Deep eutectic solvent

Deep eutectic solvents are systems formed from a eutectic mixture of Lewis or Brønsted acids and bases which can contain a variety of anionic and/or cationic species.[1] They are classified as types of ionic solvents with special properties. They incorporate one or more compound in a mixture form, to give a eutectic with a melting point much lower than either of the individual components.[2] One of the most significant deep eutectic phenomenon was observed for a mixture of choline chloride and urea in a 1:2 mole ratio. The resulting mixture has a melting point of 12 °C (far less than the melting point of choline chloride, 302 °C and urea, 133 °C),[3] which makes it liquid at room temperature.

The first generation eutectic solvents were based on mixtures of quaternary ammonium salts with hydrogen bond donors such as amines and carboxylic acids. There are four types of eutectic solvents:[4]

Type IQuaternary ammonium salt + metal chloride
Type IIQuaternary ammonium salt + metal chloride hydrate
Type IIIQuaternary ammonium salt + hydrogen bond donor
Type IVMetal chloride hydrate + hydrogen bond donor

Type I Eutectics therefore also include the wide range of chlorometallate ionic liquids widely studied in the 1980s, such as the ever-popular imidazolium chloroaluminates which are based on mixtures of AlCl3 + 1-Ethyl-3-methylimidazolium chloride.[5] In addition to ionic liquids with discrete anions, the electrodeposition of a range of metals has been previously carried out in deep eutectic solvents (DESs). These are quaternary ammonium salts (e.g. choline chloride, ChCl), metal salts or metal salt hydrates and hydrogen bond donors (e.g. urea) and are commonly divided into four groups (Table 1),[6] have been particularly successful on a large scale for metal polishing and immersion silver deposition. While most ionic liquids and DESs include a quaternary ammonium ion as the cationic component, it has recently been shown that eutectics can also be formed between a metal salt (hydrate) and a simple amide or alcohol to form a metalliferous solution composed of cations and anions via disproportionation processes e.g.

2AlCl3 + urea ↔ [AlCl2•urea]+ + [AlCl4]−
These so-called Type 4 eutectics are useful as they produce cationic metal complexes, ensuring that the double layer close to the electrode surface has a high metal ion concentration.[6]

Physicochemical Properties

In contrast with ordinary solvents, such as Volatile Organic Compounds (VOC), DESs have a very low vapour pressure, and thus are non-flammable.[7] The same reference mentions that DESs have a relatively high viscosities which might hinder their industrial applications as they might not flow easily in process streams. DESs possess favorably low densities and can be liquid at a wide range of temperatures, going to around -50 °C for some DESs.[8]

Research

Compared to modern ionic liquids based on discrete anions, such as bistriflimide, which share many characteristics but are ionic compounds and not ionic mixtures, DESs are cheaper to make and sometimes biodegradable.[9] Therefore, DESs can be used as safe, efficient, simple, and low–cost solvents. To date, there are numerous applications that have been studied for DESs. By varying the components of the DES and their molar ratios, new DESs can be produced. For this reason, many new applications are presented in the literature every year. Some of the earliest applications of DESs were the electrofinishing of metals using DESs as electrolytes.[10] Organic compounds such as benzoic acid (solubility 0.82 mol/L) have great solubility in DESs, and this even includes cellulose.[11] For this reason, DESs were applied as extraction solvents for such material from their complex matrices. They were also studied for their applicability in the production and purification of biodiesel,[12][13] and their ability to extract metals for analysis.[14] Incorporating microwave heating with deep eutectic solvent can efficiently increase the solubility power of DES and reduce the time required for complete dissolution of biological samples at atmospheric pressure.[15] It is noteworthy that proton-conducting DESs (e.g. the mixture of imidazolium methanesulfonate and 1H-1,2,4-triazole in a 1:3 mole ratio or the mixture of 1,2,4-triazolium methanesulfonate and 1H-1,2,4-triazole in a 1:3 mole ratio, wherein the Brønsted base may act as the hydrogen bond donor) have also found applications as proton conductors for fuel cells[16] .[17]

Owing to their unique composition, DES are promising solvating environments, affecting the structure and self-assembly of solutes. For example, the self-assembly of sodium dodecyl sulfate (SDS) in DES has recently been studied, implying DES can form microemulsions different from those in water.[18] In another case, the solvation of the polymer polyvinylpyrrolidone (PVP) in DES is distinct from water, whereby the DES appear to be a better solvent for the polymer.[19] It has been also shown that depending on state of matter of the solute homogeneous or heterogeneous mixtures are formed.[20]

DES have also been studied for their potential use as more environmentally sustainable solvents for extracting gold and other precious metals from ore.[21] Some solvent extraction work has been done using DES solvents, Mark Foreman at Chalmers has in recent years published several papers on this topic. He wrote about the use of the solvents for battery recycling from an applied point of view[22] and he also published what may be the first ever serious study of solvent extraction of metals from DES.[23] Foreman has also published two pure research papers on the activity issues in DES, in the first[24] he pointed out that activity coefficients in DES do appear to deviate wildly away from their values in sodium chloride solution while in his later paper[25] he provides a mathematical model for the activity coefficients in DES using the SIT equation.

References
  1. Emma L. Smith; Andrew P. Abbott; Karl S. Ryder (2014). "Deep Eutectic Solvents (DESs) and Their Applications". Chemical Reviews. 114 (21): 11060–11082. doi:10.1021/cr300162p. PMID 25300631.
  2. "Deep Eutectic Solvents" (PDF). kuleuven.be. University of Leicester. Retrieved 17 June 2014.
  3. Andrew P. Abbott; Glen Capper; David L. Davies; Raymond K. Rasheed; Vasuki Tambyrajah (2003). "Novel solvent properties of choline chloride/urea mixtures". Chem. Commun. 0 (1): 70–71. doi:10.1039/B210714G. PMID 12610970.
  4. Andrew Abbott; John Barron; Karl Ryder; David Wilson (2007). "Eutectic-Based Ionic Liquids with Metal-Containing Anions and Cations". Chem. Eur. J. 13 (22): 6495–6501. doi:10.1002/chem.200601738. PMID 17477454.
  5. J. S. Wilkes; J. A. Levisky; R. A. Wilson; C. L. Hussey (1982). "Dialkylimidazolium chloroaluminate melts: a new class of room-temperature ionic liquids for electrochemistry, spectroscopy and synthesis". Inorganic Chemistry. 21 (3): 1263–1264. doi:10.1021/ic00133a078.
  6. Abbott, Andrew P.; Al-Barzinjy, Azeez A.; Abbott, Paul D.; Frisch, Gero; Harris, Robert C.; Hartley, Jennifer; Ryder, Karl S. (2014). "Speciation, physical and electrolytic properties of eutectic mixtures based on CrCl3·6H2O and urea". Physical Chemistry Chemical Physics. 16 (19): 9047–55. Bibcode:2014PCCP...16.9047A. doi:10.1039/c4cp00057a. ISSN 1463-9076. PMID 24695874.}
  7. Gregorio García; Santiago Aparicio; Ruh Ullah; Mert Atilhan (2015). "Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications". Energy & Fuels. 29 (4): 2616–2644. doi:10.1021/ef5028873.
  8. Mukhtar A. Kareem; Farouq S. Mjalli; Mohd Ali Hashim; Inas M. AlNashef (2010). "Phosphonium-Based Ionic Liquids Analogues and Their Physical Properties". Journal of Chemical & Engineering Data. 55 (11): 4632–4637. doi:10.1021/je100104v.
  9. Clarke, Coby J.; Tu, Wei-Chien; Levers, Oliver; Bröhl, Andreas; Hallett, Jason P. (2018-01-24). "Green and Sustainable Solvents in Chemical Processes". Chemical Reviews. 118 (2): 747–800. doi:10.1021/acs.chemrev.7b00571. hdl:10044/1/59694. ISSN 0009-2665.
  10. Abbott, Andrew P.; McKenzie, Katy J.; Ryder, Karl S. (2007). Ionic Liquids IV. ACS Symposium Series. 975. pp. 186–197. doi:10.1021/bk-2007-0975.ch013. ISBN 978-0-8412-7445-7. ISSN 1947-5918.
  11. Richard F. Miller. 2010. Deep eutectic solvents and applications. Patent number: 8022014. Filing date: Mar 25, 2009. Issue date: Sep 20, 2011. Application number: 12/410,662. (http://www.google.com/patents/US8022014)
  12. Maan Hayyan; Farouq S. Mjalli; Mohd Ali Hashim; Inas M. AlNashef (2010). "A Novel Technique For Separating Glycerine From Palm Oil-Based Biodiesel Using Ionic Liquids". Fuel Processing Technology. 91: 116–120. doi:10.1016/j.fuproc.2009.09.002.
  13. Adeeb Hayyan; Mohd Ali Hashim; Maan Hayyan; Farouq S. Mjalli; Inas M. AlNashef (2013). "A Novel Ammonium Based Eutectic Solvent for Pre-treatment of Low Grade Crude Palm Oil and Synthesis High Quality Biodiesel Fuel". Industrial Crops and Products. 46: 392–398. doi:10.1016/j.indcrop.2013.01.033.
  14. Habibi, Emadaldin (2013). "A novel digestion method based on a choline chloride–oxalic acid deep eutectic solvent for determining Cu, Fe, and Zn in fish samples". Analytica Chimica Acta. 762: 61–67. doi:10.1016/j.aca.2012.11.054. PMID 23327946.
  15. Ghanemi, Kamal; Navidi, Mohammad-Amin; Fallah-Mehrjardi, Mehdi; Dadolahi-Sohrab, Ali (2014). "Ultra-fast microwave-assisted digestion in choline chloride–oxalic acid deep eutectic solvent for determining Cu, Fe, Ni and Zn in marine biological samples". Anal. Methods. 6 (6): 1774–1781. doi:10.1039/C3AY41843J. ISSN 1759-9660.
  16. Jiangshui Luo; Tran Van Tan; Olaf Conrad; Ivo F. J. Vankelecom (2012). "1H-1,2,4-Triazole as solvent for imidazolium methanesulfonate". Physical Chemistry Chemical Physics. 14 (32): 11441–11447. Bibcode:2012PCCP...1411441L. doi:10.1039/C2CP41098B. PMID 22801556.
  17. Jiangshui Luo; Jin Hu; Wolfgang Saak; Rüdiger Beckhaus; Gunther Wittstock; Ivo F. J. Vankelecom; Carsten Agert; Olaf Conrad (2011). "Protic ionic liquid and ionic melts prepared from methanesulfonic acid and 1H-1,2,4-triazole as high temperature PEMFC electrolytes". Journal of Materials Chemistry. 21 (28): 10426–10436. doi:10.1039/C0JM04306K.
  18. Pal, M; Rai, R.; Yadav, A.; Khanna, R.; Baker, GA.; Siddharth, P. (2014). "Self-Aggregation of Sodium Dodecyl Sulfate within (Choline Chloride + Urea) Deep Eutectic Solvent". Langmuir. 30 (44): 13191–13198. doi:10.1021/la5035678. PMID 25314953.
  19. Sapir, L.; Stanley, CB.; Harries, D. (2016). "Properties of Polyvinylpyrrolidone in a Deep Eutectic Solvent". The Journal of Physical Chemistry A. 120 (19): 3253–3259. Bibcode:2016JPCA..120.3253S. doi:10.1021/acs.jpca.5b11927. OSTI 1424493. PMID 26963367.
  20. Häkkinen, Riina; Alshammari, Odeh; Timmermann, Vanessa; D’Agostino, Carmine; Abbott, Andrew (2019). "Nanoscale Clustering of Alcoholic Solutes in Deep Eutectic Solvents Studied by Nuclear Magnetic Resonance and Dynamic Light Scattering". ACS Sustainable Chemistry & Engineering. 17 (7): 15086–15092. doi:10.1021/acssuschemeng.9b03771.
  21. Jenkin, Gawen R.T.; Al-Bassam, Ahmed Z.M.; Harris, Robert C.; Abbott, Andrew P.; Smith, Daniel J.; Holwell, David A.; Chapman, Robert J.; Stanley, Christopher J. (March 2016). "The application of deep eutectic solvent ionic liquids for environmentally-friendly dissolution and recovery of precious metals". Minerals Engineering. 87: 18–24. doi:10.1016/j.mineng.2015.09.026.
  22. J.J. Albler, K. Bica, M.R.S. Foreman, S. Holgersson and M.S. Tyumentsev, A comparison of two methods of recovering cobalt from a deep eutectic solvent: Implications for battery recycling, 2017, volume 167, pages 806-814
  23. M.R.S. Foreman, Progress towards a process for the recycling of nickel metal hydride electric cells using a deep eutectic solvent, Cogent Chemistry, 2016, volume 2, UNSP 1139289
  24. M.R.S. Foreman, S. Holgersson, C. McPhee, M.S. Tyumentsev, Activity coefficients in deep eutectic solvents: implications for the solvent extraction of metals, New Journal of Chemistry, 2018, volume 42, pages 2006-2012
  25. Peng Cen, Mikhail S. Tyumentsev, Kastriot Spahiu and Mark Foreman, Metal extraction from a deep eutectic solvent, an insight into activities, PCCP, 2020, https://doi.org/10.1039/C9CP05982B
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