Deep Eutectic Solvents (DESs) are gathering growing attention as sustainable solvents in different fields ranging from synthesis to electrochemical devices. Albeit DES are widely employed, the fundamental knowledge on their interspecies relations is still partial. Understanding the chemistry of this class of green solvent is an essential step to further tune their properties. In this study, we report a detailed experimental and theoretical investigation of two choline-chloride glycerol mixtures using electrochemical, spectroscopic (Raman/Far Infrared), diffraction (X-ray) and molecular simulation methods. Remarkably different Far-infrared spectra have been surprisingly collected for the two mixtures. Differences are attributed to the deconstruction of the extended hydrogen bond network characteristic of pure glycerol and of the 1:2 mixture and absent in the glycerol-richer mixture 1:3. From the analysis of X-ray profiles, that are very well reproduced by molecular dynamics, it was found that the lack of the glycerol H-bond interactions in the glycerol-richer mixture (Ch:Gly 1:3) can be attributed to the establishment of a full coordination shell of polyalcohol molecules around the chloride anion. In the 1:2 composition the coordination is probably defective, as signaled by the FIR spectrum that significantly maintains the features observed for the precursor glycerol, and the chloride stabilization is ensured by interaction with both choline hydroxyl and electrostatic interactions.

A combined electrochemical, infrared and EDXD tool to disclose Deep Eutectic Solvents formation when one precursor is liquid: Glyceline as case study / Bonomo, Matteo; Gontrani, Lorenzo; Capocefalo, Angela; Sarra, Angelo; Nucara, Alessandro; Carbone, Marilena; Postorino, Paolo; Dini, Danilo. - In: JOURNAL OF MOLECULAR LIQUIDS. - ISSN 0167-7322. - (2020), p. 114292. [10.1016/j.molliq.2020.114292]

A combined electrochemical, infrared and EDXD tool to disclose Deep Eutectic Solvents formation when one precursor is liquid: Glyceline as case study

Bonomo, Matteo
;
Gontrani, Lorenzo
;
Capocefalo, Angela
;
Nucara, Alessandro;Postorino, Paolo;Dini, Danilo
2020

Abstract

Deep Eutectic Solvents (DESs) are gathering growing attention as sustainable solvents in different fields ranging from synthesis to electrochemical devices. Albeit DES are widely employed, the fundamental knowledge on their interspecies relations is still partial. Understanding the chemistry of this class of green solvent is an essential step to further tune their properties. In this study, we report a detailed experimental and theoretical investigation of two choline-chloride glycerol mixtures using electrochemical, spectroscopic (Raman/Far Infrared), diffraction (X-ray) and molecular simulation methods. Remarkably different Far-infrared spectra have been surprisingly collected for the two mixtures. Differences are attributed to the deconstruction of the extended hydrogen bond network characteristic of pure glycerol and of the 1:2 mixture and absent in the glycerol-richer mixture 1:3. From the analysis of X-ray profiles, that are very well reproduced by molecular dynamics, it was found that the lack of the glycerol H-bond interactions in the glycerol-richer mixture (Ch:Gly 1:3) can be attributed to the establishment of a full coordination shell of polyalcohol molecules around the chloride anion. In the 1:2 composition the coordination is probably defective, as signaled by the FIR spectrum that significantly maintains the features observed for the precursor glycerol, and the chloride stabilization is ensured by interaction with both choline hydroxyl and electrostatic interactions.
Deep Eutectic Solvent Glyceline Vibrational spectroscopy EDXD Electrochemistry
01 Pubblicazione su rivista::01a Articolo in rivista
A combined electrochemical, infrared and EDXD tool to disclose Deep Eutectic Solvents formation when one precursor is liquid: Glyceline as case study / Bonomo, Matteo; Gontrani, Lorenzo; Capocefalo, Angela; Sarra, Angelo; Nucara, Alessandro; Carbone, Marilena; Postorino, Paolo; Dini, Danilo. - In: JOURNAL OF MOLECULAR LIQUIDS. - ISSN 0167-7322. - (2020), p. 114292. [10.1016/j.molliq.2020.114292]
File allegati a questo prodotto
File Dimensione Formato  
Bonomo_A combined Electrochemical_2020.pdf

solo gestori archivio

Tipologia: Documento in Post-print (versione successiva alla peer review e accettata per la pubblicazione)
Licenza: Tutti i diritti riservati (All rights reserved)
Dimensione 1.47 MB
Formato Adobe PDF
1.47 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1437072
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 11
  • ???jsp.display-item.citation.isi??? 10
social impact