dimerization reaction was more likely to proceed at SCNs of 8 or 9 compared to SCN of 7 because of the stability of the *OCCO intermediate.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	100543
citation_title	Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction
citation_author	Ohashi, Keitaro
	Nishimura, Kosei
	Nagita, Kaito
	Hashimoto, Takuya
	Nakahata, Shoko
	Harada, Takashi
	Ina, Toshiaki
	Nakanishi, Shuji
	Kamiya, Kazuhide
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2025-02-14
citation_journal_title	ChemSusChem
citation_firstpage	e202402576
citation_doi	https://doi.org/10.1002/cssc.202402576
citation_public_url	https://hdl.handle.net/11094/100543

Size-Dependency of Electrochemically Grown Copper Nanoclusters Derived from Single Copper Atoms for the CO Reduction Reaction

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