Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates

Shimada, Jin; Sugahara, Takeshi; Tani, Atsushi; Ueda, Takahiro; Tsugaya, Riko; Tsunashima, Katsuhiko; Hirai, Takayuki

doi:https://doi.org/10.1021/acs.energyfuels.4c00161

Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates

Shimada, Jin; Sugahara, Takeshi; Tani, Atsushi et al.

Energy and Fuels, 2024, 38(7), 6471-6477

アクセス数:50件（2025-04-04 09:53 集計）

固定URL: https://hdl.handle.net/11094/94974

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タイトル	Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates
著者	著者名 Shimada, Jin
	NRID 1000020335384 1000020335384 ORCID 0000-0002-5236-5605 0000-0002-5236-5605 researchmap permalink read0191169 read0191169 Scopus Author ID 56212469300 56212469300 著者名 Sugahara, Takeshi
	NRID 1000010335333 1000010335333 著者名 Tani, Atsushi
	NRID 1000070294155 1000070294155 researchmap permalink Takahiro_ueda Takahiro_ueda Scopus Author ID 7403982331 7403982331 著者名 Ueda, Takahiro
	著者名 Tsugaya, Riko
	NRID 1000090550070 1000090550070 著者名 Tsunashima, Katsuhiko
	NRID 1000080208800 1000080208800 researchmap permalink read0013780 read0013780 Scopus Author ID 7402768651 7402768651 著者名 Hirai, Takayuki
キーワード等	Semiclathrate hydrate
	Electrical conductivity
	Water reorientation
	Proton conduction
	Halide anion
内容	Shimada J., Sugahara T., Tani A., et al. Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates. Energy and Fuels , (2024); https://doi.org/10.1021/acs.energyfuels.4c00161.
抄録	Semiclathrate hydrates are electroconductive materials for possible solid electrolytes and are also useful for monitoring their formation and dissociation processes. In the present study, the electrical conductivities and electrical relaxation times in the single-crystalline tetra-n-butylammonium (TBA) chloride and fluoride semiclathrate hydrates were measured and compared with those of the TBA-bromide semiclathrate hydrate. In the descending order of the electrical conductivity, the largest was the TBA-bromide semiclathrate hydrate, followed by TBA-chloride and TBA-fluoride semiclathrate hydrates. On the other hand, 2H NMR spin-lattice relaxation times in their deuterates were similar. Although the reorientation motion of water molecules should be a significant factor to govern the electrical conductivity in these semiclathrate hydrates, the present results reveal that the difference between the electrical conductivities in three TBA-halide semiclathrate hydrates would be caused by the concentration of the proton, a conduction carrier, rather than the diffusion processes. Additionally, electrical conductivity in the single-crystalline TBA-hydroxide semiclathrate hydrate was measured. The electrical conductivity even in single crystals was much higher than those in the TBA-halide semiclathrate hydrates.
出版者	American Chemical Society
収録物名	Energy and Fuels
巻(号)	38(7)
ページ	6471-6477
刊行年月	2024-04-04
言語	英語
ハンドルURL	https://hdl.handle.net/11094/94974
PISSN	08870624
eISSN	15205029
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1021/acs.energyfuels.4c00161
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 Energy and Fuels, © 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/acs.energyfuels.4c00161.
権利情報	The full-text file will be made open to the public on 4 April 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
DCMI資源タイプ	text
DCTERMS.bibliographicCitation	Energy and Fuels. 2024, 38(7), p. 6471-6477
DC.title	Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates
DC.creator	Shimada, Jin
	Sugahara, Takeshi
	Tani, Atsushi
	Ueda, Takahiro
	Tsugaya, Riko
	Tsunashima, Katsuhiko
	Hirai, Takayuki
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-04-04
DC.identifier	https://doi.org/10.1021/acs.energyfuels.4c00161
DC.subject	Semiclathrate hydrate
	Electrical conductivity
	Water reorientation
	Proton conduction
	Halide anion
DC.description	Shimada J., Sugahara T., Tani A., et al. Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates. Energy and Fuels , (2024); https://doi.org/10.1021/acs.energyfuels.4c00161.
DCTERMS.abstract	Semiclathrate hydrates are electroconductive materials for possible solid electrolytes and are also useful for monitoring their formation and dissociation processes. In the present study, the electrical conductivities and electrical relaxation times in the single-crystalline tetra-n-butylammonium (TBA) chloride and fluoride semiclathrate hydrates were measured and compared with those of the TBA-bromide semiclathrate hydrate. In the descending order of the electrical conductivity, the largest was the TBA-bromide semiclathrate hydrate, followed by TBA-chloride and TBA-fluoride semiclathrate hydrates. On the other hand, 2H NMR spin-lattice relaxation times in their deuterates were similar. Although the reorientation motion of water molecules should be a significant factor to govern the electrical conductivity in these semiclathrate hydrates, the present results reveal that the difference between the electrical conductivities in three TBA-halide semiclathrate hydrates would be caused by the concentration of the proton, a conduction carrier, rather than the diffusion processes. Additionally, electrical conductivity in the single-crystalline TBA-hydroxide semiclathrate hydrate was measured. The electrical conductivity even in single crystals was much higher than those in the TBA-halide semiclathrate hydrates.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Energy and Fuels, © 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/acs.energyfuels.4c00161.
DC.rights	The full-text file will be made open to the public on 4 April 2025 in accordance with the publisher's policy.
DC.format	94974
citation_title	Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates
citation_author	Shimada, Jin
	Sugahara, Takeshi
	Tani, Atsushi
	Ueda, Takahiro
	Tsugaya, Riko
	Tsunashima, Katsuhiko
	Hirai, Takayuki
citation_publisher	American Chemical Society
citation_language	英語
citation_date	2024-04-04
citation_journal_title	Energy and Fuels
citation_volume	38
citation_issue	7
citation_firstpage	6471
citation_lastpage	6477
citation_doi	https://doi.org/10.1021/acs.energyfuels.4c00161
citation_public_url	https://hdl.handle.net/11094/94974

Effects of Halide Anions on the Electrical Conductivity in Single-Crystalline Tetra-n-butylammonium Salt Semiclathrate Hydrates

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