Tetra-n-butylammonium Tricarboxylate Semiclathrate Hydrates as Phase Change Materials: Phase Equilibrium Relations and Memory Effect in Reformation

Minamikawa, Kazuhiro; Shimada, Jin; Sugahara, Takeshi; Hirai, Takayuki

doi:https://doi.org/10.1021/acs.energyfuels.5c00502

Tetra-n-butylammonium Tricarboxylate Semiclathrate Hydrates as Phase Change Materials: Phase Equilibrium Relations and Memory Effect in Reformation

Minamikawa, Kazuhiro; Shimada, Jin; Sugahara, Takeshi et al.

Energy and Fuels, 2025, 39(14), 7104-7109

アクセス数:84件（2025-06-05 03:19 集計）

固定URL: https://hdl.handle.net/11094/100988

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タイトル	Tetra-n-butylammonium Tricarboxylate Semiclathrate Hydrates as Phase Change Materials: Phase Equilibrium Relations and Memory Effect in Reformation
著者	著者名 Minamikawa, Kazuhiro
	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 1000080208800 1000080208800 ORCID 0000-0003-4747-4919 0000-0003-4747-4919 researchmap permalink read0013780 read0013780 Scopus Author ID 7402768651 7402768651 著者名 Hirai, Takayuki
内容	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.5c00502.
抄録	Semiclathrate hydrates (SCHs), one of the phase change materials for cold energy storage, are crystalline compounds consisting of host water molecules and appropriate guest substances. The typical guest substances of SCHs are tetra-n-butylammonium (TBA) salts. In the present study, we investigated the phase equilibrium relations of (TBA)3 tricarboxylate SCHs, where citrate (−Cit) and 1,2,3-propanetricarboxylate (−123Pro) were used as environmentally friendly tricarboxylate anions. The maximum equilibrium temperatures of (TBA)3-Cit and (TBA)3-123Pro SCHs, whose phase diagrams exhibited a congruent-type phase behavior, were 286.02 ± 0.05 and 286.34 ± 0.05 K, respectively. Their dissociation enthalpies were 186 ± 3 and 193 ± 3 kJ/kg, respectively, which are as large as that of TBA-bromide SCH that has been put to practical use in cold energy storage applications. As an index for suppressing the degree of supercooling in SCH reformation, we have focused on the memory effect. The ability to retain the memory effect in the (TBA)3-Cit and (TBA)3-123Pro SCHs was relatively large. The (TBA)3-Cit and (TBA)3-123Pro SCHs would be superior phase change materials for cold energy storage.
出版者	American Chemical Society
収録物名	Energy and Fuels
巻(号)	39(14)
ページ	7104-7109
刊行年月	2025-03-26
言語	英語
ハンドルURL	https://hdl.handle.net/11094/100988
PISSN	08870624
eISSN	15205029
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1021/acs.energyfuels.5c00502
アクセス権	embargoed access
権利情報	© 2025 American Chemical Society.
権利情報	The full-text file will be made open to the public on 26 March 2026 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
DCTERMS.bibliographicCitation	Energy and Fuels. 2025, 39(14), p. 7104-7109
DC.title	Tetra-n-butylammonium Tricarboxylate Semiclathrate Hydrates as Phase Change Materials: Phase Equilibrium Relations and Memory Effect in Reformation
DC.creator	Minamikawa, Kazuhiro
	Shimada, Jin
	Sugahara, Takeshi
	Hirai, Takayuki
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	英語
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-03-26
DC.identifier	https://doi.org/10.1021/acs.energyfuels.5c00502
DC.description	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.5c00502.
DCTERMS.abstract	Semiclathrate hydrates (SCHs), one of the phase change materials for cold energy storage, are crystalline compounds consisting of host water molecules and appropriate guest substances. The typical guest substances of SCHs are tetra-n-butylammonium (TBA) salts. In the present study, we investigated the phase equilibrium relations of (TBA)3 tricarboxylate SCHs, where citrate (−Cit) and 1,2,3-propanetricarboxylate (−123Pro) were used as environmentally friendly tricarboxylate anions. The maximum equilibrium temperatures of (TBA)3-Cit and (TBA)3-123Pro SCHs, whose phase diagrams exhibited a congruent-type phase behavior, were 286.02 ± 0.05 and 286.34 ± 0.05 K, respectively. Their dissociation enthalpies were 186 ± 3 and 193 ± 3 kJ/kg, respectively, which are as large as that of TBA-bromide SCH that has been put to practical use in cold energy storage applications. As an index for suppressing the degree of supercooling in SCH reformation, we have focused on the memory effect. The ability to retain the memory effect in the (TBA)3-Cit and (TBA)3-123Pro SCHs was relatively large. The (TBA)3-Cit and (TBA)3-123Pro SCHs would be superior phase change materials for cold energy storage.
DC.rights	© 2025 American Chemical Society.
DC.rights	The full-text file will be made open to the public on 26 March 2026 in accordance with the publisher's policy.
DC.format	100988
citation_title	Tetra-n-butylammonium Tricarboxylate Semiclathrate Hydrates as Phase Change Materials: Phase Equilibrium Relations and Memory Effect in Reformation
citation_author	Minamikawa, Kazuhiro
	Shimada, Jin
	Sugahara, Takeshi
	Hirai, Takayuki
citation_publisher	American Chemical Society
citation_language	英語
citation_date	2025-03-26
citation_journal_title	Energy and Fuels
citation_volume	39
citation_issue	14
citation_firstpage	7104
citation_lastpage	7109
citation_doi	https://doi.org/10.1021/acs.energyfuels.5c00502
citation_public_url	https://hdl.handle.net/11094/100988

Tetra-n-butylammonium Tricarboxylate Semiclathrate Hydrates as Phase Change Materials: Phase Equilibrium Relations and Memory Effect in Reformation

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