Structure, Hydrogen Bond Dynamics and Phase Transition in a Model Ionic Liquid Electrolyte | Sciact - CRIS-system of Boreskov Institute of Catalysis

Structure, Hydrogen Bond Dynamics and Phase Transition in a Model Ionic Liquid Electrolyte Full article

Journal

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

Output data

Year: 2022, Volume: 24, Pages: 6064-6071 Pages count : 8 DOI: 10.1039/d2cp00452f

Tags

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

Authors

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

Affiliations

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

Funding (3)

1	Alexander von Humboldt Foundation
2	Russian Science Foundation	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 AN PMID OpenAlex

Submitted:	Jan 27, 2022
Accepted:	Feb 11, 2022
Published online:	Feb 11, 2022
Published print:	Mar 14, 2022

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

DB	Citing
Web of science	9
Scopus	9
Elibrary	5
OpenAlex	10