Deep eutectic solvent

Deep eutectic solvents or DESs are solutions of Lewis or Brønsted acids and bases which form a eutectic mixture.[1] Deep eutectic solvents are highly tunable through varying the structure or relative ratio of parent components and thus have a wide variety of potential applications including catalytic, separation, and electrochemical processes.[1][2] The parent components of deep eutectic solvents engage in a complex hydrogen bonding network which results in significant freezing point depression as compared to the parent compounds.[3] The extent of freezing point depression observed in DESs is well illustrated by a mixture of choline chloride and urea in a 1:2 mole ratio. Choline chloride and urea are both solids at room temperature with melting points of 302 °C (decomposition point) and 133 °C respectively, yet the combination of the two in a 1:2 molar ratio forms a liquid with a freezing point of 12 °C.[4] DESs share similar properties to ionic liquids such as tunability and lack of flammability yet are distinct in that ionic liquids are neat salts composed exclusively of discrete ions.[1] In contrast to ordinary solvents, such as Volatile Organic Compounds (VOC), DESs are non-flammable, and possess low vapour pressures and toxicity.[5]

The first generation eutectic solvents were based on mixtures of quaternary ammonium salts with hydrogen bond donors such as amines and carboxylic acids. DESs are classified into four types based on composition:[6]

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 include a wide range of chlorometallate ionic solvents which were widely studied in the 1980s, such as imidazolium chloroaluminates which are based on mixtures of AlCl3 + 1-Ethyl-3-methylimidazolium chloride.[7] Type II eutectics are identical to Type I eutectic in composition yet include the hydrated form of the metal halide. Type III eutectics consist of hydrogen bond acceptors such as quaternary ammonium salts (e.g. choline chloride) and hydrogen bond donors (e.g urea, ethylene glycol) and include the class of metal-free deep eutectic solvents.[2][8] Type III eutectics have been successfully used in metal processing applications such as electrodeposition, electropolishing, and metal extraction. Type IV eutectics are similar to type III yet replace the quaternary ammonium salt hydrogen bond acceptor with a metal halide hydrogen bond acceptor while still using an organic hydrogen bond donor such as urea. Type IV eutectics are of interest for electrodeposition as they produce cationic metal complexes, ensuring that the double layer close to the electrode surface has a high metal ion concentration.[8]

Wide spread practical use of DESs in industrial process or devices has thus far been hindered by relatively high viscosities and low ionic conductivities. Additionally, lack of understanding of the relationship between parent compound structure and solvent function has prevented development of general design rules. Work to understand structure-function relation is on-going.

Natural deep eutectic solvents

Natural deep eutectic solvents (NADES) are bio-based[9][10] deep eutectic solvents which are composed of two or more compounds that are generally plant based primary metabolites, i.e. organic acids, sugars, alcohols, amines and amino acids.[11][12] Work done by Choi, Spronsen et al.[11] showed that water can be present as part of the solvent, being strongly retained in the liquid and which cannot be evaporated.

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, DES are cheaper to make and sometimes biodegradable.[13] Therefore, DES can be used as safe, efficient, simple, and low–cost solvents.

To date, there are numerous applications that have been studied for DES. By varying the components of the DES and their molar ratios, new DES can be produced. For this reason, many new applications are presented in the literature every year.[14] Some of the earliest applications of DES were the electrofinishing of metals using DES as electrolytes.[15] Organic compounds such as benzoic acid (solubility 0.82 mol/L) have great solubility in DES, and this even includes cellulose.[16] For this reason, DES were applied as extraction solvents for such material from their complex matrices. DES as extraction solvents in the separation of aromatic hydrocarbons from naphtha was also studied and promising results were published in 2012[17][18] and 2013.[19]

They were also studied for their applicability in the production and purification of biodiesel,[20][21] and their ability to extract metals for analysis.[22] 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.[23] It is noteworthy that proton-conducting DES (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.[24][25]

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.[26] 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.[27] It has been also shown that depending on state of matter of the solute homogeneous or heterogeneous mixtures are formed.[28]

DES have also been studied for their potential use as more environmentally sustainable solvents for extracting gold and other precious metals from ore.[29] 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[30] and he also published what may be the first ever serious study of solvent extraction of metals from DES.[31] Foreman has also published two pure research papers on the activity issues in DES, in the first[32] 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[33] he provides a mathematical model for the activity coefficients in DES using the SIT equation. Lastly, DES involvement in thermoelectrical field was researched through the incorporation of DES in thermoelectric polymer for the synthesis of improved thermoelectric polymer films.[34]

References
  1. Smith, Emma L.; Abbott, Andrew P.; Ryder, Karl S. (12 November 2014). "Deep Eutectic Solvents (DESs) and Their Applications". Chemical Reviews. 114 (21): 11060–11082. doi:10.1021/cr300162p. PMID 25300631.
  2. Gurkan, Burcu; Squire, Henry; Pentzer, Emily (19 December 2019). "Metal-Free Deep Eutectic Solvents: Preparation, Physical Properties, and Significance". The Journal of Physical Chemistry Letters. 10 (24): 7956–7964. doi:10.1021/acs.jpclett.9b01980. OSTI 1608304. PMID 31804088. S2CID 208643425.
  3. "Deep Eutectic Solvents" (PDF). kuleuven.be. University of Leicester. Retrieved 17 June 2014.
  4. Abbott, Andrew P.; Capper, Glen; Davies, David L.; Rasheed, Raymond K.; Tambyrajah, Vasuki (19 December 2003). "Novel solvent properties of choline chloride/urea mixtures". Chemical Communications (1): 70–71. doi:10.1039/b210714g. PMID 12610970.
  5. García, Gregorio; Aparicio, Santiago; Ullah, Ruh; Atilhan, Mert (16 April 2015). "Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications". Energy & Fuels. 29 (4): 2616–2644. doi:10.1021/ef5028873.
  6. Abbott, Andrew P.; Barron, John C.; Ryder, Karl S.; Wilson, David (27 July 2007). "Eutectic-Based Ionic Liquids with Metal-Containing Anions and Cations". Chemistry: A European Journal. 13 (22): 6495–6501. doi:10.1002/chem.200601738. PMID 17477454.
  7. Wilkes, John S.; Levisky, Joseph A.; Wilson, Robert A.; Hussey, Charles L. (March 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.
  8. 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): 9047–9055. Bibcode:2014PCCP...16.9047A. doi:10.1039/c4cp00057a. PMID 24695874.
  9. Abbott, Andrew P.; Boothby, David; Capper, Glen; Davies, David L.; Rasheed, Raymond K. (July 2004). "Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids". Journal of the American Chemical Society. 126 (29): 9142–9147. doi:10.1021/ja048266j. PMID 15264850.
  10. Dai, Yuntao; van Spronsen, Jaap; Witkamp, Geert-Jan; Verpoorte, Robert; Choi, Young Hae (22 November 2013). "Ionic Liquids and Deep Eutectic Solvents in Natural Products Research: Mixtures of Solids as Extraction Solvents". Journal of Natural Products. 76 (11): 2162–2173. doi:10.1021/np400051w. hdl:1887/3193548. PMID 24188074. S2CID 5813169.
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  12. Dai, Yuntao; van Spronsen, Jaap; Witkamp, Geert-Jan; Verpoorte, Robert; Choi, Young Hae (March 2013). "Natural deep eutectic solvents as new potential media for green technology". Analytica Chimica Acta. 766: 61–68. doi:10.1016/j.aca.2012.12.019. hdl:1887/3193533. PMID 23427801. S2CID 19255174.
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  14. Svigelj, Rossella; Dossi, Nicolò; Grazioli, Cristian; Toniolo, Rosanna (January 2021). "Deep Eutectic Solvents (DESs) and Their Application in Biosensor Development". Sensors. 21 (13): 4263. Bibcode:2021Senso..21.4263S. doi:10.3390/s21134263. PMC 8271379. PMID 34206344.
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  16. US Patent 8022014, Richard F. Miller, "Deep eutectic solvents and applications", published 2010, issued Sep 20, 2011
  17. Kareem, Mukhtar A.; Mjalli, Farouq S.; Hashim, Mohd Ali; Hadj-Kali, Mohamed K. O.; Bagh, Fatemeh Saadat Ghareh; Alnashef, Inas M. (15 November 2012). "Phase equilibria of toluene/heptane with tetrabutylphosphonium bromide based deep eutectic solvents for the potential use in the separation of aromatics from naphtha". Fluid Phase Equilibria. 333: 47–54. doi:10.1016/j.fluid.2012.07.020.
  18. Kareem, Mukhtar A.; Mjalli, Farouq S.; Hashim, Mohd Ali; AlNashef, Inas M. (25 January 2012). "Liquid–liquid equilibria for the ternary system (phosphonium based deep eutectic solvent–benzene–hexane) at different temperatures: A new solvent introduced". Fluid Phase Equilibria. 314: 52–59. doi:10.1016/j.fluid.2011.10.024.
  19. Kareem, Mukhtar A.; Mjalli, Farouq S.; Hashim, Mohd Ali; Hadj-Kali, Mohamed K. O.; Ghareh Bagh, Fatemeh Saadat; Alnashef, Inas M. (1 October 2013). "Phase equilibria of toluene/heptane with deep eutectic solvents based on ethyltriphenylphosphonium iodide for the potential use in the separation of aromatics from naphtha". The Journal of Chemical Thermodynamics. 65: 138–149. doi:10.1016/j.jct.2013.05.046.
  20. Hayyan, Maan; Mjalli, Farouq S.; Hashim, Mohd Ali; AlNashef, Inas M. (January 2010). "A novel technique for separating glycerine from palm oil-based biodiesel using ionic liquids". Fuel Processing Technology. 91 (1): 116–120. doi:10.1016/j.fuproc.2009.09.002.
  21. Hayyan, Adeeb; Hashim, Mohd Ali; Hayyan, Maan; Mjalli, Farouq S.; AlNashef, Inas M. (April 2013). "A novel ammonium based eutectic solvent for the treatment of free fatty acid and synthesis of biodiesel fuel". Industrial Crops and Products. 46: 392–398. doi:10.1016/j.indcrop.2013.01.033.
  22. Habibi, Emadaldin; Ghanemi, Kamal; Fallah-Mehrjardi, Mehdi; Dadolahi-Sohrab, Ali (January 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.
  23. 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.
  24. Luo, Jiangshui; Tan, Tran Van; Conrad, Olaf; Vankelecom, Ivo F. J. (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.
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  26. Pal, Mahi; Rai, Rewa; Yadav, Anita; Khanna, Rajesh; Baker, Gary A.; Pandey, Siddharth (11 November 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.
  27. Sapir, Liel; Stanley, Christopher B.; Harries, Daniel (19 May 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.
  28. 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. S2CID 201218446.
  29. 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. Bibcode:2016MiEng..87...18J. doi:10.1016/j.mineng.2015.09.026.
  30. Albler, Franziska-Jane; Bica, Katharina; Foreman, Mark R. StJ.; Holgersson, Stellan; Tyumentsev, Mikhail S. (20 November 2017). "A comparison of two methods of recovering cobalt from a deep eutectic solvent: Implications for battery recycling". Journal of Cleaner Production. 167: 806–814. doi:10.1016/j.jclepro.2017.08.135.
  31. Foreman, Mark R.StJ. (31 December 2016). "Progress towards a process for the recycling of nickel metal hydride electric cells using a deep eutectic solvent". Cogent Chemistry. 2 (1): 1139289. doi:10.1080/23312009.2016.1139289. S2CID 21834215.
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  33. Cen, Peng; Spahiu, Kastriot; Tyumentsev, Mikhail S.; Foreman, Mark R. St. J. (2020). "Metal extraction from a deep eutectic solvent, an insight into activities". Physical Chemistry Chemical Physics. 22 (19): 11012–11024. Bibcode:2020PCCP...2211012C. doi:10.1039/C9CP05982B. PMID 32367089. S2CID 218504859.
  34. Rahman, Shahriar Mufid; Mohd Said, Suhana Binti; Subramanian, Balamurugan; Long, Bui Duc; Kareem, Mukhtar A.; Soin, Norhayati (3 August 2016). "Synthesis and Characterization of Polymer Electrolyte Using Deep Eutectic Solvents and Electrospun Poly(vinyl alcohol) Membrane". Industrial & Engineering Chemistry Research. 55 (30): 8341–8348. doi:10.1021/acs.iecr.6b01754.
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