Structure, Hydrogen Bond Dynamics and Phase Transition in a Model Ionic Liquid Electrolyte | Sciact - CRIS-система Института катализа

Structure, Hydrogen Bond Dynamics and Phase Transition in a Model Ionic Liquid Electrolyte Научная публикация

Журнал

PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084

Вых. Данные

Год: 2022, Том: 24, Страницы: 6064-6071 Страниц : 8 DOI: 10.1039/d2cp00452f

Ключевые слова

Deuterium; Electrolytes; Enthalpy; Hydrogen bonds; Ionic liquids; Negative ions; Nuclear magnetic resonance spectroscopy; Positive ions

Авторы

Khudozhitkov Alexander E. ^1,2 , Stange Peter ³ , Stepanov Alexander G. ¹ , Kolokolov Daniil I. ^1,2 , Ludwig Ralf ^3,4

Организации

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3	Universität Rostock, Institut für Chemie, Abteilung für Physikalische Chemie, Dr-Lorenz-Weg 2, 18059 Rostock, Germany
4	Leibniz-Institut für Katalyse an der Universität Rostock e.V, Albert-Einstein-Str. 29a, 18059 Rostock, Germany

Информация о финансировании (3)

1	Alexander von Humboldt Foundation
2	Российский научный фонд	21-13-00047
3	German Research Foundation	LU 506/15 (401427621)

We show that solid-state NMR spectroscopy is a suitable method for characterizing the structure, hydrogen bond dynamics and phase transition behavior in protic ionic liquids (PILs). Deuteron line shape and spin relaxation time analysis provide a description of the structural and dynamical heterogeneity in the solid state of the model PIL triethyl ammonium bis(trifluoromethanesulfonyl)amide [TEA][NTf2]. Therein, we observed two deuteron quadrupole coupling constant for the ND bond of the TEA cation, indicating differently strong hydrogen bonds to the nitrogen and oxygen atoms of the NTf2 anion, as we could confirm by DFT calculations. The transition processes in the dynamically heterogeneous phase are characterized by two standard molar enthalpies and thus different stages of melting. We provide geometry, rates and energetics of the cation in the solid and liquid states of the PIL. Comparison with PILs having stronger interacting anions shows higher enthalpy change between the solid and liquid states, lower activation barriers of tumbling motion and higher amplitude of librational motion for the TEA cation in the presence of the weakly interacting anion NTf2. We provide reasonable relations between microscopic and macroscopic properties, as is relevant for any kind of application.

Khudozhitkov A.E. , Stange P. , Stepanov A.G. , Kolokolov D.I. , Ludwig R.
Structure, Hydrogen Bond Dynamics and Phase Transition in a Model Ionic Liquid Electrolyte
PCCP: Physical Chemistry Chemical Physics. 2022. V.24. P.6064-6071. DOI: 10.1039/d2cp00452f WOS Scopus РИНЦ CAPlus PMID OpenAlex

Поступила в редакцию:	27 янв. 2022 г.
Принята к публикации:	11 февр. 2022 г.
Опубликована online:	11 февр. 2022 г.
Опубликована в печати:	14 мар. 2022 г.

Web of science:	WOS:000760906400001
Scopus:	2-s2.0-85126072285
РИНЦ:	48190045
Chemical Abstracts:	2022:493224
PMID (PubMed):	35212342
OpenAlex:	W4211077779

БД	Цитирований
Web of science	7
Scopus	7
РИНЦ	5
OpenAlex	8