Evolution of microscopic heterogeneity and dynamics in choline chloride-based deep eutectic solvents

Stephanie Spittle; Derrick Poe; Brian Doherty; Charles Kolodziej; Luke Heroux; Md Ashraful Haque; Henry Squire; Tyler Cosby; Yong Zhang; Carla Fraenza; Sahana Bhattacharyya; Madhusudan Tyagi; Jing Peng; Ramez A Elgammal; Thomas Zawodzinski; Mark Tuckerman; Steve Greenbaum; Burcu Gurkan; Clemens Burda; Mark Dadmun; Edward J Maginn; Joshua Sangoro

doi:10.1038/s41467-021-27842-z

Evolution of microscopic heterogeneity and dynamics in choline chloride-based deep eutectic solvents

Nat Commun. 2022 Jan 11;13(1):219. doi: 10.1038/s41467-021-27842-z.

Authors

Stephanie Spittle^#¹, Derrick Poe^#², Brian Doherty³, Charles Kolodziej⁴, Luke Heroux^{5

6}, Md Ashraful Haque⁷, Henry Squire⁸, Tyler Cosby⁹, Yong Zhang², Carla Fraenza¹⁰, Sahana Bhattacharyya¹⁰, Madhusudan Tyagi^{11

12}, Jing Peng¹³, Ramez A Elgammal¹, Thomas Zawodzinski¹, Mark Tuckerman^{3

14

15}, Steve Greenbaum¹⁰, Burcu Gurkan⁸, Clemens Burda⁴, Mark Dadmun^{7

16}, Edward J Maginn¹⁷, Joshua Sangoro¹⁸

Affiliations

¹ Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN, 37996, USA.
² Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN, 46556, USA.
³ Department of Chemistry, New York University, New York, NY, 10003, USA.
⁴ Department of Chemistry, Case Western Reserve University, Cleveland, OH, 44106, USA.
⁵ Department of Materials Science and Engineering, University of Tennessee, Knoxville, TN, 37996, USA.
⁶ Oak Ridge National Laboratory, Neutron Sciences Division, Oak Ridge, TN, 37830, USA.
⁷ Department of Chemistry, University of Tennessee, Knoxville, TN, 37996, USA.
⁸ Department of Chemical and Biomolecular Engineering, Case Western Reserve University, Cleveland, OH, 44106, USA.
⁹ School of Mathematics and Sciences, University of Tennessee Southern, Pulaski, TN, 44106, USA.
¹⁰ Department of Physics and Astronomy, Hunter College, New York, NY, 10065, USA.
¹¹ NIST Center for Neutron Research, Gaithersburg, MD, 20899, USA.
¹² Department of Materials Science and Engineering, University of Maryland, College Park, MD, 20742, USA.
¹³ School of Materials Science and Engineering, Beihang University, Beijing, China.
¹⁴ Courant Institute of Mathematical Science, New York University, New York, NY, 10012, USA.
¹⁵ NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai, China.
¹⁶ Oak Ridge National Laboratory, Chemical Sciences Division, Oak Ridge, TN, 37830, USA.
¹⁷ Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN, 46556, USA. ed@nd.edu.
¹⁸ Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN, 37996, USA. jsangoro@utk.edu.

^# Contributed equally.

Abstract

Deep eutectic solvents (DESs) are an emerging class of non-aqueous solvents that are potentially scalable, easy to prepare and functionalize for many applications ranging from biomass processing to energy storage technologies. Predictive understanding of the fundamental correlations between local structure and macroscopic properties is needed to exploit the large design space and tunability of DESs for specific applications. Here, we employ a range of computational and experimental techniques that span length-scales from molecular to macroscopic and timescales from picoseconds to seconds to study the evolution of structure and dynamics in model DESs, namely Glyceline and Ethaline, starting from the parent compounds. We show that systematic addition of choline chloride leads to microscopic heterogeneities that alter the primary structural relaxation in glycerol and ethylene glycol and result in new dynamic modes that are strongly correlated to the macroscopic properties of the DES formed.

Grants and funding

DE-SC0019409/U.S. Department of Energy (DOE)