NMR investigation of the structure and single-particle dynamics of inorganic salt solutions in a protic ionic liquid

Vladimir V. Matveev, Alexandr V. Ievlev, Mikhail A. Vovk, Oscar Cabeza, Josefa Salgado-Carballo, Juan J. Parajó, Julio R. Rodríguez, Raúl de la Fuente, Erkki Lähderanta, Luis M. Varela

Research output

1 Citation (Scopus)

Abstract

With the aim to analyze the microstructure of the polar nanoregions of mixtures of ionic liquids and inorganic salts and the single particle dynamics of metal cations in these densely ionic environments, solutions of inorganic nitrate salts (lithium, magnesium, calcium and aluminium nitrates) in the protic ionic liquid ethylammonium nitrate have been characterized by means of nuclear magnetic resonance. The measured spectra reveal that, despite being dried under vacuum, all the studied mixtures contained variable amounts of water, but, while in those with the salt cations of lower ionic potentials (Li+, Ca2+) only bulk free water that can be almost completely removed from the mixture is found, mixtures with the cations of higher ionic potentials (Mg2+, Al3+) contain only hydration water structurally anchored in the primary solvation shells of the metal cations forming coordination complexes inside the polar nanoregions of the densely ionic solvent and, thus, non-removable under vacuum. This hydration water is not properly detected by common Karl Fisher methods and these solutions are sometimes mistakenly considered anhydrous. Moreover, our NMR measurements confirm the nanostructured solvation paradigm, since they show that the influence of the addition of salt on the chemical shifts of the signals associated to hydrogen atoms in the apolar regions of the protic ionic liquid is negligible. Single-particle dynamics of cations of low and high ionic potentials was also studied, and our observations for the diffusion coefficients of lithium and aluminium cations support the conclusion that Li+ diffusion takes place inside anhydrous [Li(NO3)(4)](3-) complexes, while kinetic complexes with Al3+ gather around [Al(H2O)(6)](3+)) aqua ions. (C) 2019 Published by Elsevier B.V.

Original languageEnglish
Pages (from-to)239-246
Number of pages8
JournalJournal of Molecular Liquids
Volume278
DOIs
Publication statusPublished - 15 Mar 2019

Fingerprint

Ionic Liquids
Ionic liquids
Cations
Salts
Positive ions
Nuclear magnetic resonance
salts
cations
nuclear magnetic resonance
liquids
Nitrates
Water
Solvation
Lithium
Hydration
water
solvation
inorganic nitrates
hydration
nitrates

Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Matveev, Vladimir V. ; Ievlev, Alexandr V. ; Vovk, Mikhail A. ; Cabeza, Oscar ; Salgado-Carballo, Josefa ; Parajó, Juan J. ; Rodríguez, Julio R. ; Fuente, Raúl de la ; Lähderanta, Erkki ; Varela, Luis M. / NMR investigation of the structure and single-particle dynamics of inorganic salt solutions in a protic ionic liquid. In: Journal of Molecular Liquids. 2019 ; Vol. 278. pp. 239-246.
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NMR investigation of the structure and single-particle dynamics of inorganic salt solutions in a protic ionic liquid. / Matveev, Vladimir V.; Ievlev, Alexandr V.; Vovk, Mikhail A.; Cabeza, Oscar; Salgado-Carballo, Josefa; Parajó, Juan J.; Rodríguez, Julio R.; Fuente, Raúl de la; Lähderanta, Erkki; Varela, Luis M.

In: Journal of Molecular Liquids, Vol. 278, 15.03.2019, p. 239-246.

Research output

TY - JOUR

T1 - NMR investigation of the structure and single-particle dynamics of inorganic salt solutions in a protic ionic liquid

AU - Matveev, Vladimir V.

AU - Ievlev, Alexandr V.

AU - Vovk, Mikhail A.

AU - Cabeza, Oscar

AU - Salgado-Carballo, Josefa

AU - Parajó, Juan J.

AU - Rodríguez, Julio R.

AU - Fuente, Raúl de la

AU - Lähderanta, Erkki

AU - Varela, Luis M.

PY - 2019/3/15

Y1 - 2019/3/15

N2 - With the aim to analyze the microstructure of the polar nanoregions of mixtures of ionic liquids and inorganic salts and the single particle dynamics of metal cations in these densely ionic environments, solutions of inorganic nitrate salts (lithium, magnesium, calcium and aluminium nitrates) in the protic ionic liquid ethylammonium nitrate have been characterized by means of nuclear magnetic resonance. The measured spectra reveal that, despite being dried under vacuum, all the studied mixtures contained variable amounts of water, but, while in those with the salt cations of lower ionic potentials (Li+, Ca2+) only bulk free water that can be almost completely removed from the mixture is found, mixtures with the cations of higher ionic potentials (Mg2+, Al3+) contain only hydration water structurally anchored in the primary solvation shells of the metal cations forming coordination complexes inside the polar nanoregions of the densely ionic solvent and, thus, non-removable under vacuum. This hydration water is not properly detected by common Karl Fisher methods and these solutions are sometimes mistakenly considered anhydrous. Moreover, our NMR measurements confirm the nanostructured solvation paradigm, since they show that the influence of the addition of salt on the chemical shifts of the signals associated to hydrogen atoms in the apolar regions of the protic ionic liquid is negligible. Single-particle dynamics of cations of low and high ionic potentials was also studied, and our observations for the diffusion coefficients of lithium and aluminium cations support the conclusion that Li+ diffusion takes place inside anhydrous [Li(NO3)(4)](3-) complexes, while kinetic complexes with Al3+ gather around [Al(H2O)(6)](3+)) aqua ions. (C) 2019 Published by Elsevier B.V.

AB - With the aim to analyze the microstructure of the polar nanoregions of mixtures of ionic liquids and inorganic salts and the single particle dynamics of metal cations in these densely ionic environments, solutions of inorganic nitrate salts (lithium, magnesium, calcium and aluminium nitrates) in the protic ionic liquid ethylammonium nitrate have been characterized by means of nuclear magnetic resonance. The measured spectra reveal that, despite being dried under vacuum, all the studied mixtures contained variable amounts of water, but, while in those with the salt cations of lower ionic potentials (Li+, Ca2+) only bulk free water that can be almost completely removed from the mixture is found, mixtures with the cations of higher ionic potentials (Mg2+, Al3+) contain only hydration water structurally anchored in the primary solvation shells of the metal cations forming coordination complexes inside the polar nanoregions of the densely ionic solvent and, thus, non-removable under vacuum. This hydration water is not properly detected by common Karl Fisher methods and these solutions are sometimes mistakenly considered anhydrous. Moreover, our NMR measurements confirm the nanostructured solvation paradigm, since they show that the influence of the addition of salt on the chemical shifts of the signals associated to hydrogen atoms in the apolar regions of the protic ionic liquid is negligible. Single-particle dynamics of cations of low and high ionic potentials was also studied, and our observations for the diffusion coefficients of lithium and aluminium cations support the conclusion that Li+ diffusion takes place inside anhydrous [Li(NO3)(4)](3-) complexes, while kinetic complexes with Al3+ gather around [Al(H2O)(6)](3+)) aqua ions. (C) 2019 Published by Elsevier B.V.

KW - Ionic liquids

KW - NMR

KW - Water

KW - Ethylammonium nitrate

KW - Inorganic salts

KW - Diffusion

KW - Coordination complexes

KW - AQUEOUS-ELECTROLYTE SOLUTIONS

KW - CHEMICAL-SHIFTS

KW - LITHIUM-SALTS

KW - MIXTURES

KW - SOLVATION

KW - HYDRATION

KW - WATER

KW - NANOSTRUCTURE

KW - COMPLEXES

KW - NUMBER

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UR - http://www.mendeley.com/research/pt-20081294

U2 - https://doi.org/10.1016/j.molliq.2019.01.010

DO - https://doi.org/10.1016/j.molliq.2019.01.010

M3 - статья

AN - SCOPUS:85060240704

VL - 278

SP - 239

EP - 246

JO - Journal of Molecular Liquids

JF - Journal of Molecular Liquids

SN - 0167-7322

ER -