Accepted Article

Title: CO2 capture with Ionic liquids (ILs) and Deep Eutectic Solvents
(DESs): a new generation of sorbents

Authors: shokat sarmad, Jyri-Pekka Mikkola, and Xiaoyan Ji

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To be cited as: ChemSusChem 10.1002/cssc.201600987

Link to VoR: http://dx.doi.org/10.1002/cssc.201600987

A Journal of

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ChemSusChem 10.1002/cssc.201600987

REVIEW

CO2 capture with Ionic liquids (ILs) and Deep Eutectic Solvents
(DESs): a new generation of sorbents
Shokat Sarmad, * [a] Jyri-Pekka Mikkola,[b,c] and Xiaoyan Ji [a]

This article is protected by copyright. All rights reserved.

ChemSusChem 10.1002/cssc.201600987

REVIEW

Abstract: High cost and high energy penalty for carbon ammonia production also emit significant amounts of CO2.
dioxide (CO2) uptake from flue gases are important The greatest anthropogenic portion of CO2 emitted to the
obstacles in large-scale industrial applications, and environment is from the flue gases in power plants.
developing efficient technology for CO2 capture from Therefore, decreasing CO2 emissions from flue gases is
technic and economic points is crucial. Ionic liquids (ILs) very important.[4]
show the potential for CO 2 separation due to their inherent CO2 capture and storage (CCS) has been proposed as one
advantages and have been proposed as alternatives in of the most important inventions to mitigate CO 2
order to overcome the drawbacks of conventional sorbents. emissions.[5] The process of CCS includes capturing waste
Chemical modification of ILs to improve their performance CO2, transporting the captured CO 2 to a storage site and
in CO2 absorption has received more attention. Deep depositing it in a safe place. Due to the high cost of
eutectic solvents (DESs) as a new generation of ILs are separating CO2 in CCS, comprehensive efforts have been
considered as more economical alternatives to cope with put to develop efficient technologies to capture and
the deficiencies of high cost and high viscosity of separate CO2 from flue gas, atmospheric air, and synthesis
conventional ILs. This review discusses the potential of the gas.[6,7]
functionalized ILs and DESs as CO2 sorbents. Incorporation One of the most common techniques to remove CO 2 from
of CO2-philic functional groups like amine in cation and/or gas streams is the absorption by liquid solvents. In the
anion moiety of ILs can be promoted their absorption absorption cycle, the CO2-rich solution from the absorber is
capacity. In general, the functionalization of anion part of transferred to the regenerator to release CO2 typically by
ILs is more effective than cation part. DESs represent increasing the temperature and/or decreasing pressure.
favourable solvent properties and are capable of capturing The regenerated solution is recirculated to the top of the
CO2, but the research work is scarce and undeveloped absorber, thus completing the cycle. The gas from the
compared to the studies conducted on ILs. It is possible to regenerator is concentrated in CO2 and ready for
develop novel DESs with promising absorption capacity. dehydration and compression to a liquid phase for the
However, more investigation needs to be carried out on the purpose of storage. The absorption can be either a physical
mechanism of CO2 sorption of DESs to clarify how these or chemical absorption process. In a physical absorption
novel sorbents can be adjusted and fine-tuned to best process, CO2 is physically absorbed into the solvent and
tailored as optimized media for CO2 capture. removed in the absorber column via the rich solvent. The
CO2 solubility in the physical absorption process follows the
Henry’s Law, and the process favours high-pressure and
1. Introduction low-temperature operations. This technology is mature and
has been widely applied to treat both natural- and synthesis
Nowadays, the threat of global warming attracts ever more gas streams.[8] In a chemical absorption process, the
attention. The exponential increase in the concentration of chemical reagents capture CO2 by a reversible chemical
greenhouse gases in the atmosphere is considered as one reaction, and weakly bonded intermediates are formed.
of the most important reasons for climate change. Carbon Consequently, the intermediate compounds upon heating
dioxide (CO2) is the most significant anthropogenic are broken down into streams of solvent and CO 2 in the
greenhouse gas and thus makes a major contribution in regenerator. The chemical absorption process is more
global warming. Naturally, CO2 exists in the atmosphere as suitable for the gas streams with a low partial pressure of
part of the earth’s carbon cycle, but human activities are CO2, and it has been widely developed and
influencing the carbon cycle by emitting more CO 2 to the commercialized.[9-11] Traditionally, aqueous amine solutions
atmosphere.[1-3] have been used as chemical solvents upon trapping CO 2 by
The main source of CO2 emission is the combustion of chemical absorption since they exhibit excellent absorption
fossil fuels for transportation or production of electricity; capacity, high reactivity, high selectivity and low price. The
meanwhile, the industrial processes such as cement main disadvantages associated with these solutions are the
manufacturing, natural gas processing, iron smelters, and high energy demand for the regeneration of solvent, the
corrosion induced, and the loss of the solvent because of
their volatility.[12] Therefore, researchers have been focused
[a] Dr. Shokat Sarmad, Department of Engineering Science and on developing more efficient solvents for CO2 separation.
Mathematics, Devision of Energy Science, Luleå University of
During the last decades, ionic liquids (ILs) have received
Thechnology, 971 87 Luleå Sweden
E-mail: shokat.sarmad@ltu.se great attention as potential alternatives to common amine
Professor Xiaoyan Ji, xiaoyan.ji@ltu.se solutions due to their almost unlimited tunability in terms of
[b] Professor Jyri-Pekka Mikkola, Technical Chemistry, Department of the chemical properties, e.g. the low melting point and
Chemistry, Chemical-Biological Centre, Umeå University, SE-90871,
negligible vapour pressure.[13, 14] They belong to a class of
Umeå, Sweden
E-mail: jyri-Pekka.Mikkola@umu.se organic salts with lattice energies lower than those of
[c] Industrial Chemistry & Reaction Engineering, John Gadolin Process common inorganic salts like NaCl, and they are highly
Chemistry Centre, Åbo Akademi University, Biskopsgatan 8, Fl- affected by their asymmetric structure. Hence, it is possible
20500, Åbo-Turku, Finland
for them to exist in the liquid state at room temperature.
E-mail: jpmikkol@abo.fi

This article is protected by copyright. All rights reserved.

[15.Sc. as a first author or main contributor. they are green and Tabriz.[23] Zhang et al. They Chemical technology) at both Umeå Univ. pyrrolidinium. thermodynamics and transport CO2 separation needs to be improved. conventional and IL-based technologies particularly Since 2008 he is a professor (Sustainable including switchable ILs (SILs) for CO2 separation. and they also suggested further PhD in chemical engineering from Åbo developments. discussed CO2 capturing using ILs based on the solubility measured Xiaoyan Ji was born in Jiangsu. Meanwhile. meanwhile. Besides. has worked at Luleå University of Technology The research work on developing conventional ILs for CO2 as a postdoctoral fellow in a research group which focuses on CO 2 separation has been reviewed. their synthesis and properties were also discussed. CH4.ChemSusChem 10. such as their potential toxicity and low improve the absorption capacity by altering their structures biodegradability as well as often high-cost. in Zhao et al. and how to adjust their viscosity to an many common properties with them. reviewed progress in CO2 trapping using chemical engineering from Åbo Akademi conventional ILs. technology. Since DESs are properties of IL solutions. the toxicity and low biodegradability of ILs from gas streams. and the mechanisms of chemisorption and physisorption Up to now. Shokat Sarmad received her PhD in The properties of these solvents can be rendered for CO 2 physical chemistry from the University of separation. the acceptable range is crucial. so that also affect their properties. Finland in 1992. compared to conventional ILs. They reviewed the CO2 solubility in the ILs 1971.[17. and the view-cell the area of Chemical Engineering and methods were also described. . Åbo-Turku.). similar to conventional ILs. pyridinium and other in 2000. It is important to conventional ILs. economics was provided. discussed applications of task-specific ILs for CO2 capture activation and This article is protected by copyright. chemical kinetics. it will be of importance to gain authored 10 publications in peer-reviewed the experiences from ILs on how to improve their scientific journals and one book chapter.16] have been discussed. born in Nousiainen. fluids (ionic liquids) with interface (confined). DESs possess analogous properties to ILs and share high viscosity. promising gas separation solvents. more recently. capture. polymerized ILs and the mixtures of ILs with returned to the academia to complete his molecular solvents. Tabriz-Iran in 2011. She performance. China in experimentally. Dr. She got PhD in Chemical Engineering based on imidazolium. synthesis of DESs is simple.. 1999. However. discussed separation/capture and storage using the novel ionic liquid-based recent progress and development in using ILs in CO 2 technology.. supported IL membranes and polymerized ILs were included in this review.[20] Yu and coworkers investigated Prof. The principal from the aspects of environment. Different experimental techniques like experiences of research and development in gravimetric analysis. she has published 70+ were explained with experimental characteristics and journal articles. Importantly. molecular simulation.1002/cssc. Finland.. DESs. Her principle biodegradable. IL technologies.[21] In another work. Finland. task-specific ILs. and the performance of these solvents on materials. etc. research work on DESs is still in its infancy and characterization of ILs. He has systems. and the presence of impurities may In many common ILs. Åbo-Turku. [19] In disadvantage of ILs that has been widely discussed is their fact. reviewed Akademi Univ. and areas of interest are green chemistry. the areas of interest are synthesis. the absorption capacity is lower industrial applications. Privalova et al. reviewed the Energy Engineering. To cope with the deficiencies of than that of commercial amine solutions.[22] Torralba et al. and polymeric undeveloped. However. the pressure drop. She has co.18] These aforementioned the removal of CO2 requires less energy in comparison to drawbacks combined with the high price of ILs restrict their amine solutions. CO2 capture by absorption and adsorption technologies. focused on both traditional solvents and different advanced Sweden and Åbo Akademi. After spending a few years at the industry he membranes. The suitability of different ILs as and novel materials. functionalized ILs. 5 books/book-chapters and 30+ conference contributions. the comparison of these technologies co-authored >200 papers and holds a number of patents. CO2 is physically absorbed. They discussed fundamental theoretical modelling and and compared the CO2 absorption capacities of pure ILs experimental measurements for the complex (conventional and task-specific ILs) and mixtures of ILs. Jyri-Pekka Mikkola. ILs are capable to selectively separate CO2 cation. as well generally. another important deep eutectic solvents (DESs) have been introduced. or mixing with other solvents.201600987 REVIEW Since CO2 is more soluble in ILs than other common gases This can be targeted by choosing appropriate anion and/or (N2. [11] Finland in 1966 received his M. Her expertise is on research progress on CO2 capture using ILs with a specific applied thermodynamics focused on attention to potential industrial applications. and the room temperature ILs.[24] Yang et al. All rights reserved. She has more than 20 years’ common cations. supported IL Univ. Hasib et al. and almost all DESs can be prepared by mixing a hydrogen bond donor (HBD) with a hydrogen bond acceptor (HBA) in appropriate molar ratios.

[36-38] amine hybrid solvents as an adjustable approach for removal of ILs since several years back are known as potent CO 2 CO2. The motivation is that the ammonium alkylcarbonate and their applications in gas separation. reviewed. the ILs as out to summarize how to functionalize the conventional ILs physical absorbents for CO2 separation were tackled at first. The studies indicate that the supercritical achievements and difficulties that have been faced in CO2 is highly soluble in ILs (almost up to 0. All rights reserved. ILs have been recognized as potential sorbents for CO2 whereas Zhang et al. to our best knowledge. During the past decade. reviewed the differences between the reactive physicochemical properties are tunable via a myriad of structural and reversible ILs and conventional ILs reported in the modifications of cation or anion. They have absorption occurs via a physical absorption mechanism. Ramdin’s group discussed state-of-the-art of absorbents. The role of these ILs as physical solvents or that of supported ionic liquid Obviously. and they thus can be called as literature. 41] All this renders ILs promising for CO2 separation. the salt formed during the CO2 uptake exhibited excellent review on how to functionalize DESs is still unavailable. ILs are capable of CO2 sorption either by physical or pressure and thus are similar to IL solutions. and a lot of research work has been carried out.[29] forth.[25] Kumar functional groups on improving the performance of ILs and and coworkers reviewed applications of aqueous amines. To achieve this. In This article is protected by copyright.[28] Room temperature ILs by the salts. The research work on DESs was also reviewed binding organic liquids) was less energy consuming.1002/cssc. IL-CO2 systems have been CO2 capture using ILs. The most predominant advantage is that their Shannon et al. biodegradable. but discovering a proper IL for CO2 capture with the consideration of the normal volume expansion is not observed in the liquid due to economical and envionmental issue. 39] fluorination of the ions had no influence on CO 2 solubility while Meanwhile. frequently negligible vapor pressures as well as of-the-art results to deduce the possibility of ILs as appropriate high thermal and chemical stabilities. Ionic liquids (ILs) room temperature ILs as CO2 separation media. reactivity in terms of catalytically converting the captured The goal of this work was to review the influence of different CO2 into organic molecules under low pressures. explained that Ils did not exhibit higher physical low vapor pressure of ILs and the incapacity of CO2 to sorption of CO2 compared to the n-alkanes and stated that the sufficiently solvate ions in the supercritical phase. no work has been carried ILs with selected organic solvents. to render solvents great potential to chemically capture CO2. ILs as physical absorbents for CO2 separation with the focus on their properties.201600987 REVIEW subsequent conversion of CO2. and combination of ILs with secondary. In this section. provided a short knowledge on improving DESs for CO2 capture.[26] Zhang et al. and properties and CO2 absorption capacity of ILs was the stripping of CO2 from the so-called CO2BOLs (CO2. Smith et al. DESs to achieve an efficient CO2 capture as well as on the ILs and IL-amine blends for natural gas sweetening and interaction between CO2 and IL. a class of novel solvents typically made up of asymmetric combination with amine groups in anion or cation part exhibit bulky cations and organic/inorganic anions. solubility.[40. . 510-7 mole fraction of CO2 solubility in ILs. CO2 prepared as very low-cost solutions as well.[13. or SO2. designer solvents.[32] The heavy alkanes possess very low vapor In principle. targeting catalytic and applications of DESs. reviewed the syntheses. separation. Conventional ILs are defined as the ILs chemically and thermally stable. For deep eutectic solvents. summary regarding the development of CO2 separation and conversion using ILs.1. three review papers were found 2.[35] Therefore. ILs belong to one of the potential alternatives for CO2 membranes (SILMs) as highly permeable and selective transport capture owing to their specific characteristics. ILs exhibit coworkers discussed the use of ILs as alternative fluids for CO2 unique properties such as low melting point (often near room capture and natural gas sweetening as well analyzed the state. H2S. by modest heating or inert gas bubbling. recently transformation of CO2 under low pressures (preferably at 1 provided a summary of physicochemical properties of DESs atm).34] Garcia et al. tertiary and sterically the effect of CO2-philic functional groups on physical hindered amines were highly efficient in CO2 capturing.[33.[32] functionalization of ILs or using binary mixtures of ILs or mixing However.ChemSusChem 10. and in order to optimize their performance for CO2 separation as then it was followed by a review of the functionalized varieties.[30] They introduced imidazolium and imidazolium.g. properties. They discussed that the research work on CO2 capture with ILs was surveyed. For from the aspect of functional groups. temperature).[31] the strong Coulombic forces between the ions. The effect of the alkyl chain CO2 absorption capacity of ILs can be improved by length on the CO2 solubility was also investigated. and can be that do not possess any functional groups and thus. Alkanes are chemical absorption.75 mole fraction). which is associated with the a references.[27] Bara et al. very recently discussed some myths about the dissolve in supercritical CO2 (e. CO2 is more soluble in ILs than in common organic the existence of the oxygenation slightly decreased the CO 2 solvents. They are organic medium was investigated. The moderately high molecular weight. reviewed the research work using imidazolium-based 2.[32] They used CO2 solubility in eicosane as [C4MIM][PF6] in CO2-rich phase). discussed the properties of DESs and their applications in different areas. ILs do not Carvalho et al.[28] Karadas and with a polar (even as a non-aqueous solution) nature.[31] They provided an overview of the investigated in detail. well as the underlying mechanisms. CO 2 ILs and the requirements of CO2 uptake will provide could be stripped. the their healthy/environmental effects. The experiences on example. non-flammability and so alternatives to conventional amine-based absorbents.

FFV can be defined as the difference between the molar volume and Van der Waals Importantly. [Tf2N]) may be due to the presence of a IL participate in Coulombic interactions and form a rigid packing. free volume increases that resulting in providing more free space for gas molecules. It has been stated that both the cation and the anion of an fluorinated anions (e. It was revealed that the increasing the molar volume and free volume of ILs.1. Huang et al. CO2 solubility on classical thermodynamics.34 MPa at 283.1002/cssc.[50] It was believed that the fluorination of the anion than solute−solvent interactions as claimed by Carvalho and was the main reason for the increased CO2 solubility. The high CO2 solubility is needed to achieve Vm a cost-effective process.[44.[51] The high CO2 solubility in the ILs containing CO2. S=O group (referred the Henry’s Law constants listed in Table Further. the CO2 separation takes place via physical molecular dynamics simulations. The full name and imidazolium-based ILs and demonstrated that the volume. On the basis of ab initio calculations.[46] observation was further confirmed by Pringle et al. revealed that CO2 solubility and selectivity in ILs observation of the solubility measurements and the results from were controlled by the free volume of the IL. the CO2 solubility in ILs increases by increasing pressure at a constant a) The influence of anion temperature but at very high pressures reaches to a steady level because there is no free volume occupied by CO2 molecules. All rights reserved.3Vvdw FFV  (1) of amine solutions.1. originally available. This Coutinho.[42. rearranged by a small angular displacement in order to form large voids around imidazolium rings or near the alkyl chains to This article is protected by copyright. it was found the S=O comparison to organic solvents.5.ChemSusChem 10.[49] These results further confirm the hypothesis Fractional free volume (FFV) is attributed to the ratio of empty that the cations and anions of ILs form a rigid network with space to occupied space in a material.56-364. these free spaces can be occupied atom of CO2. with increasing alkyl chain length.[47] The rigid network of cations group increased the CO2-philicity of molecules due to Lewis and anions in ILs potentially includes a large amount of free acid-base interactions between the S=O group and the carbon volume. as a consequence. and the results demonstrated absorption mechanism.[52] by the CO2 molecules. who studied Due to Coulombic interactions between the ions of ILs. several review articles have been published with the hold CO2 molecules. by and different anions were examined. just a certain amount of CO 2 molecules could be associated even at high pressures.[48] coworkers studied the physicochemical properties and CO 2 Furthermore. in the case Vm  1.04 K.2. the [PF6]− anions were investigate the effect of the anion. This could be inferred on the basis of the Shannon et al. CO2 capture using ILs through physical absorption volume of a component as bellow: is favorable as they consume less energy upon solvent regeneration compared to chemical absorption. e. Upon the physical absorption of CO2 Van der Waals volume of the ILs calculated using methods using ILs. This result approved the idea that entropic those with non-fluorinated anions ([CF3SO3] ˂ [(CF3SO2)2N] ˂ effects had a more dominant contribution in CO2 solubility in ILs [(CF3SO2)3C]). The influence of the anion on the CO2 solubility was also studied This indicates that addition of further CO 2 molecules is by Aki et al. which can be explained by the concept that the CO2 molecules were five times more mobile than the of free volume..1.[49] Their molecular dynamics simulations results were compared with C6MIM-based ILs in order to indicated that after introducing CO2. Mota-Martinez and solutions.[31. also showed that the arrangement tetracyanoborate-based ILs rendered them as an attractive of ions was not disturbed by the addition of CO 2 into IL sorbent for the CO2 separation process. in the work by Huang et al. 44] According to free volume theory. while the rearrangement of the initially focus on summarizing the experimental findings. structure of investigated ILs in this paper are represented in normalized solubility of CO2 was proportional to the free volume Table 1. reported that the size of the originally solubility of 1-hexyl-3-methylimidazolium tetracyanoborate available free spaces in [C4MIM][PF6] was not big enough to [C6MIM][TCB] up to 12.[53] The incorporate CO2. ILs to achieve an efficient separation and the mechanism behind This also indicated that due to the finite free volume that was the experimental findings was analyzed as well. 45] They used the molecular dynamics simulations. The focus of available spaces would not result in a great volumetric this part was to investigate how to improve the performance of expansion during CO2 dissolution even at high concentrations. It can be concluded that Coulombic interactions and thus they are less mobile. The structure of the cation of COSMOtherm program to calculate the free volume of several an IL also influences the CO2 solubility. Physical absorption and Coulombic interactions Meanwhile. In summary. . 2. CO2 CO2 solubility in the ILs with fluorinated anions was higher than solubility increases. the diffusion coefficients for [C4MIM]+. in which seven ILs with the same [C4MIM] cation impossible unless the structure of ILs broken. only a the CO2 absorption capacity in [C2MIM][Tf2N] and small volume expansion is observed in ILs upon dissolution of [C2MIM][Mes2N]. Based 2.g.g. [PF6]− and CO2 molecules were calculated with In common ILs. to the power −0. ions of the IL. the thermal expansion coefficients of ILs are small in 2). 43] CO2 solubility. The molecular dynamics simulations The non-fluorinated nature and low viscosity of carried out by Cadena et al. the size of anions is the main factor influencing the proposed by Bondi.201600987 REVIEW addition.

201600987 REVIEW Table 1. 1-butyl-3-methylimidazolium isobutyrate + N N O [C4MIM][LEV] 1-butyl-3-methylimidazolium levulinate N + O- N O This article is protected by copyright. .3-dimethylimidazolium [C2MMIM][Tf2N] O O N N+ F3C S N S CF3 bis(trifluoromethylsulfonyl)imide O O 1-Methoxymethyl-3-methylimidazolium tetrafluoroborate [C2OMIM][BF4] N+ F O - F B F HN F O 1-ethylpyridinium ethylsulfate [C2py][EtSO4] OH N+ O S O OH F 1-(3-hydroxypropyl)-3-methylimidazolium [C3OHMIM][BF4] - N+ N F B F F 1-butyl-3-methylimidazolium acetate [C4MIM][Ac] - N+ O N O F 1-butyl-3-methylimidazolium tetrafluoroborate [C4MIM][BF4] - N+ N F B F F OH 1-butyl-3-methylimidazolium dibutylphosphate [C4MIM][Bu2PO4] O N+ N P O O O [C4MIM][IBS] O .1002/cssc. Full name and structure of investigated ILs Structure Name Abbreviation O O 1-hexyl-3-methylimidazolium acesulfamate [C6MIM][ACE] S O N N+ N (Z) O (3-aminopropyl)tributylphosphonium alanine [aP4443][Ala] O (S) OH + H2N P NH2 (3-aminopropyl)tributylphosphonium glycine [aP4443][Gly] + O H2N P H2N OH 1-butyl-nicotinic acid butyl ester [b2-Nic][Tf2N] N O O O bis(trifluoromethylsulfonyl)imide F3C S N S CF3 (Z) (E) O O O HO bis(2-hydroxyethyl)ammonium lactate [bheal] H2 N - HO OH O O 1-ethyl-3-methylimidazolium acetate [C2MIM][Ac] - N+ O N O O 1-ethyl-3-methylimidazolium diethylphosphate [C2MIM][Et2PO4] + OH N P N O O O 1-ethyl-3-methylimidazolium ethylsulfate [C2MIM][EtSO4] OH N+ S N O O 1-ethyl-3-methylimidazolium bis(methanesulfonyl)amide [C2MIM][Mes2N] N+ O H3C S N O S CH3 N O O O O 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C2MIM][Tf2N] N+ F3C S N S CF3 N O O O F 1-ethyl-3-methylimidazolium trifluoroacetate [C2MIM][TFA] N+ F N - O F 1-ethyl-2.ChemSusChem 10. All rights reserved.

1-butyl-3-methylimidazolium trimethylacetate [C4MIM][TMA] + N N O F F 1-butyl-3-methylimidazolium [C4MIM][methide] O F S F O O F S C- tris(trifluoromethylsulfonyl)methide F O O + S N O F N F F F F [C5MIM][bFAP] F F 1-pentyl-3-methylimidazolium F F F tris(nonafluorobutyl)trifluorophosphate F F F FF F F F F F . F F P N+ N F F F F F FF F FF F 1-methyl-3-(nonafluorohexyl) [C6H4F9MIM][Tf2N] N F FF F imidazoliumbis(trifluoromethylsulfonyl) imide N+ F O O F3C S N S CF3 F F F F O O F [C6MIM][BF4] + .3-dimethylimidazolium dimethylphosphate [DMIM][Me2PO4] OH + N P N O O O.ChemSusChem 10. All rights reserved. Ecoeng 41M 1-butyl-3-methylimidazolium2-(2-methoxyethoxy) + O S O N N ethylsulfate O O O O Ecoeng 500 O OH PEG-5 cocomonium methylsulfate C13H27 O S O CH3 N O O O H3C OH F 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate [heMIM][BF4] + N N - F B F OH F This article is protected by copyright. F F + F F F N N F F F F O O 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) [C6MIM][Tf2N] N+ N F3C S N S CF3 O O imide F F 1-octyl-3-methylimidazolium hexafluorophosphate [C8MIM][PF6] - N+ N F P F F F - O O OH (2-hydroxyethyl)-trimethyl-ammonium (S)-2-pyrrolidine. [Choline][Pro] (S) + carboxylic acid N HN O 1. [C4MIM][MDEGSO O 4] N + O S O methylimidazoliumdiethyleneglycolmonomethylethersulfate N OH F F 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] - N+ N F P F F F 1-butyl-3-methylimidazolium propionate [C4MIM][PRO] O N+ N - O O O 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4MIM][Tf2N] N+ N F3C S N S CF3 O O O F 1-butyl-3-methylimidazolium trifluoroacetate [C4MIM][TFA] + F N N - O F O.1002/cssc. .201600987 REVIEW O O 1-butyl-3. 1-hexyl-3-methylimidazolium tetrafluoroborate N N F B F F F [C6MIM][eFAP] F F 1-hexyl-3-methylimidazolium F F F tris(pentafluoroethyl)trifluorophosphate F F F - F F P F FF F N + F F N F F [C6MIM][pFAP] F F 1-hexyl-3-methylimidazolium F F tris(heptafluoropropyl)trifluorophosphate F F F F F F F F F F P.

7.2. .7.3.1002/cssc.211OH][Tf2N] N+ O O HO F3C S N S CF3 bis(trifluoromethylsulfonyl) imide O O N-propyl-N-methyl-piperidinium bis(fluorosulfonyl)imide [p(3)mpip][FSI] + O O N F S N S F O O O O [p(3)mpyrr][FSI] N-propyl-N-methyl-pyrrolidinium bis(fluorosulfonyl)imide N+ F S N S F O O O O [p(5)mpyrr][Tf2N] N-methyl-N-pentylpyrrolidinium N+ F3C S N S CF3 O O bis(trifluoromethylsulfonyl)imide tetrabutylphosphonium 2-cyano-pyrrolide [P4444][2-CNPyr] + N P N - tetrabutylphosphonium 3-trifluoromethyl-pyrazolid [P4444][3-CF3Pyra] H F P + HN N F F tetrabutylphosphonium 6-bromo-benzimidazolide [P4444][6-BrBnIm] - N + P Br N This article is protected by copyright.8-hexahydro-1-methyl-2H-pyrimido[1.3.ChemSusChem 10.8-hexahydro-1-methyl-2H-pyrimido[1.4. [MTBDH+]2[HFPD2- F F ] N N a]pyrimidine]-[2.4. [MTBDH+][TFE-] N N F a]pyrimidine][2.2-Trifluoroethanol] (Z) OH N F F F F [1.5-diol] (Z) HO F N F OH (S) O tetraethylammonium α-alanine [N2222][L-Ala] + N H2N OH Triethylbutylammonium acetate [N2224][CH3COO] + - N O O O O N-propyl-N-methyl-N.2.6. All rights reserved.7.6.4. [MTBDH ][Im ] N N a]pyrimidine][imidazole] (Z) HN N N 1. 2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium [hhemea] OH O acetate NH HO 2-hydroxy-N-(2-hydroxyethyl)-N-methylethanaminium lactate [hhemel] OH O HO NH HO O- + - [1.4.N-dimethylammonium [N1223][FSI] N+ F S N S F bis(fluorosulfonyl)imide O O CH3 [N4444][doc] O tetrabutylammonium docusate O CH3 H3C O S O N+ H3C O O O 2-hydroxyethyl(dimethyl)-isopropylammonium [Nip.4-hexafluoropentan-1.2.3.2.3.201600987 REVIEW F F 1-(2-hydroxyethyl)-3-methylimidazolium [heMIM][PF6] N+ N - F P F hexafluorophosphate OH F F O O [heMIM][Tf2N]: 1-(2-hydroxyethyl)-3-methylimidazolium [heMIM][Tf2N] + N N F3C S N S CF3 OH O O bis(trifluoromethylsulfonyl)imide F O 1-(2-hydroxyethyl)-3-methylimidazolium [heMIM][TfO] - N+ F S O N trifluoromethanesulfonate OH F O O.8-hexahydro-1-methyl-2H-pyrimido[1.6.2.3.

b) The influence of cation Recently.[57] Moreover. Due to the smaller Nevertheless. and the viscosity is more than twice of the strongly as [Tf2N]-. [C2MIM][TCB] exhibited higher solubility in most CO2-philic ILs. All rights reserved.201600987 REVIEW tetrabutylphosphonium benzimidazolide [P4444][BnIm] N + P N - trihexyltetradecylphosphonium.ChemSusChem 10. which is known as one of the molar volume. trihexyltetradecylphosphonium dodecylbenzenesulfonate [P66614][C12H25PhS O S O O3] P+ trihexyltetradecylphosphonium imidazole [P66614][Im] P+ HN N trihexyltetradecylphosphonium methioninate [P66614][Met] O (S) S - P+ O NH2 trihexyltetradecylphosphonium prolinate [P66614][Pro] H N (S) O P+ O- - O THEAL tri-(2-hydroxy ethyl)-ammonium lactate HO NH OH O OH HO trihexyltetradecylphosphonium chloride [P66614][Cl] P+ Cl- trihexyltetradecylphosphonium [P66614][Tf2N] O O bis(trifluoromethylsulfonyl)imide P+ F3C S N S CF3 O O O N. this IL was considered unsuitable for sustainable applications. investigated the performance of tetracyanoborate [TCB]. dilution revealed that the [TCB].[54-56] conductivity compared to [C2MIM][Tf2N].2-cyanopyrrolide [P66614][2-CNPyr] - N P+ N trihexyltetradecyphosphonium 4-Hydroxybenza ldehyde [P66614][4-CHO- PhO] P+ HO O O.O 1-hexyl-3-methylimidazolium saccharinate [C6MIM][SAC] S O + N N 1-hexyl-3-methylimidazolium dicyanamide [C6MIM][DCA] N+ O N HN N C C N N [C4Py][TCB] 1-butylpyridinium tetracyanoborate N B.[58] viscosity of [C6MIM][TCB]. Makino et al.[58] They The Comparison revealed that at 333 K. . Therefore. N + N N [Tf2N]--based ILs as attractive solvents for CO2 capture. represented a bit higher solubility than molality scale under the studied condition.1002/cssc. The standard [C6MIM][TCB]. [C6MIM][eFAP].anion interacted with CO2 as biodegradable. [C6MIM][TCB] exhibited reported that [C2MIM][TCB] showed superior transport higher solubility than [C6MIM][PF6] or [C6MIM][BF4]. the presence of fluorine atoms in enthalpy of dissolution and partial molar volume of CO 2 at infinite [C6MIM][eFAP] rendered this IL highly toxic and non. as well as lower viscosity and higher electrical the same as [C6MIM][Tf2N].and bis(trifluoromethanesulfonyl) amide This article is protected by copyright. and almost properties.

15 [62] absorption was triggered by the interaction between ILs and CO2 [62] [C6MIM][FAP] 2.98 313.15 [51] [67] [C2MIM][Nmes2] 7.73 298.15 [48] five tetracyanoborate ([TCB]−) based ILs by integrating ab [48] initio calculations and molecular simulations.[68] The results revealed that [62] [C4MIM][IAAC] 15.10 298. and N-((dimethyl-amino) methylene)-N- [C4MIM][Tf2N] 3. [C4MIM][TFA] 4. which can be inferred by comparison of the [57] Henry’s Law constants listed in Table 2.[48] were focused on investigating the factors that control the [C4MIM][IBS] 0. and the CO2 solubility and diffusivity [62] [C4MIM][BF4] 5.15 [62] [NC-C1MIM]+>[(N11)2CH]+> [HCC-C1MIM]+> [C4MIM]+ >[C4Py]+.15 [62] CO2 solubility in imidazolium-based ILs.15 [65] [C4Py][TCB] could be considered as a promising candidate for [62] CO2 capture.15 Ionic liquid HCO2 [MPa] T [K] References [60] [P4441][Tf2N] 3.15 The influence of the cation on the CO2 solubility was also [C6MIM][Tf2N] 3.29 313. 1- + [60] butylpyridinium [C4Py] . more free volume within the [57] [C6H4F9MIM][Tf2N] 2. [C4Py][TCB] with the lowest cation-anion [C4MIM][PF4] 5.15 the ability of imidazolium-based ILs to donate a hydrogen bond [62] was considerably greater for the IL with hydrogen in the C2 [C4MIM][LEV] 0.29 298.15 [63] [67] [C2MIM][BF4] 2. [62] The decrease in the fractional free volume.15 position rather than a methyl group.[68] [C4MIM][Ac] 0.15 the binding energy of anion-cation followed the order: [C4MIM][SUC] 7. 50.15 Recently.18 298.15 Table 2. Henry’s Law constants for some ILs [60] [p(5)mpyrr][Tf2N] 3. 1- [C4MIM][PF6] 5.94 298.30 298.1002/cssc.00137 298.62 303. Gupta et al. All rights reserved.15 [62] binding energy was predicted to exhibit the highest [62] CO2 solubility and possess the largest fractional free volume.57 298.15 [N1223][FSI] 3.15 investigated how the replacement by a methyl group against a [48] hydrogen atom at the C2 position of the imidazolium ring would [C4MMIM][BF4] 6.80 298.[48] examined three different ILs and [48] [C4MIM][BF4] 5.15 [62] [57] [C2MIM][TFA] 5. As mentioned above.00286 298.15 [64] [C4MIM]+.15 length of the alkyl chain appended into the cation resulted in an [57] increase in CO2 solubility. investigated mainly the cation effect of [C2MIM][Tf2N] 3. The investigation revealed that the [C4MMIM][PF6] 6.34 298.70 293.[60] An increase in the [57] [C6MIM][eFAP] 2. the percentage of [C4MIM][TFES] 6. in which the CO2 molecules occupied the free space [57] within the IL structure via Van der Waals forces and a large [C6MIM][ACE] 3. [68] The ILs studied [C2MMIM][Tf2N] 3.00993 298. [62] [C4MIM][TMA] 0.84 298.15 were those with the cations namely 1-butyl-3-methylimidazolium [C4MIM][Bu2PO4] 4.15 influence the CO2 solubility.15 This article is protected by copyright.15 molecules. .15 [51] [67] [C2MIM][Tf2N] 4. [C6MIM][SAC] 11.10 298.15 Their studies suggested that low cation-anion interactions [62] [C4MIM]2[IDA] 2.26 298.00 298.50 298.28 298. By increasing the alkyl chain length of ILs.31 298. [C5MIM][bFAP] 2.15 [48] this.08 298.16 298. Cadena et al.15 [hmpy][Tf2N] 3.15 [62] [C2MIM][Tf2N] 3.00512 298.34 298.52 298.ChemSusChem 10. particularly at higher pressures (as [C6MIM][pFAP] 2.28 298.15 [Et3NBH2MIM][Tf2N] 3.84 303.56 298.35 303. 1-propargyl-3-methylimidazolium [HCC-C1MIM]+.10 298.16 298.15 [57] the density increases.15 [48] presence of hydrogen on the C2 position only slightly influenced [60] [C4MMIM][Tf2N] 3.29 333.00222 298.15 can be seen from Table 2).15 [57] studied by Aki et al.15 followed this trend too.201600987 REVIEW [62] The experimental and molecular modeling studies by Cadena et [C4MIM][PRO] 0. [C8MIM][Tf2N] 3.65 298.15 [mp(3)pyrr][FSI] 4.15 longer chain is available for a CO2 molecule to vacate this [66] space.09 298.10 298.02 298.18 298. 59] In order to prove [C4MIM][PF6] 5.15 al.15 quadrapole moment.20 298.000229 298.15 methylmethanaminium [(N11)2CH]+. and thus. physical [C6MIM][Tf2N] 2.[48.[50] and Anthony et al.[48] According to literature.15 the CO2 solubility.10 298.70 293.15 [62] [C2MIM][Ac] 0.15 CO2 regeneration in the ILs.20 [mp(3)pip][FSI] 4.30 298.15 played the key role in their high CO2 solvation ability and [C4MIM][CF3CF2CF2COO] 1.96 298.2 [57] [C8H4F13MIM][Tf2N] 2.30 333.15 [61] ethanenitrile-3-methylimidazolium [NC-C1MIM]+.15 [61] [57] [C2MIM][eFAP] 1.

anion was almost an and carbonyl groups.1002/cssc. the electron showed that phosphonium-based ILs dissolved more CO2 than deficient hydrogen atoms can interact with oxygen atoms of imidazolium-based ILs with the same anion. CO2 was considered as a nonpolar [P66614][Tf2N] indicated a stronger interaction between CO2 and solvent due to its low dielectric constant. and this mode of molar entropy of CO2 in [P66614][Cl] observed in their study interactions can be identified as a stabilizing force upon the indicated stronger structural solvation in [P66614][Cl]-based ILs. The higher partial CO2 through weak C-H···O interactions. phosphonium-based ILs (e. it is preferred studied. interaction between an aldehyde or acetate group and and the observed higher partial molar enthalpy for the case of CO2. and the electron deficient where TfO-.contain one. Since fluorine atoms have a substituted at the C2 position of the imidazolium cations was higher electronegativity than hydrogen atoms. 73.201600987 REVIEW c) Novel ILs developed recently based ILs. the solvent [P66614][Cl]. 74] Although.[75] The result indicated that the nature of higher CO2 absorption capacity in comparison to [ P66614][Tf2N] or interactions between CO 2 and fluorocarbons and those [P66614][Cl]. [P66614][C12H25PhSO3]) could Raveendran et al. although being energetically similar. phosphonium.:[50] solubility in ILs. Further. All rights reserved. CO 2 can be [NO3]-˂ [DCA].≈ [PF6]. ILs..[67] They observed that the functional groups.[71] The results indicated that CO2 explains its solvation power of other molecules. The dissociation energies In summary. among the studied ILs. capacity. fluorination may result in a phosphonium-based ILs: namely [P66614][Tf2N] and [P66614][Cl]. one method is to Recently.and Tf3C. a higher CO2 absorption capacity. [P66614][C12H25PhSO3] even exhibited a with CO2. Similar performance was reported in the case of pyridinium-based ILs which are 2. the CO2 solubility in three fluorinated hydrocarbons must be proportional to the [Tf2N]-based ILs with pyrrolidinium. Zhang’s group proposed the following trend for the CO2 solubility in the ILs with different cations: In the case of physical absorption of CO2.˂ [BF4].g. have performed quantum chemical dissolve more CO2 than the respective imidazolium-based ILs calculations to figure out the specific interactions between ([C4MIM][MDEGSO4]).˂ [TfO].˂ [Tf2N]. To improve the performance of ILs. the CO2-philicity of In the work reported by Tagiuri et al. considered as a Lewis acid. those that contain the anion optimal density of fluorine atoms that resulted in a with fluoroalkyl group exhibited a high CO2 absorption maximum CO2-philicity. carbonyl group of the acetate moiety.2. compared to the cation. i.ChemSusChem 10.g. Furthermore.[70] rivalry among the neighbouring electronegative fluorine They reported the highest recorded solubility observed without atoms and thus result in worse Lewis-base potential.[52. In fact. respectively. and phosphonium the carbon atom of CO2 interacts as a Lewis acid with the cations could dissolve more CO2 compared to imidazolium. Their Henry’s law constants are replacement of the hydrogen atoms of common solvents also listed in Table 2. The weak Lewis-base units can imidazolium > phosphonium. they reported the largest observed CO2 and fluorine atom of fluorinated organic materials by CO2 solubility in the ILs when concerning physical absorption comparing the reaction of methane and perfluoromethane (95 g CO2 per kg of ILs). Tf2N. between CO2 and hydrocarbons was completely different. and one oxygen atom This article is protected by copyright. It was observed that the CO2 solubility in molality scale to carry out a stepwise fluorination of hydrocarbons leading followed the trend of pyrrolidinium > methyl substituted to weak Lewis-base units. a negligible effect of the cation on the CO2 One useful method to increase CO2 solubility is the solubility was reported as well. Among the studied ILs.˂ [Tf3C]. groups.e. most of the studied thiouronium > guanidinium > pyridinium > imidazolium. such as amine groups. [Tf2N]. compared the CO2 solubility in three ILs introduce CO2-philic groups in the cation and/or anion of based on bis(fluorosulfonyl)imide [FSI] ([p(3)mpip][FSI]. an acetate group) indicated that CO 2 can contain imidazolium cation with longer alkyl chain exhibited simultaneously act as a Lewis acid and a Lewis base.[69] interact with the carbon atom of CO2 due to the generation Carvalho and coworkers examined the CO 2 solubility of two of polar C-F bonds. Meanwhile. From the interaction viewpoint. with fluorine atoms. those group (e. The results also d) Summary observed clear and specific interactions in the case of partially fluorinated compounds. property of this supercritical CO2 is anyhow similar to the Chen et al. the interactions between CO2 and a carbonyl functional For the case of cations. Their results case of partially fluorinated compounds. . [N4441][FSI]). fluorine atoms solubility of CO2 in the ILs containing [FSI]. and methyl density of fluorine atoms. and they followed the order suggested by Aki et Carbonyl groups are commonly used to improve the CO2 al. Tagiuri et al. compared the CO2 solubility in [C4MIM][MDEGSO4] alkane of hexane. In the chemically binding in terms of CO2 absorption. In fact. Functionalization of ILs cheaper and more easily biodegradable compared to imidazolium ones.[72] ILs were based on imidazolium cations. the large quadrupole moment of and [P66614][C12H25PhSO3]. meanwhile. is capable of improving the CO 2 par compared with those containing more fluorinated anion like absorption capacity of ILs. The literature survey indicates that the presence of [p(3)mpyrr][FSI]. the anion is more as a function of the number of fluorine atoms replaced on important in order to improve the CO 2 absorption capacity the hydrocarbon chain demonstrated that there might be an of ILs. two and three CF 3 carbon atom can interact with carbonyl groups.

and the fluorine atom. Cation functionalization hydrogen atoms via cooperative C-H···O hydrogen bond. The unhindered (primary or secondary) amines introducing the functional groups in their structures. and so forth.[75] permission)[80] Amine functional groups can be added to IL structure to insert specific chemical reactivity with CO2. . In addition. and a partial negative charge can then reside on the oxygen Bates group functionalized the cation moiety with a primary atoms.e.[76] Reaction of primary and primary or tertiary amine. Due to the quadrupolar charge separation in CO 2. contributes to the reaction between amine paired with [DCA] and [BF4] with both a hydroxyl group and a aqueous solutions and CO2. After five cycles there functional groups absorbed CO2 via two different paths: was no loss of efficiency.[57] They Secondary > Tertiary). Their results also revealed that for dissociates to produce CO2 and amine. the amine solutions achieved the regenerate the absorbent. capacity for ammonium carbamate). For this IL. Reaction between CO2 and amine group (adapted with groups to be weaker Lewis-bases. Consequently. whilst for the form a stable carbamate. this kind of strong Lewis acid. This reflected a fact that the carbamate. and some for the cation and some for the anion of ILs. examples The carbonyl group belongs to one of the promising candidates of functionalization of ILs were reviewed. Regeneration of tertiary amines requires less heat energy Fluorination: than for unhindered amines. Tertiary amines have a high theoretical absorptions of CO2. the formation of carbonate and carbamate Sanchez et al. Upon heating.2 MPa).[77] The primary amine maximum capacity and further increasing the CO2 loading was functionalized ILs uptake CO2 via formation of particular not feasible. They observed that of the zwitterion and base-catalyzed deprotonation of the the CO2 loading of ILs increased almost three-folds by zwitterion. the gas carbamate salt. These functional groups can be either in cation or in anion of ILs. the double bonds of CO 2 can carried out via the formation of ammonium carbamate. All rights reserved. 79] [C6H4F9MIM][Tf2N] (as can be seen in Table 2). amine environment challenges. on the literature.1. Besides. Since As a conclusion. CO2 can act as either an electron acceptor or amine in an imidazolium-based IL. loading could be continuously boosted by ascending pressure Tertiary amines in reaction with CO2 form an unstable because of physical absorption. it is evident that CO 2 can act as a weak fluorinated molecules are expensive and lead to potential Lewis acid and Lewis base. capacity to absorb CO2 (one mol of CO2 per mol of amine). Thus. similar to aqueous amine solutions. each CO2 reacted calculations of Raveendran et al.[81] These types of functionalized ILs secondary amines with CO2 consists of two steps: formation were capable of chemical absorption of CO2.5 strong Lewis acid-base interactions with stronger Lewis mol CO2 per mol of the IL (i. The quantum chemical iso-propanol amine. theoretical maximum CO2 capture base groups. in the case of functionalized ILs.1 MPa) the chemical absorption carbamate during absorption is completely stable. However. the formation of ammonium formation of carbamate and formation of carbonate. and only half a mol of CO2 is traditional amine solutions the maximum gas loadings were absorbed per mol of amine.[78. to improve the CO2-philicity of ILs because they are capable of This article is protected by copyright. other functional Carbonylation: groups have also been proposed. This amount was base interactions will render the oxygen atoms of CO 2 comparable with amine solutions like mono-ethanol amine. Amine The process was completely reversible. In the next section.[80] fluorination. At high requires a lot of heat energy to break the bonds and to pressures (above 0. also indicated that the with two amines (1:2 stoichiometry) as shown in the scheme CO2-philicity of carbonyl functions can be influenced by 1. the low rates of CO 2 absorption make tertiary amines difficult to apply for CO2 Muldoon and coworkers investigated the influence of gas removal (reactivity of amines with CO 2: Primary > fluorination in the cation of ILs on the CO2 solubility. and the reaction leads to the formation of task-specific ILs were capable of both chemical and physical bicarbonate ions. This is because the replacement of H O 2 NH2 + CO2 N H3N electronegative fluorine atoms on the carbon atoms N N  N N O N N neighbouring the functional groups resulted in diminished electron density.1002/cssc. 2. The CO2 capture process an electron donor. di- better Lewis-base groups. the carbamate stoichiometrically restricted. Also. a partial Amination: positive charge can be generated on the carbon atom. the molar uptake of CO2 reached 0. non-fluorous CO2-philic groups group.2. The CO2 absorption rates of tertiary deduced that the presence of fluorinated alkyl chains on the amines can be enhanced by adding small amounts of imidazolium cation could improve the CO 2 solubility by primary or secondary amines or some other absorption comparing the CO2 solubility in [C6MIM][Tf2N] and activators like piperazine. it took place.ChemSusChem 10. and the C-H bond (via C-H···O interactions) can were studied further. consequently rendering the carbonyl Scheme 1. Based carbamate was confirmed by FTIR and NMR spectroscopy. After be easily polarized and thus CO2 can take part in relatively almost 3 hours’ exposure. functionalized the imidazolium-based cations generally.201600987 REVIEW of CO2 can interact as a Lewis-base with one of the R. promote the CO2-philicity. Since the formed ILs at low pressures (below 0. whereas.

The very pressure. The Another recognized option was the addition of ether functionality absorption process of the IL-superbase systems was gently into the alkyl chains of ILs. leading to 30. halide ions are capable of interacting with amines in organic This article is protected by copyright. these hydroxyl functionalized ILs exhibited (ethylene glycol) functional groups. the molar ratio of 1. MTBD.[92] In comparison to aqueous Bara’s group synthesized imidazolium-based ILs with oligo.[87] equimolar mixtures of hydroxyl-functionalized imidazolium-based Sharma et al. All rights reserved.201600987 REVIEW participating in Lewis acid-Lewis base interactions. thus leading to increased free volumes. The observations based on FTIR and 13CNMR bubbling CO2 in the conventional ILs resulted in precipitating of spectroscopy confirmed that one mol of these ILs chemically the MEA-carbamate salts. a groups in the side chain of imidazolium cation increased the value higher than that for pure [heMIM][Tf2N]. revealed that the hydroxyl functionalization of ammonium-based Methoxyethyl)-3-methylimidazolium bis(trifluoromethane) ILs did not considerably affect the CO2 absorption capacity while sulfonimide) demonstrated a higher CO2 solubility than the the hydroxyl functionalization of pyridinium-based ILs led to a corresponding alkyl polyethylene analogues.[88] These ILs studied a mixture of [C3OHMIM][BF4] and MEA and compared to showed high absorption capacity (almost 0. these PEG-based ILs (e.9 mol CO2 per mol of the mixture of the conventional IL [C4MIM][BF4] and MEA. 91] The results indicated that the Ecoeng 500® was connected to its large free volume induced by CO2 solubility in hydroxy-functionalized imidazolium-based ILs the long alkyl chain.[91] Huang et al. reported that the CO2 solubility in a series of impressive performance. for the system composed of [heMIM][Tf2N] by Pensado et al. The molar ratio of CO2 to DBU surpassed the theoretical maximum Etherification: for chemical absorption (1. Molecular simulations heating. It is known that DCA  PF6  TfO < Tf2N.[38] The formation of biodegradability of these ILs but did not affect the solvation of amidinium alkylcarbonate due to the reaction of CO2 with an IL CO2 considerably. The IL at 30 C). The similar behavior was shown in [heMIM][BF4] solubilities of N2 and CH4 in these ILs were lower.211OH][Tf2N] as the IL and DBU.[82. reported the CO2 solubility in a series of ether ILs and monoethanolamine (MEA) for CO2 uptake. and the good performance of anions ([PF6].[94] They functionalized imidazolium-based ILs [C2OMIM][X]. and the This could be inferred that the introduction of hydroxyl functional dissolution of CO2 in this IL resulted in a reduced viscosity groups was a good tactic for improving CO2 absorption. reported that introducing a butyl ester group in pyridinium based ILs [b2-Nic][Tf2N] led to a negligible influence on the CO2 Wang et al. demonstrating that both chemical and physical absorptions took place.[84] and a superbase was confirmed by NMR spectroscopy.[93] This behavior could be attributed to capable of dissolving the same amount of CO 2 as their alkyl the undesirable entropic contribution to the Gibbs energy of functionalized analogues [C4MIM][Tf2N]. meanwhile.[57] At high pressures. Ecoeng 500® are not environmentally detrimental. These ILs were decreased CO2 solubility.ChemSusChem 10. [b2-Nic][Tf2N] functionalized IL and superbase to achieve a rapid and exhibited a slightly higher CO2 solubility due to the secondary reversibly chemical absorption of CO2 at the ambient interactions between the cation and CO2 molecules. It should be mentioned that the ions in was higher than [C2MIM]+-based ILs containing the same anions.g. All this could improve the CO2 absorption capacity. The CO2 and [C4MIM][BF4]/MEA). Ecoeng introducing hydroxyl groups in the imidazolium cations. the solvation. . the oxygen of ether could interact with the Hydroxylation: carbon atom of CO2. and the highest Waals complex due to the reaction of ether oxygen atoms as the capacity was exhibited by the IL with THEAL (tri-(2-hydroxy Lewis-base with the carbon atoms of CO2 as the Lewis acid.[57] The performance of Ecoeng 500® was measured the CO2 solubility in [heMIM]+-based ILs with different similar to that of [C6MIM][Tf2N]. introduced an equimolar (1:1) mixture of an alcohol solubility at low pressures. 1-(2. proposed analogues. ether functionalized alkyl sulfate anion did not give rise to a very Yuan et al. [TfO]). BEMP or [C2MMIM][Tf2N]. amine solutions. system which exhibited a lower CO2 solubility than the 75% higher selectivity than their alkyl functionalized conventional IL of [C2MIM][BF4]. flexibility of the alkyl chain. [Tf2N]. and it could be almost one mol CO2 per mol of superbase.[86] Due to the presence of much lower CO2 solubility. In both cases ([C3OHMIM][BF4]/MEA reacted with one mol of CO2 to form a carbamic acid. For example. The CO2 absorption capacity was did not provide a good performance as expected.[89] The system consisted of [heMIM][Tf2N] or similar behavior was reported for [C2MIM][Tf2N] and [Nip. [57] In absorption capacity in the studied systems followed the trend: contrast.1002/cssc. 83] Muldoon Alcoholation: et al. hydroxyl-functionalized ILs (hydroxylammonium) is higher than Ether functionalization of ILs led to the formation of 1:1 van der [C2MIM][EtSO4] but lower than [C4MIM][PF6]. To illustrate the influence of ether groups. the CO2 Jalili’s group synthesized hydroxyl-functionalized ILs by solubility in two ILs with ether groups (Ecoeng 500.[90.04 (CO2:DBU) was reached. In addition. They 41M) was studied.[85] ethyl)-ammonium lactate) species. and the absorbed attributed to the change of the electronegativity for oxygen atom CO2 could be released by bubbling of an inert gas or mild directly attached to the pyridinium cation.[48] The cation functionalization with ester groups EtP2(dma) as the superbase. revealed that introducing ester functional and DBU. the absorption took place very quickly absorption capacity of the studied ILs followed the trend: BF 4 < and resulted in almost 0. The ether groups increased the exothermic and resulted in a rapid uptake of CO2.378 mol CO2/mol MEA. The CO2 thereby facilitating faster sorption rates under good mixing. Ecoeng 41M which contained C4MIM cation paired with [heMIM][Tf2N] > [heMIM][TfO] > [heMIM][PF6] > [heMIM][BF4].0 mol per mol of DBU). The results of Deng and coworkers polar ether linkages.

[57] protonated. and the presence of a minimum in GE at around 33 advantage of the carbonyl in interaction with CO 2. These ILs showed a large negative further increase in CO2 solubility was observed. effect of fluorine was observed by comparing the results with [C2MIM][Ac].and the fluoroalkyl groups in [Tf2N]. the aldehyde carbonyl group was the most promising fluoroalkyl-functionalized ILs exhibited almost 10% increase one with a high CO2 absorption capacity. These ILs exhibited solubility in [SAC]. proposed that fluorinated aromatic rings provide a introduced hydroxyl functionalized phenolic-based IL. Yokozeki et al. Carbonyl groups are known as one of the promising CO 2-philic 2. implied that the heat of mixing HE was more negative than that This is because the electronegative fluorine atoms reduced the of TSE.ChemSusChem 10. confirmed that the replacement of three fluorine atoms with C(CH3)3 and CH2CH2C=OCH3) also showed a powerful influence fluoroethyl groups significantly increased the CO 2 solubility. They also examined the fluorinated carboxylate anions and thermodynamic excess functions.g. Combined mol% suggested the formation of 1:2 (CO2:IL) complex. .[82.on the absorption (chemically absorbing) with [C2MIM][TFA] (physically capacity was also studied. the long branched alkyl chain as well as bonding interaction itself is weak. This behavior was also explained with 2). 83] Meanwhile.[32. By on the formation of complexes with CO2. evaluated the solubility of CO2 in ILs. The results indicated that even absorbing). spectroscopy and cyclic voltammetry. CH3. Introducing promising candidates among fluorinate anions. Anion functionalization groups and could interact with the acidic carbon of CO2 through the free electrons on the oxygen atoms. the negative values of GE observed a lower CO2 solubility in [C4MIM][TFA] as expected. one with other studies. high stability. 1-(2. For example.imidazolium phenoxide.24 mol CO2 per mol of ILs. the addition of acetate group was expected to be an efficient fluorination and introducing other CO2-philic groups to enhance method to improve the CO2 solubility.2. compared the CO2 solubility in [C2MIM][Ac] be strengthened. The research showed that the stability and absorption capacity of the hydroxylated IL/MEA CO2 solubility in [C2MIM][Ac] was reduced when a methyl group system and prevented the precipitation of carbamate salts. the effect of Cl . and the strength of this the low toxicity render the docusate anion as one of the interaction affects the CO2 absorption capacity.15 K as can be seen in Table took place.[96] absorption capacities for [P66614][4-CHO-PhO] and [P66614][PhO] Similar to [Tf2N]-. CH3CH2.1002/cssc. a strong chemical absorption.[75] The CO2 solubility in [N4444][doc] absorption capacities up to 1.g. Therefore. positive effect on the CO2 solubility. i.increased the thermal physical and chemical absorption. the capacity could be and carbonyl groups were not enough to increase the CO 2 increased to 1. When the amine was played an important role to enhance the dissolution of CO 2.[95] In addition.e.201600987 REVIEW solutions via hydrogen bonding.01 and 0. [C4MIM][PRO]. The in the acetate anion was replaced with a fluorinated methyl hydrogen bonding and electrostatic attraction forces between Cl . proposed by Ding et al. the anions [SAC].5 molar CO2 absorption under ambient enhance the CO2 affinity. reported that studied.and [ACE]. deviation from Raoult’s law.2.contain sulfonyl could be 1. and it is has never been used to design the functionalized ILs in order to capable of 1. thus resulting in a increasing the length of the fluoroalkyl chain on the anion.[99] The developed ILs exhibited extremely high decrease of CO2-philicity.02 MPa at 298.or [ACE]. which was confirmed by anion by decreasing the electron density. to develop ILs via the non-covalent and further increasing the number of fluorine atoms led to a interaction. The C-H···O hydrogen carbonyl functionality.ions with Cl. i. nevertheless. The positive observed in the ILs with [X-COO]. several Fluorination: studies have shown that the oxygen atoms of CO2 could interact with the acidic hydrogens on the methyl group of acetate. As can the case that the ILs contained carbonyl groups with stronger be seen from Table 2. but unfortunately. CH(CH3)2.3-dimethyl.with CF3-COO-). [C4MIM][IBS]. therefore justifying the assumption the highest value was reported for [C5MIM][bFAP] by physical that both chemical absorption and chemical complex formation absorption (kH= 2. In and carbonyl groups neighboring to the nitrogen atom. such as [C4MIM][Ac]. 98] conditions. the interaction between halide ion and amines could Shiflett et al.[97] The mixture of two ILs showed a combination of partially replacing BF4. [C4MIM][TMA] and those in [C6MIM][PF6] (it was shown in Table 2). group (replacing CH3-COO.e. respectively.81 mol CO2 per mol of IL. The plausible and protonated amine (MEAH+) or cation (C3OHMIM+) resulted reason is that the CF3 group weakened the Lewis basicity of the in the advantages mentioned above. Among the carbonyl groups fluoroalkyl group. the phenolic ILs are cheap and thus can be practical compounds with improved absorption capacity Carbonylation: almost up to 1 mol CO2/mol IL. [P66614][4-CHO-Im]). For example.[74] and Muldoon and coworkers investigated the effect of anion. Bara et al.24 mol CO2 per mol of IL and great was reported as high as in the case of [C6MIM][eFAP] that is one reversibility because of the Lewis acid-base and cooperative C- of the best performings fluorinated ILs reported until today. Vafaeezadeh et al. it was concluded that there was an optimal CO2 molecule was sandwiched by two ILs. this idea hydroxyethyl)-2. All rights reserved. they compared the CO2 solubility in CO2 solubility with a strong chemical absorption was only [C6MIM][eFAP]. the CO 2 in CO2 capture over their analogues. [57] The results carbonyl groups to the anion strengthened the C-H···O indicated that the CO2 solubility increased by introducing hydrogen bonding interaction. Besnard et al.[57] To investigate the influence of the CO2 solubility in 18 different ILs and reported that the high fluorinating anions. The H···O hydrogen bonding interaction.[54] This [C4MIM][LEV]. it was clear that the introducing sulfonyl basicity (e. Therefore. A new strategy was number of fluorine atoms to reach the maximum CO2-philicity. [C6MIM][pFAP] and [C5MIM][bFAP]. the electron-withdrawing nature of the This article is protected by copyright.[62] The X group (e.

especially in the case of alanine as the anion. introducing an amine to the cation of ILs favors the dialkylimidazolium acetate ILs using X-ray diffraction and NMR formation of the carbamate. phenol or fluorinated [N2222][L-Ala] exhibited lower viscosities than amino acids and alcohols directly. The superbase played the decisive role reactivity of amino acids in terms of CO2 capture. charge center and amine were close enough to each other. they were more the capacities higher than 0. NMR spectroscopy functionalized ILs exhibited higher CO2 absorption capacities and DFT calculations demonstrated that CO2 reacted with than cation-functionalized ILs. thus reflecting the instability of the acetate-based ILs was proved using ab initio calculations and product di-anion. the carboxylate was observed using NMR spectroscopy. For solvents for CO2 uptake. FTIR spectrum of [P66614][Pro]. and attaching the absorption solvents or designing novel amino acid-based carbonyl group to anion was more efficient than to cation. functionalized the anion with amine groups. The influence was most noticeable when the high resolution spectroscopy. As well. However. In addition. After 24 hours characterized by FTIR spectroscopy at 298 K.5 mol CO2 per mol of ILs at low tolerant to oxidative degradation and less toxic than common pressures (below 1 bar). the stoichiometry of the reaction could be increased from [C4MIM][Ac] and [C4MIM][TFA] with CO2.[109] ILs with a capacity of 0. The chemical absorption of CO2 alkanol amine solvents. contrast.06 mol per mol of IL. and availability. and the presence of water can decrease the viscosity as well as equipped with chiral centers. [111] They viscosity. Decreasing the number of hydrogen should point out that these ILs are high-quality functional atoms on anion available for hydrogen bonding can reduce the solvents. [105. Specifically. and the deprotonated basic form was different superbase-derived PILs on the absorption of CO2.[100] An acid-base type of solvation mechanism in formation of carbamic acid. They used very strong superbases to deprotonate weak proton proposed that the amino acid functionalized ILs composed of donors of imidazole. their significantly.13 (mol CO 2 per mol PIL) and [MTBDH+]2 This article is protected by copyright. before reaction with CO2. For example. by introducing amine functional group to the Carvalho et al. so preventing 1:1. On the basis of the calculations. According to the 13CNMR results. studied the reaction of glycine with CO2 and provided and reversibly capture CO2 with high capacity (more than 1 insight into how functional groups could affect the amine mol per mol of ILs). Jiang et al. moreover. they are biodegradable and biocompatible viscosity. especially the at atmospheric pressure. the studied ILs weak proton donors are available. confirmed the chemically absorption of CO2 in 1.[101] observed. This information was Most of the studied PILs showed high absorption capacity valuable for determining the operation conditions. and the location of the functional [C4MIM][Ac] to form an imidazolium carboxylate and acetic acid groups (anion or cation) was another important factor upon the via the deprotonation of the C2 of the imidazolium ring.[108] In aqueous upon the formation of reactive PILs as strong proton media.3. introduced an efficient system for CO2 capture the tetraethylammonium cations resulted in solvents with lower based on anion functionalized protic ILs (PILs). ray diffraction analysis exhibited that imidazolium carboxylate The peak disappeared after reaction with CO2. exhibited low melting points and were capable of rapidly Guo et al. The properties of PILs could be easily contributed to a high CO2 absorption potential (0. They realized that. [102] design of functionalized ILs for specific applications. 104] Amino acids were used to resulted in an increase in viscosity due to the formation of a functionalize common ILs in either anion or cation. peak at 3290 cm-1 was assigned to [prolinate] N-H stretch bond. also using Raman. Goodrich et al. high Amino acids exhibited potential benefits over amines due to their thermal stability.5 mol per mol adjusted because a variety of organic superbases and of IL). Indeed the N-H bending was decreased after reacting with CO2. . neutral or acceptors. All rights reserved. The studied PILs chemically reacted with CO2.[100] The results one CO2 for every two amine molecules (1:2) to one for each revealed that CO2 solubility in [C4MIM][Ac] due to the differences amine molecule (1:1).[101] They examined the reactivity of CO2 with stability of the zwitterion product is favored. the formation of 1-ethyl-3-methylimidazolium-2. amino acids can exist as protonated. The 1:1 [C2MIM][Ac] by bubbling CO2 through the acetate-based IL at stoichiometry of the reaction of CO2 with the studied ILs was atmospheric and ambient temperature conditions.[110] All the studied ILs exhibited considerably lower vapor pressure. also investigated the performance of deprotonated basic form. X. [MTBDH +][TFE-] pH of the medium in the case of employing amino acid as liquid resulted in 1. pyrrolidinone. infrared. synthesized low-viscosity amino acid ILs (AAILs) using Protic ILs: symmetric tetra alkyl ammonium species as the cation precursors and amino acids as the anions.[107] They found that Wang et al. in the bubbling.1002/cssc. Wang et al. comparison. investigated the specific interactions of anion. the ammonium formation was the CO2 reaction. more reactive than the neutral form. in enthalpies of solvation was spontaneous unlike in introducing an amine group to the anion of ILs favored the [C4MIM][TFA]. while in the case of 1:2. No water was shown to inhibit the interaction of acetate with the evidence confirmed the formation of ammonium in the case of proton at the C2 position of the imidazolium ring. The intensity of and acetic acid were formed in the absence of water. indicating that the electrostatic spectroscopy. In Gurau et al. 106] One hydrogen bond network.[103.201600987 REVIEW carbonyl group resulted in a great reversibility. introduced new amine-functionalized anion- Amination: tethered ILs as CO2 absorbents with the trihexyl (tetradecyl)phosphonium cation (P66614) due to its low price. Their results also revealed that the anion- Besnard et al.ChemSusChem 10. viscosities are high and thus limit their applications. the carbonyl group to cation can only give rise to Gurkan et al.

The CO2 solubility in [P2222][BnIm] reached anions. triazolide. NMR and IR spectroscopy. the synthesis of an IL did not require.[116] However. the IL became a liquid by introducing CO2 into the reaction cell. The studied PCILs exhibited absorption process was attributed to the low viscosity of the the following trend in CO2 solubility: [P4444][BnIm] > [P4444][6- PILs (e. They are capable of reversibly and one mol of CO2 to form stable carbamate ions through Lewis stoichiometrically reacting (one mol CO2 per mol of salt) with acid-base interactions.[117] For phenolate ILs. The generated heat during the phase decrease the CO2 molar capacity due to reprotonation of the transition was used to reduce the parasitic power consumption. imidazolide. and the sample initially formed a slurry at Wang and coworkers developed a new anion-functionalized IL low pressures (˂ 0. AHAs. an equimolar absorption process could be pure [P2222][BnIm] as dry solid.85 mPa·s BrBnIm] > [P4444][2-CNPyr] > [P4444][3-CF3Pyra].[113. Thus.[112] Indeed. the increase of the [P2222][BnIm] was the most promising candidate in the CO2 viscosity was not observed upon the functionalization and the capture.[30] At 333 K. synthesized a family of ILs containing the alkyl- of CO2. This derivatives and phosphonium cations.[114] The formation of viscous or solid like gels. and the phase was changed from solid to liquid during the studied. the Seo et al.1002/cssc. the water effect was further CO2. phosphonium salt as cations and AHAs as anions was studied. no capacity reduction The melting point of the complex formed with CO2 (PCIL-CO2) was observed at all. Among the studied PCILs. at 343 K by using a vacuum and the sample was fully back to consequently. the absorption capacity increased from at high temperatures due to the exothermic nature of the CO 2 0.95 mol CO2 per mol of IL by increasing the pKa of the absorption reaction. At 323 K and below. highly stable. the reaction between IL and CO2. the IL did not fully liquidize but could dissolve a considerable amount of CO 2.[120] This class of ILs can This article is protected by copyright. and the melting point could be tuned by changing the react with acid gas to form an IL or IL-like product in situ. these CO2 saturated ILs remain liquid. each mol of IL was capable of binding chemical reaction. increased with the addition of water.201600987 REVIEW [HFPD2-] showed even higher capacity (2 mol per mol PIL) indicated a considerable difference between the melting point of due to the presence of two reactive groups. by using chemistries. out at various temperatures. The anions in the studied ILs are PCILs are attributed to salts that are solid at temperatures 313. In addition.[118.1 bar). By alkyl chain length of the corresponding phosphonium salt. 115] viscosity of [P66614][Im] was even decreased with the dissolution Seo et al.9 to 13. while the CO2 solubility was slightly was below that of the pure PCIL. these basic ILs results revealed that cations had just minor effect on absorption. the enthalpy of reaction with CO2 could be easily starting with one or more neutral organic molecules that can adjusted. as well as carbamate or phenolate salts.[30] In fact. composed of a tertiary amine that is associated with a 353 K and have a high CO2 absorption capacity due to the heterocyclic ring. e. the viscosity was increased considerably and resulted in the pyrazolide. indicating the fully reversibility of demonstrated by tuning the pKa values of the anion in basic ILs. anion.[114] were formed as characterized by NMR and IR The CO2 solubility measurements in [P2222][BnIm] were carried spectroscopy. By increasing the pressure (almost that is capable of reversible. ILs. After cooling down to ambient on substituted cyclic and acyclic guanidine or amidine temperature.ChemSusChem 10. tuning the chemical structures of these molecules the physical. The CO2 solubility in four different PCILs composed of tetrabutyl chemical or thermodynamic properties such as viscosity. they affected the physical properties of AHA ILs like viscosity. heat of absorption can be controlled. rapid.1 MPa. AHA ILs are Reversible ILs were considered as an alternative and highly promising candidates as efficient and environmental-friendly promising material that exhibited tunable properties and absorbents in post-combustion CO2 capture. 119] (AHAs). In fact. for [P66614][2-CNPyr]. The AHA-derived ILs remain liquid under ambient conditions due Phase-change ionic liquids (PCILs): to the presence of bulky and unsymmetrical alkyl chains coupled to the phosphonium groups. investigated the CO2 solubility in PCILs based on tetra CO2 absorption capacity increased due to the formation of butyl phosphonium salts with aprotic heterocyclic anions bicarbonate with the addition of water. As mentioned in the former text. energy-saving above 0. Basic ILs: At 333 K and over.9 in DMSO (Dimethyl sulfoxide) and. . During the reaction of CO 2 with PILs.g. but it reduced slightly absorption capacity. Taking these advantages into consideration.g. and indazolide). 8. a carbamate that the PCILs were more energy-efficient candidates than the or carbonate salt was formed based on the observations from aqueous amine solutions. This order was for [MTBDH+][Im-]). Therefore. for amine-functionalized phosphonium cation with AHA-based anions (pyrrolide. their viscosities do not increase upon the reaction with CO2 and they can bind with CO2 in the Reversible ILs: range of reaction enthalpies that are suitable for gas separation.17 to 0. Furthermore. are promising in CO2 separation. as reported earlier. Hence. It was expected that the water in solutions would reaction with CO2.15 bar). CO2 was fully desorbed from [P2222][BnIm] anion from 11.[113] For these AHAs. the basicity of the ILs influenced the to 1 mol CO2 per IL at 333 K and 0. it could be concluded During the absorption process with these basic ILs. compatible with the decreasing enthalpies of anion-CO2 reaction liquid carbonates. All rights reserved. also. these ILs were solid.63 mPa·s for [MTBDH+][TFE-] and 31. stability. but they transformed to liquid Reversible ILs are considered as a special group of ILs based quickly upon reaction with CO2. most of the sample transformed to liquid and and equimolar chemisorption of CO2 due to the reactivity of the saturated with CO2. The rapid pure PCIL and PCIL-CO2 complex.

[121] They showed that introducing CO2 into a nonionic guanidine derivatives 1.ChemSusChem 10. alkanolguanidines and diamines reacted with imidazolium cation and taurine anioin [aeMMIM][Tau] that was CO2 to form reversible ILs.. the main drawback was on unstable carbonate was formed that could easily release CO 2. the al. the difficult recovery from the reaction mixture.[122] Heldebrant and coworkers studied the reaction of DBU (amidine) with CO2 in presence and absence of water.1.[131] Due to the high CO2 solubility. the absorption mechanism included the formation of carbamate as shown N + CO2 N + ROH O below in scheme 3. The studied IL was capable of rapid and Scheme 2. IL-IL or IL-small organic molecules mixtures around 50 °C. The was able to be reversed upon heating or sparging with nitrogen mechanism of reaction (scheme 3) was investigated by both to release CO2.3.9 mol per mol of IL at ambient chemisorption capacity was achieved. in longer substituents (n>4). It could be deduced that each primary amine group of the IL reacted with a [124] CO2 molecule. revealed that when Xue et al. .1002/cssc. for hydroxyalkyl guanidine which containing short hydroxyalkyl Double salt ionic liquids (DSILs) are considered as salts which substituents (n<3). DSILs have gained more interest to use as liquid sorbents. NMR and FTIR spectroscopy verified a chemical to the alcohol on alkanolamidines and alkanolguanidines as process.[129] Two-component According to the spectroscopic analysis.2. Cyclic time.0]dec-5-ene (TBD) liquid like alcohol or amine resulted in the formation a salt (IL) and its methyl analogue (MTBD) can be used as cation which can be converted to its nonionic initial state by exposing it precursors of reversible ILs. The studies of Heldebrant et al. Chatel et al. an due to their strong basicity.[125] Therefore. The R2 R2 R R3 . Schemes for one. 126] As reported by Hildebrant et al. In both systems.CO2 C OR (Z) N N O O H O H2N N NH2 + CO2 H2N N N N N H H N N + CO2 O + ROH C OR Scheme 3. The This article is protected by copyright.[120] chemisorption of CO2 since 1.3-tetramethylguanidine-alcohol mixtures can be used as one strategy was to convert these superbases into IL.3-di(2′-aminoethylene)-2-methylimidazolium molecular liquids reacted with CO2 at 1 atm to form ILs which bromide) was bound with two primary amine groups.CO2 R3 R3 2 O results indicated a value around 1. Dual functionalization of ILs solvents.3. reversible IL generated from silylated amines. reversible IL systems mol CO2 per mol IL for both [aP4443][Gly] and [aP4443][Ala]. Instead of a stable cyclic carbonate. Additionally. the CO2 addition product easily cyclized to stable form at low temperatures (lower than 373 K).[124] FTIR and NMR spectroscopy before and after CO2 exposure.[125] CO2 chemically bound pressure.3. CO2 absorption mechanism with dual amino-functionalized IL N N N N . a considerably better CO2 capable of absorbing CO2 up to 0.4. DSILs are in liquid Therefore. where [AA] is represented by the natural amino water but no reaction was observed in the absence of water. All the mentioned reversible ILs can be reverted to their non-ionic forms by thermally stripping CO2 at temperatures 2.2.CO2 O [129] (adapted with permission) One-component + CO2 H Two amine groups bind to the cation and thus the maximum R1 R1 R 2 Si NH2 Si NH3 + O N Si 1 absorption capacity can reach 1 mol of CO2 per mol of IL. [123] acids. However.5-triazabicyclo[4.[125.05 mol CO2 per mol of IL that was close to the theoretical absorption capacity.[125] composed of more than two types of ions. recently reviewed product easily cyclized to stable carbonate and did not release the physical properties. the cation (1. All rights reserved.[128] component.4. Cyclic guanidinium In contrast.201600987 REVIEW also be described as organosuperbase ILs. reported a series of dual amino-functionalized ILs Their spectroscopic results revealed that an IL [DBUH]+[HCO3].. the synthesized IL could be recycled zwitterionic alkylcarbonates while on diamines as zwitterionic under vacuum or at a higher temperature. thermal behavior. synthesized dual amino IL with amino functionalized alkanolamidines. the CO2 addition can act as a single set of ions. the chemically bound CO2 even by heating to around 100 °C. .[124] For the dual amino-functionalized ILs investigated by Zhang et Scheme 2 depicted the mentioned systems. and they can carbonate and did not release the chemically bound CO 2 even exhibit unique glass transition temperature and melting point or by heating around 100 °C. this kind of ILs could be used in the reversible uptake of CO2. The chemical absorption capacities of CO 2 were almost 1 Blasucci et al. the chemisorption of and amidinium derivatives were widely used as basic catalysts CO2 was reversible.3.1.[127] to an inert gas. and based on amidines or guanidines and alcohols as well as one. 1.[121] Since the polarity of these solvents can be tuned upon reaction with CO2 they considered as switchable 2. which was more industrially feasible and practical alternative for the helpful in recycling the salt. To cope with this. described two-component.3-tetramethylguanidine was This approach was introduced by Jessop et al. for the first easily available and manufactured on an industrial scale. based on (3-aminopropyl) tributyl phosphonium amino acid salts was formed via the reaction of DBU and CO2 in the presence of ([aP4443][AA]).and two-component reversible ILs reversible absorption of CO2. solvent properties.[125] and applications of DSILs. the chemisorption of CO2 was irreversible. [123] Zhang et al.[130] carbamates.

[133] The CO2 solubility increased by increasing the released by increasing the temperature or decreasing the content of [C2MIM][Tf2N]. indicated that the solubility in all IL mixtures increased with due to the acidity of hydrogen at the C2 position.4 and the mixed system exhibited an effective regeneration performance.[137] a plausible compromise.[136] They used a mixture of [C6MIM][Tf2N] with monoethanol amine and (b) hydroxyl-terminated IL [140] with diethanolamine imidazolium-based ILs mixed with an aqueous solution of a non- ionic surfactant.[141] The good performance was from the large free This article is protected by copyright.[139] For imidazolium-based ILs. thus rendering this system fascinating as a new kind to their high CO2 absorption capacity and low viscosity. less toxic and non-fluorinated IL could be easily regenerated by introducing N2 through the solution. All rights reserved.1002/cssc.25 mol CO 2 per mol of however. introduced a new kind of CO2 absorbent Scheme 4. Wang et al. IL-amine combination used for CO 2 capture. Wang et al. Low viscosity and low cost of the sorption media Triethylbutylammonium acetate and its water complexes together with low IL consumption and good reproducibility were ([N2224][CH3COO]-H2O) are fascinating as CO2 absorbents due achieved. and The results illustrated that both chemical and physical thus the absorption capacity increased by increasing the content absorptions occurred in this solution.798 mol/L CO2 at ambient temperature and low pressure (0. Mixing with [Choline][Pro]/PEG200 could capture CO2 efficiently and be this IL with a cheaper. studied the CO2 strong interaction between the basic groups in [Choline][Pro] absorption in a mixture of [C2MIM][Tf2N] and a non-fluorinated and CO2. The best result fluoroalkyl group and long alkyl chain length was chosen to was obtained with 30%wt MEA + 40%wt [C4MIM][BF4] + 30%wt achieve high CO2 solubility. and the viscosity of this mixture was close to the viscosity or [C4MIM][BF4] because of the high selectivity. they were not increasing pressure and decreasing temperature. It was also observed that at high carboxylate salt. imidazolium cation with pyridinium.[131] 0. giving the possibility to maintain almost The gas was mainly absorbed by [Choline][Pro] due to a very the same CO2 absorption capacity. However. The selectivity for CO2 with respect to CH4 and N2 corrosion of the equipment. Almost the same behavior was observed for Camper and coworkers used a mixed solution of a room the binary mixtures of imidazolium-based ILs such as temperature IL and an alkanol amine the IL-amine combinations [C2MIM][Tf2N]+[C2MIM][EtSO4] and [C2MIM][Tf2N]+[C4MIM] are shown in Scheme 4. [132] The Henry’s constant improving the kinetics of absorption and desorption of the CO 2. demonstrated one of the highest physical absorption capacities Li et al. . took increased with increasing the amount of [C8MIM][Tf2N]. thus balance of the preferred properties.[135] Recently. Zhang et al. which was capable to capture to the nature of ions.[135] The best performance achieved when the mole F3C S N S CF3 O O (b) O O (a) fraction of [NH2e-mim][BF4] was 0. and the other IL was [C2MIM][BF4] H2O. The IL [C2MIM][Tf2N] has performance to alkanolamine solutions. and the advantage of the inherent acidity of imidazolium cations and Henry’s Law constant at the same content of [C8MIM][Tf2N] mixed with an organic superbase for CO2 capture at atmospheric followed the trend of: [C8MIM][Tf2N]+[C4MIM][BF4] > pressure. The solubility completely inert under most conditions. By increasing the amount of PEG200. and by replacing the Functional ILs have great potential to apply as CO2 absorbent. only 0. Increasing the IL concentration led in pure [C2MIM][BF4] was improved by the addition of 5 mol% to an increase in viscosity of the solution and a decrease in the [C2MIM][Tf2N].[134] Their results revealed that the solubilities of behaved similarly to aqueous amine solution but offered the CO2 and CH4 decreased with increasing the concentration of advantages of increased energy efficiency and diminished [C2MIM][BF4]. energy consumption for the solvent regeneration.[138] The absorbed CO2 could be [EtSO4]. their high viscosity considerably influence CO2 IL could be captured. improved the CO2 capture capability. Wang of absorbent for CO2. (a) with high efficiency and low cost.ChemSusChem 10. low vapor pressure and Finotello et al.[66] The [C8MIM][Tf2N] with a than in the case of aqueous amine solutions. high CO2 solubility. the CO2 pyridinium-based IL [C2py][EtSO4] in order to find an optimal solubility decreased. The pressures the mixed ILs provided the probability of adjusting the results indicated that the C2 proton of an imidazolium cation selectivity and solubility for physical absorption of CO2. improved the performance of H H2N N amine functionalized imidazolium-based IL [NH2e-mim][BF4] by N N OH HO OH N N OH mixing with low viscosity conventional ILs [C2MIM][BF4]/ O O O O F3C S N S CF3 [C4MIM][BF4]. This mixture combined the advantages of ILs such as was not higher than that of the pure fluorinated ILs. but the viscosity was also decreased. This renders the solvent system equivalent in terms of the and solubility upon capturing CO2. absorption process. The results of a traditional amine solution. studied the solubility and selectivity of the binary high thermal stability with those of low viscosity and fast capture mixtures of ILs with imidazolium cations ([C2MIM][Tf2N] and performance of alkanol amines. and equimolar CO2 capture was attained. and Lei and coworkers examined the CO2 solubility in binary particularly.6 Using DSILs provides the opportunity to adjust the selectivity MPa). the capacity of the mixtures pressure. but it of ILs. Pinto et al.[127] The superbase reacted with CO2 to form [C8MIM][Tf2N]+[C2MIM][BF4]. of the fluorinated IL. The best result was shown in [8% Tween 80 (surfactant) is possible to adjust physical properties and solubility according + 10% [C2MIM][TfO] + water]. This IL-alkanolamine solution [C2MIM][BF4]). low heat capacity.201600987 REVIEW CO2 solubility in DSILs is lower than the corresponding ILs. The results indicated that the absorption and coworkers used these solutions for reversible CO 2 capacity increased with increasing pressure and concentration absorption. reported that both the pure [Choline][Pro] and its mixture for CO2 although it is to some extent toxic and expensive. decreased as the molar ratio of [C2MIM][Tf2N] increased. the amine loss per ton of CO2 was remarkably lower mixtures of imidazolium-based ILs.

a new generation of green solvents.75 molar fraction) [C2MIM][Ac] + (0. This quaternary ammonium salt confirmed by NMR and FTIR spectroscopy. non-toxicity. amines and metal salts can be used as freezing point of the mixture can be as low as 285 K. 146] less energy to break the bonds then caused to a depression in The first generation of DESs has been based on the mixture of the freezing point. the absorption capacity for the mixture design a task-specific DES.1002/cssc. biocompatible. carboxylic form an eutectic being a liquid at room temperature. [27. The CO2 absorption in [C2MIM][Ac] (chemically absorbed CO2) DESs can be designed by combining different components. In this section. Once the mixing with a common HBD. In addition. containing (0. For example. restrict their industrial applications. DESs which common ILs since they can be prepared simply with high-purity are constituted of larger ions with smaller charges are needed and low-cost on a large-scale. and their a combination of chemical and physical absorptions took place physicochemical properties have been reported. recyclability. Consequently.[144] Eutectic mixtures are composed of at least two solid DESs were obtained by mixing two components with an components and the freezing point of the mixture is lower than appropriate molar ratio to form an eutectic solution with a the freezing points of the individual components. the combination of water molecules with acetate anion 3. formyl. how the CO2 absorption depends on the Generally. we discussed the factors that affect the physicochemical properties 3. density. thiol and carboxyl are capable of forming DES upon The chemical reaction proceeded to equilibrium. bicarbonate. All rights reserved. 154. reacting CO2 with IL.[89] properties. non-toxic and low freezing point. and how the properties are affected will be essential to and CO2. Therefore. Meanwhile. 153] van der Waals forces. energy of salt and HBD as well as the entropy changes volatility. liquid phase in DESs is controlled by the freezing point of ionic low-price. Many DESs have been synthesized. DESs are considered as economical alternatives to occurring upon formation of a liquid. The depression melting point lower than each individual component.[147-151] Low-cost and environmental for ChCl and 406 K for urea). It is clear that by increasing the amount of water. the absorption process was then of the resulting DES can be altered by changing the HBD or controlled by the physical mechanism via hydrogen bonding or modifying the relative ratios of ChCl/HBD. have been developed. the halide salts with a low freezing be considerably changed by altering HBD. Deep Eutectic Solvents (DESs) of DESs such as freezing point. and acetic acid were formed.201600987 REVIEW volume and basicity of the triethylbutylammonium cation and 2-hydroxy-N.[156] quaternary ammonium or phosphonium salts with hydrogen Amide functional groups exhibit a great ability to form hydrogen bond donors (HBD). it is possible to obtain task-specific and significantly lower than those of the constituents (mp are 575 K inexpensive eutectic ILs.[152. This noticeable depression of the compatibility are crucial factors in developing new solvents for freezing point was attributed to the interaction between the urea CO2 separation. and the physicochemical properties acetate anion lost its basicity.25 molar The application of DESs in CO2 separation requires sufficient fraction) [C2MIM][EtSO4] at higher pressures was almost the information about their thermodynamic. and eutectic-based IL analogues are thus more and chloride ions.N. ChCl and protic ammonium salts with hydroxyl. high thermal stability and non. hydrogen bond formation could also be used in the preparation This article is protected by copyright. composition. species. alcohols. recently Deep Eutectic Solvents Freezing point: (DESs).N-trimethylethanaminium chloride (choline acetate anion.[157] Other functional groups that are capable of promising than the conventional ILs.[143] In the binary mixture.ChemSusChem 10. Formation of a general. results along with the proposed mechanism indicated that by Meanwhile. physical. be prepared. or chemical same as that of pure [C2MIM][Ac]. proposed that the water molecules were connected DESs. pH value. In optimal for any eutectic mixture composition. . The main drawback was the low thermal stability. a mixture of ChCl and urea can biodegradable as well as a wide array of amides. Considering that point can form complexes with HBDs to achieve a DES with a quaternary salts are generally inexpensive. biodegradability. The properties of the resulting solvent can bonds with ChCl. These properties are influenced by the temperature.1.[142] The analytical can be produced as an important additive used in animal feed. viscosity and surface tension. non-flammability. and and [C2MIM][EtSO4] (physically absorbed CO2) and their binary task-specific DESs with specific physicochemical properties can mixtures was studied by Pinto’s group. with the acetate anion through hydrogen bond which was biodegradable and inexpensive. DESs exhibit desirable properties. and the acids.[145. All these problems adjusted were also reviewed. The process of IL well as how much CO2 absorption capacity in DESs can be synthesis is seldom environmentally friendly. the synthesis of ILs is complicated and requires a strength of inter-intramolecular interactions or the free volume as large amount of expensive raw materials. Choline chloride (ChCl) is non-toxic. 155] and the addition of [C2MIM][EtSO4] to [C2MIM][Ac] restricted the Physicochemical properties are determined by the structure of solidification due to the chemical reaction between [C 2MIM][Ac] DESs. Functional groups for adjusting the properties of DESs and the affinity between CO2 and acetate anion were decreased. such as availability. To cope with the high price and toxicity of common ILs. This is complexing agents. The of freezing point appears from the establishment of strong decrease in the freezing point of the resulting DES is related to intermolecular interactions between the HBD-HBA pairs and is the strength of interactions between the two components. and water content. chloride) is the most prevalent chemical used upon the design of Quinn et al. and freezing temperature is influenced by the lattice biocompatibility.

174] the viscosity of DESs acid > glutaric acid > levulinic acid).[165-168] Interestingly. for the volumetric factors are more effective than interactions between a tetraalkylammonium bromide. Meanwhile. the viscosity of DESs is related to the temperature.[162]According to the hole theory. For example. the distribution of the hole sizes is length of the cation resulted in decreasing density.[147. hole radius or free volume increases with increasing the chain levulinic acid) resulted in increased viscosity.[35. This is Viscosity: because the high temperature increases the kinetic energy and reduces the cohesion forces between molecules. their density increases with increasing the number of minimal. The viscosities of DESs are generally high compared to other therefore weakening the interactions among the solvent organic solvents and thus give rise to problems in applications. glutaric acid.[176] viscosity of water saturated ChCl-oxalic acid system at 293. the ammonium-based DESs is lower than that of phosphonium. and the density of the DESs with o-cresol is Surface tension is one of the most important properties that lower than those with phenol. All rights reserved.g. the type of HBDs. components. 165-168. thus leading to increase viscosity. o-cresol) also decreases the density of DESs.5-pentandiol. [164] dependent on the HBD and salt type. for ChCl-phenol. 170] Increasing the alkyl chain length of salt also leads to an increase The temperature dependency of viscosity can be explained in surface tension. This may attribute to the smaller influence the mass transfer. whilst for ChCl-glucose and ChCl-sorbitol. By tension. activation energy indicated it is more difficult for the ions to move In addition. the density of However. . the ChCl and carboxylic acids with those of cholinium-based ILs density decreases with increasing chain length of HBDs.[163. the increase in the alkyl chain salt and a HBD. a comparison of the viscosity of DESs based on pentandiol presented the lowest density.[161] decreases with increasing chain length (oxalic acids > malonic Based on the hole theory. it is expected to follow the same trend as the type of salt. the introduction of an Surface tension: aromatic group in HBDs (phenol. the temperature molecules are smaller than o-cresol. and it appeared that The type of the salts in DESs has a strong effect on the density the water of hydration plays an important role in this case. A temperature increase leads to a decrease of surface tension.[173. the DES with the longest chain in 1. [170-172] The density of DESs relates to the functional groups and the A comparison of the viscosity of DESs containing carboxylic chain length. 158. [158] are low.3-propanediol. Moreover. 159] Moreover.201600987 REVIEW of eutectic mixtures with low freezing points. The surface tension of DESs is steric hindrances induced by phenol because the phenol sensitive to the nature of salt and HBD. [163] However. On the basis of this theory. [34] The freezing used to evaluate the strength of the intermolecular forces in the point depression of choline salts with urea exhibit the following DES as well as their connection with viscosity. which indicates the stronger hydrogen solvent are strongly affected by their viscosity.[160] Compared to conventional ILs. For example. glycerol additional hydrogen bonds.[175] viscosity of DESs hinders the mobility of any dissolved species. the surface The mass and heat transfer ability and the conductivity of tension of DESs is higher. the density (oxalic acids > glycolic acid).15 K).[163] and 1. the addition of corresponds to the holes available in the fluid which allows the number of carboxylic groups also leads to an increase in appropriate ionic motions.1002/cssc. oxalic hydroxyl groups. the addition of water to DES mixtures significantly decreases the density.ChemSusChem 10. the type of salt has a strong effect on surface was 200 times lower than the case of dried sample.[161] Therefore. The higher order: F-> NO3->Cl->BF4.[34] the average acid. their viscosities and activation energies permit two ChCl molecules to form hydrogen bonds.5. for the DESs containing dicarboxylic acids. 163] Therefore. For the DESs formed by HBDs with the hydroxyl acids showed that the influence of HBDs on viscosity was groups. ChCl and D-glucose mixtures also exhibit eutectic past each other. Interestingly. and the activation energies can be surface tension because it will lead to a weakened hydrogen This article is protected by copyright. the ChCl assists in breaking the intermolecular forces in glycerol. showed that the viscosity of these DESs was lower than those of Similarly. number of hydrogen bonds between ChCl and NiCl 2 increased based DESs with a fixed HBD such as ethylene glycol. 1. This is because length of HBD and leads to a decrease in density. and the high bonds formed between a salt and a HBD.15 K In general. intermolecular forces. [159-161] and resulted in an increase in viscosity. The involvement of water will decreased the surface tension of glycerol. decreased. Since surface tension is a measure of the strength of Principally. the viscosity of DESs a high surface tension due to their hydrogen bonding ability. This is because that significantly decrease the viscosity of DESs. the density ILs. and volumetric properties. Increasing the amount of salt decreases the using Arrhenius equation. For example. the existence of extra carboxylic or hydroxyl groups creates among the DESs of ethylene glycol. their viscosities and activation energies are high. by increasing the mole fraction of NiCl26H2O. ChCl-o-cresol and between hydroxyl groups and chloride anion is more desirable to ChCl-ethylene glycol. D-glucose contains 5 interactions between ions-HBDs have a key role in DES’s hydroxyl groups in a cyclic form and the angle of the interaction viscosity. the water content and the the viscosity.[169] and the molar ratio of a salt to a HBD. and the presence of hydroxyl groups in a salt resulted in increasing the amount of water. Density: The addition of NiCl26H2O to ChCl-urea mixture considerably reduced the viscosity of the resulting DES. the addition of 30 mol % ChCl molar ratio of salt:HBD. The presence of one extra carboxylic group (e. intermolecular point at 2:1 molar ratio (288. For example.g. Meanwhile. 158-160. glycolic acid) or a hydroxyl group (e.

5:1 resulted in the highest.2. Although that the CO2 solubility in DES decreased with an increase in the viscosity of DESs is generally high.g.14][C12H25PhSO3]). investigated the DES composed of ChCl solubility in DESs depends on pressure. Surface tensions of [C4MIM][Bu2PO4]. 2.5 MPa and 313. The CO2 solubility in a binary aqueous solution of reline (ChCl- for example. The CO2 solubility glycol. [C2MIM][BF4] or of molecules. . and 1:2. they plotted the enthalpy of the by mixing DES with common solvents.[189] The results indicated CO2 separation due to their unique characteristics. Generally. studied the solubility of CO2 in the DESs composed corresponding ethylene glycol DESs.201600987 REVIEW bond network whereupon the dissociated cations and anions capacity of ChCl-urea is higher than ChCl-glycerol and ChCl- occupy the free spaces between HBD molecules and weaken ethylene glycol. the CO 2 Recently. DESs have gained great interests in reline (ChCl-urea 1:2)/water solution.[165] The investigated systems included ChCl as ChCl and urea (1:2). 64.[172] in these DESs was similar to those in ammonium-based ILs For the DESs based on ChCl and D-glucose. Meanwhile.g. [bheal]. the corrosion was greatly reduced (0.15 K with different DES compositions Leron et al.[183] glycerol-based DESs exhibited higher surface tensions than Chen et al.[147] Abbott et al.[180] The CO2 solubility in the DES was ammonium salt and ethylene glycol. investigated the DES composed of ChCl and urea year). These results were very useful that the addition of glycerol as the second HBD to the DES when attempting to develop new technologies for CO2 composed of ChCl-sugar based polyols resulted in a separation. the decreased remarkably.[50.[160] Similarly. the viscosity of ChCl:glucose:glycerol urea 1:2) (50. almost all ChCl- 3. CO2 capture using DESs based DESs contain at least a small amount of water.[176] Similarly. All rights reserved. reported that by adding Above this mole fraction (at high water content). [C4MIM][Tf2N] these DESs were higher compared to ILs such as [C4MIM][BF4] or [P6. [C4MIM][PF6].5:0.1002/cssc.5. and none of the measurements indicated ChCl-based DESs: that chemical absorption of CO2 would have occurred. it can be overcome water content.3 mmol of CO2 per gram of DES at 293.6. the absorption ChCl to glycerol. 181] The CO2 absorption acid as the alternative HBDs.3-butanediol glycerol with ethylene glycol as the HBD in the K 2CO3-based and 1. [C6MIM][BF4].6.[179] solution at 303. temperature and and levulinic acid (1:2) for CO2 capture and with the focus on the the molar ratio of HBD.5) at pressures up to 13 MPa. 183] the attractive forces on the surface. CO2 solubility values were obtained for ChCl/urea (1:2) with a Lin et al.[178] solutions could be greatly improved by the addition of To use DESs for CO2 separation. The results revealed that molecular solvents but similar to imidazolium-based ILs and the ChCl-triethylene glycol (1:4) possessed the highest CO 2 high-temperature molten salts.301 mol CO2/mol DES at 12. 1:3. investigated the influence of water on the CO 2 solubility in industrial applications. presented Henry’s constants of CO2 in aqueous DES value of 0.15-313. formation of solution with a low viscosity and melting point.[182.[184] The DESs containing 2. in tetrabutylammonium DESs.231. PEG200.54 mm (1:1. For example. whilst MEA solution exhibited a corrosion rate of 0. those with mole ([hhemel]. The results the viscosity of ChCl:glucose (1:1) with a value of 34400 demonstrated that the low CO2 solubility in aqueous reline mPa·s. The CO2 solubility in the DESs of ChCl-phenol (1:2. Maugeri’s group found absorption was exothermic.027 mm per Li et al. and Leron et al.[188] Considering the hygroscopic nature of ChCl. 1:4). [C4MIM][PF6]) potential of ionization instead of the permanent dipole moments but higher than [C2MIM]-based ILs (e. It was shown that a crossover point occurred at the mole fraction of 0. the [C2MIM][C2N3]). the ratio of 2.4-butanediol.15 K decreased to mPa·s compared to monoethanolamine were investigated by Hsu et al. such as water or CO2 absorption versus the mole fraction of reline. Below that (at low water content). measurements at high pressures. [C2MIM][Et2PO4]. Their results indicated that by This article is protected by copyright. 70 wt%) and its ternary solutions with (1:0. surface tension is controlled by London forces.[55. 60. Consequently. Abbott et al. which is attributed to the 1:4).[191] The recorded CO2 absorption capacity was 2. investigated the CO2 solubility in the DES based on (20-80 wt-%).3-butanediol with a ratio of 1:4 lower number of hydrogen bonding sites found in ethylene showed the highest CO2 absorption capacity. Ullah et al.[176] The solubility of CO2 in ChCl/glycerol (1:2) was investigated by Generally. Meanwhile. 185-187] [177] or the DESs based on carboxylic acids. Water acts as an anti-solvent. The CO2 solubility in these DESs was comparable these forces depend on the diameter of molecules and the with that of [C4MIM]-based ILs (e.[190] capacity is another important factor.5) at 323. [hhemeal]) but slightly lower than ratios of 2:1 exhibited the lowest surface tensions [158] whereas imidazolium.2 K. 1:2.[147] absorption capacity. replacing of ChCl and dihydric alcohols (1. thus decreasing the solubility of CO2.ChemSusChem 10. glycerol as well as malonic comparable with C4MIM-based ILs.and phosphonium-based ILs ([DMIM][Me2PO4]. and it increases with increasing characterization of the DES and the CO2 solubility pressure and decreasing temperature.2-propanediol) with a molar ratio of ChCl to HBD (1:3 and DESs decreased the surface tension. reported that the surface tension of the DESs composed of ChCl ChCl-diethylene glycol (1:3 and 1:4) and ChCl-triethylene glycol and carboxylic acids was higher than those of common (1:3 and 1:4) was studied by Li et al.15 K and 5 MPa. the CO2 absorption monoethanolamine. Su As environmentally friendly solvents suitable for large scale et al. The highest per year. the viscosity of the resulting solution of CO2 was endothermic.

triethylene glycol. Henry’s constants Zubeir et al.[189] The same behavior was reported by Xie et al. and 1:5.and ammonium-based negative entropy reflected the high ordering degree when CO 2 DESs from glycerol. 195] but lower than fluorinated-ILs (e. however.64.and ammonium-based DESs: CO2 in DESs was favorable from the point of enthalpy. using monoethanolamine as the HBD results indicated that there is a direct relation between the could improve the CO2 solubility and provide the highest freezing point of the DESs and its topological properties.[196] The results showed that the dissolution of CO2 into DES was not spontaneous. for ChCl.[193] studied the CO2 solubility in the DES HO N + + N + O - . and then the studied DESs were suitable for CO2 uptake purposes. respectively. The CO2 solubility in these DESs was higher than those in ammonium-based ILs (e. the presence of both molecules did not cause any The general reaction of CO2 capture is shown in Scheme 5.183] confirmed the presence of chemically bound CO2. increasing its concentration decreased the released energy for CO2 capture using DESs was found to be CO2 solubility. thus indicating that the absorption process was exothermic and the dissolution of Phosphonium. ethylene glycol. reported a theoretical study to characterize the than aqueous monoethanolamine solutions.[194] Gibbs free energy. The positive Gibbs free energy revealed triflouroacetamide. N2 Cl solutions composed of levulinic acid or furfuryl alcohol as HBD. and 1.ChemSusChem 10. (Z) N The molar ratios of ChCl:HBD were 1:3. the appearance of a new peak near 160 slightly lower than those in imidazolium-based ILs (e.180. [164] The urea (1:2) system. Additionally. [C2MIM][Et2PO4].4-butanediol. and the water did not affect the CO2 chemically binding CO2 with high capacity. 2. Their capacity. and the capacity was higher than furfuryl task-specific DES (adapted with permission) [197] alcohol. higher than those of common ILs. Also. Lactate-based DESs: This article is protected by copyright. The investigation of the water effect on the To prove that for the observed DES the mass increase during physicochemical properties of DESs was very important the exposure to CO2 was due to the formation of alkylcarbonate because of the infeasibility to work with anhydrous mediums in salt. both 13C-NMR and FTIR analysis urea and glycerol as HBDs.[167] CO2 solubility increased with increasing alkyl chain length of Thermodynamic properties are useful for quantitative ammonium salt. Moreover. The absorption capacity of these DESs was similar to to the strength of interactions between the DES and CO2 other studied DESs [194. and a superbase. the 13C-NMR. All rights reserved. the effect of water on the absorption capacity of DESs was analyzed. Cl. Due to the hydrophilic Task-specific DESs: nature of ChCl. Moreover. [C6MIM][BF4].g. CO2 N O N O N+ Recently. whereupon the other two new peaks in the 1600-1650 [C4MIM][Tf2N]). whereas the dissolution entropy reflects the order degree of [C4MIM][PF6]). the common ILs. glycerol. the dissolution enthalpy is correlated solubility. the dissolution entropy was typically negative.[192] They chose three DESs the molar ratio of salt:HBD highly affected the CO2 absorption based on ChCl with different HBDs and molar ratios.1002/cssc. rivalry between them.[195] dissolution enthalpy was always negative.g.186] The CO2 solubility in the studied DESs and 1300-1350 cm-1 ranges were assigned to the asymmetric was higher than those of the DESs containing di-hydric alcohols and symmetric stretches for the monodentate bond between or lactic acid as the HBD[184. The solubility. [hhemel] and [hhemea]) [185] but After CO2 bubbling.[55. tetramethylammonium chloride with the molar ratio (2:1).2- dissolved in the DESs. Among the studied systems.2.[197] The DES capture performance due to the equivalent affinity of CO2 composed of ChCl. DESs with a molar ratio of 1:2 and 1:3 Sze et al. that the CO2 solubility in glycerol and ethylene glycol was lower Garcia et al. synthesized phosphonium.g. The superbase molecules with two active sites and the water molecules with was used to deprotonate the OH groups of ChCl and glycerol. and formation. Therefore. The mixture of ChCl:Lev (1:5) represented the Scheme 5. one active site. studied the DESs based on lactic acid as an increased (CO2 solubility decreased) as mentioned by Su et environmentally friendly and biodegradable solvent and al. The composed of ChCl and lactic acid (1:2) by Francisco et al.[179.. Lu et al. 1:4. enthalpy and entropy of dissolution were also and the DESs exhibited excellent thermophysical properties calculated by correlating the values of Henry’s constants. only one active site is thus resulting in alkoxide anions capable of reacting with CO 2 to present.[39] The similar study was conducted for the DESs intermolecular structures in the solution of CO2 and DES. .194] but lower than those containing CO2 and ChCl. For although their CO2 absorption capacity was lower than the CO2 solvation in DESs under all reported conditions. and both CO2 and H2O can be mutually captured by the reversibly form an alkylcarbonate salt under ambient conditions. and the Ali et al. the explanation of CO2 dissolution into DESs and for the design CO 2 tetrabutylammonium chloride exhibited the highest CO 2 capture process. adjusting the physicochemical properties of the solvents without H preventing their CO2 uptake ability. In the case of 1:1 DESs. and FTIR analysis was performed before and industrial scale. The type of salt and mechanism of CO2 capture in DESs. DESs. The study of the water-effect is helpful for after CO2 bubbling. introduced the first task-specific DES capable of contained two active sites.201600987 REVIEW increasing the amount of water in solution. ppm was completely consistent with the alkyl carbonate [DMIM][Me2PO4]. Mechanism for superbase-promoted CO2 capture using a highest solubility.

15 1.0240 / mol·mol-1 [196] ChCl Urea 1:4 298.0211 / mol·mol-1 [196] ChCl Urea 1:2.15 1.0000 ChCl Ethylene glycol 1:4 0.15 1. Glycerol (1:2) exhibited the best performance (3.9930 TBACl Lactic acid 1:2 0.0306 / mol·mol-1 298. Among all the studied DESs.15 0.0000 [196] 0. 1 MPa were 0.0588 / mol·mol-1 308. The CO2 solubility increased with increasing pressure viscosity increased over time after capturing CO 2. and the DESs with 1:2:7 molar ratio provided the highest water. For example.4500 0.1827 / mol·kg 293. CO2 absorption capacity (105 mg per gram of DES).0000 0.8400 0.1941/ mol·kg-1 [188] ChCl Triethylene glycol 1:4 293.1624 / mol·kg 293. For the DESs based on increase in viscosity negatively affected the mass transfer and monocarboxylate.1002/cssc. All rights reserved.1852 / mol·kg-1 [188] ChCl Diethylene glycol 1:4 293.5774 [193] -1 [182] ChCl Ethylene glycol 1:2 3. This The type of salt and the molar ratio of salt:HBD highly affected capacity is comparable with those reported for task-specific ILs the CO2 absorption capacity.0000 0.15 0.4 mmol of CO2 per gram of DES).2030 / mol·mol-1 [179] ChCl Urea 1:2.5015 ChCl Levulinic acid 1:3 0.2869 / mol·kg 303.0000 BTPPC Ethylene glycol 1:12 0. In ammonium-based DESs.15 0.0725 / mol·mol 308.2-butanediol 1:3 0. CO2 solubility values in different DESs Salt HBD Molar solubility temperature pressure References ratio [K] [MPa] -1 [184] ChCl 1.5749 -1 [193] ChCl Levulinic acid 1:5 0.15 1.15 0. The water content of DESs highly absorption capacity was associated with this DESs.8630 ChCl Phenol 1:2 0.15 1. it can be inferred that the CO2 solubility in This article is protected by copyright.0503 / mol·mol-1 298.9920 [164] DESs depended on temperature.15 1.3-butanediol 1:4 0.5092 -1 [188] ChCl Diethylene glycol 1:3 0.5145 -1 [184] ChCl 1.5085 -1 [188] ChCl Phenol 1:4 0.15 0.15 12. 198] In addition.15 1.4-butanediol 1:3 0.1441 / mol·mol-1 [196] BTPPB Ethanol amine 1:6 298.0262 / mol·mol-1 [196] ChCl Ethylene glycol 1:8 298.1687 / mol·kg 293.0000 0.863 MPa. the studied capacities of ChCl-diethanolamine (1:6) and DESs could be almost fully regenerated by heating to 333 K and tetrabutylammonium bromide-diethanolamine (1:6) at 298 K and introducing N2 (50 mL/min) within 35 min.15 5.15 0. respectively.0000 [196] ChCl Glycerol 1:8 0.15 5.15 0.8630 0.15 0.15 1.1096 / mol·mol-1 [196] ChCl Eethanol amine 1:6 298.2052 / mol·kg 293. pressure and the molar ratio of For all ternary DES systems (ChCl-HBD-superbase).5000 0.5815 ChCl Furfuryl alcohol 1:5 0. alkyl chain length of HBD.15 1.5 313.9920 [164] -1 [164] TEACl Lactic acid 1:2 0.5134 [184] -1 [184] ChCl 2.2108 / mol·kg 293.1272 / mol·mol-1 308.15 0.6540 [180] 3.0419 / mol·mol-1 [196] ChCl Triethylene glycol 1:4 298.15 1.1884/ mol·kg 293.2010 / mol·mol-1 [179] ChCl Urea 1:1.15 5.15 1.1036 / mol·mol-1 [196] TBAB Diethanol amine 1:6 298.3090 / mol·mol-1 [179] ChCl Urea 1:2 313.5088 ChCl Triethylene glycol 1:3 0.15 1. The CO2 influenced the CO2 solubility because it acted as anti-solvent absorption capacity influenced by the molar ratio of superbase to and the CO2 affinity decreased by increasing the amount of HBD. For these DESs.15 1.0230 / mol·mol-1 298.15 1.1915 / mol·kg 293.15 1.0511 / mol·mol-1 [196] ChCl Glycerol 1:12 298.0000 0.5085 -1 [184] ChCl 1.15 1.2196 / mol·kg 303.15 1.5828 -1 [193] ChCl Furfuryl alcohol 1:4 0.6929 / mol·kg-1 [183] ChCl Glycerol 1:2 303.15 0.2700 / mol·kg 303.[24. Summary: Considering all above discussions and based on the information presented in Table 3.15 11.15 0.15 1.5097 ChCl 1.5135 ChCl Urea 1:2 3.0000 0.5 313.0000 0.201600987 REVIEW Table 3.4-butanediol 1:4 0.692 mol/kg) at 303 K and 5.0000 ChCl Glycerol 1:3 0. the CO2 solubility increased by increasing the capture kinetics.0830 / mol·mol-1 [196] TBAB Triethanol amine 1:3 298.15 1.4945 [188] -1 [188] ChCl Phenol 1:3 0.5592 / mol·kg-1 303.15 0. DES composed of ChCl- capacities are remarkable (2.1189 / mol·mol-1 [196] MTPPB Ethanol amine 1:8 298.15 0. their CO 2 capture Among the studied DESs up to date.1265 / mol·kg 303.5 298.1856 / mol·kg 303.5113 -1 [184] ChCl 2.0000 [196] 0.2549 / mol·kg-1 303. the one containing DBU showed increasing the length of ammonium salt resulted in increasing only a slightly increase in viscosity and the lowest CO2 CO2 absorption capacity.5667 -1 [193] ChCl Furfuryl alcohol 1:3 0.15 0.0000 TMACl Lactic acid 1:2 0.5129 0. and the and decreasing temperature.0000 0.0000 0. .1560 / mol·kg-1 293.15 0.5700 [193] -1 [193] ChCl Levulinic acid 1:4 0.15 0.3-butanediol 1:3 0.2-butanediol 1:4 0.1254 / mol·mol-1 [196] MTPPB Ethanol amine 1:7 298.ChemSusChem 10.1501/ mol·kg 293.[199] although their viscosities are generally high.1945 / mol·kg-1 293.15 0.1909 / mol·kg-1 293. the absorption and supported amine polymers.0925 / mol·mol-1 [196] ChCl Diethanol amine 1:6 298.15 1.1168 / mol·mol-1 [196] MTPPB Ethanol amine 1:6 298.0000 [196] 0. the salt:HBD.15 0.0454 / mol·mol-1 298.15 0.2276 / mol·kg-1 303.15 12.0373 (gCO2/gDES).0408 and 0.5040 [188] 0.0000 0.

The affinity of CO2 with the ILs depends on the IL structure properties. the CO2 solubility of them can be 1. Second. TBAB: tetrabutylammonium bromide TWEEN 80: Polyethylene glycol sorbitan monooleate This article is protected by copyright. consequently. low eco-toxicity. functionalization of ATR-IR: Attenuated total reflectance. It is expected the ILs that contain a level of [bheal]: bis(2-hydroxyethyl)ammonium lactate fluorination have improved CO2 solubility. groups fluorine atoms.4.8-Diazabicyclo[5. but up to now.0]dec-5-ene decrease their viscosity and enhance reactivity and CO2 affinity MTPPB: Methyltriphenylphosphonium bromide are of great importance. This work is also a part of the be partly balanced by chemical modification of them to prepare activities of the Johan Gadolin Process Chemistry Centre at Åbo task-specific ILs. . All rights reserved. Among the functional that appropriate molar ratios are chosen among them. reversible ILs NMR: Nuclear Magnetic Resonance are highly promising approach since their tunable properties PCIL: Phase-change ionic liquids allow for tailor-made properties. As another alternative. in contrast. and IL: Ionic Liquid faster CO2 mass transfer kinetics compared to highly fluorinated MEA: monoethanolamine CO2-philic IL.0]undec-7-ene improve the CO2 affinity seems to work well based on the results DMSO: Dimethyl sulfoxide revealed by Besnard et al. but these also result in being poorly CCS: Carbon dioxide Capture and Storage biodegradable and persistent in the environment. Systematic studies in this field are in new generation of solvents to capture CO2 with a special focus demand. However. The studies carried out so far indicated that these on improving the performance by functionalization. The main tasks of future work are to design new IL or DES with Abbreviations high CO2 affinity and low viscosity to compete with commercial amine solutions in industrial scale.ChemSusChem 10. provided in terms of CO2 absorption capacity. needs to be investigated in detailed to clarify how to adjust and functionalization of anion part of ILs is more effective than cation fine-tune these novel sorbents to achieve a high CO2 absorption part. Acknowledgements We believe that ILs display certain technical advantages over other traditional amine solutions. It would be possible to functional groups to promote the CO2 absorption capacity of ILs. These advantages relate to Kempe Foundations is gratefully acknowledged for funding of tunable physicochemical properties and designer nature of this this research. there are a few studies on physical properties and the influence of salt.4.3-dimethyperhydro- groups in the structure of ILs. develop a large amount of DESs with low cost and excellent Functionalized ILs are as efficient as the alkanolamine solvents properties by sensible selection of the salt and HBD. The CO2 working capacities of ILs are still somewhat Science Center under auspices of Knut and Alice Wallenberg low as compared with a state-of-the-art amine solution but can foundation are acknowledged. there is no report EtP2(dma): regarding the functionalization of ILs using fluorinated aromatic Tetramethyl(tris(dimethylamino)phosphoranylidene)phosphorictri rings. Tetracyanoborate-based ILs can be considered as a very amid-Et-imin promising sorbent for the industrial gas separation process due FTIR: Fourier Transform Infrared to their high CO2 solubility.2-diaza-phosphorane improved.7-triazabicyclo[4. mixtures of ILs with organic solvents to MTBD: 7-methyl-1. amine groups are better to introduce in the cation of the common ILs. functional groups can improve the interactions of CO 2 with ILs and result in new sorbents as effective as amine or Keywords: CO2 capture • Ionic liquids • Deep eutectic solvents • alkanolamine solutions. The Bio4Energy program and Wallenberg Wood solvent. low viscosity. but do not need any specific synthesis. HBD and their molar ratio on the solvent This review summarized the application of ILs and DESs as a properties of DESs. the mechanism of CO2 sorption with DESs associated with the type of anion of ILs. These ILs clearly highlighted that DESs are capable of absorbing CO 2 functional groups can introduce to cation and/or anion parts of even more than ILs due to their tunable physicochemical ILs.1002/cssc. amine and carbonyl groups are Comparison of the CO2 absorption capacity of DESs with that of considered as the primary CO2-phile functional groups. In the case of fluorine atoms or carbonyl groups.201600987 REVIEW Conclusions Furthermore. it is attainable to incorporate CO 2-philic solvents of today as CO2 sorbents.3. result has been obtained when the functional groups incorporate to the anion of the ILs.5. Due to the solvents might represent an acceptable alternative to common designer nature of ILs. and amine-functionalized ILs exhibit better selectivity. Selection of cation and anions with appropriate Akademi University. the best capacity. To achieve this goal two main AHA: aprotic heterocyclic anion methods can be carried out. indeed by introducing CO 2-philic functional BEMP: 2-tert-butylimino-2-diethylamino-1. The high stability and BTPPB: n-Butyltriphenylphosphonium bromide low reactivity of the fluorinated compounds give them many BTPPC: Benzyltriphenylphosphonium chloride excellent properties. ILs containing amine or carboxylate Task-specific ionic liquid • Green sorbent moiety can be considered as chemical scrubbing solvent also have advantages for CO2 separation under low pressure. according to the specific PEG200: poly ethylene glycol 200 demands. First.Infrared conventional IL. Using CO2BOLs: Carbon Dioxide-Binding Organic Liquids fluorinated aromatic rings either in anion or cation of ILs to DBU: 1.

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......2.......... .................................................................................. 5 b) The influence of cation ........................................................ Physical absorption and Coulombic interactions ......................................................................................................................................................................................................................................... CO2 capture with Ionic Liquids (ILs) and Deep Eutectic Solvents (DESs): a new generation of sorbents Contents 2................................................................................................................... 17 2........................................................................................................................... 12 Fluorination:..................... All rights reserved.............................. 15 Protic ILs: ....................................2...................................................................................................2.............................................................. 20 Viscosity: ........................................................... Xiaoyan Ji 1 – 32........1.......................................................................................................... 16 Phase-change ionic liquids (PCILs): ........................ 20 This article is protected by copyright.................................................................... Dual functionalization of ILs ....................................................................................... 14 Carbonylation: ................................................................................................................... 14 Fluorination:........................................................................... 19 Density: .................................................................................................................................................................................................................1......................................................... 12 Amination: ............ 19 3.......................................... 17 3.... 5 2.................................................................................................................................................................................................................................................................................................1.......................................................................... 19 Freezing point: ...................................................................................................................................................................................................................................................................................... 11 2........................................................... Functional groups for adjusting the properties of DESs ............................................2.......................................................ChemSusChem 10................... 13 Hydroxylation: ........................................................................................1..............2. 4 2....................................................... 11 d) Summary ............. 5 a) The influence of anion .. CO2 solubility ..................................... 11 2.........................................201600987 REVIEW REVIEW Shokat Sarmad............................. 13 Alcoholation: ................................................................................. 9 c) Novel ILs developed recently................................. 15 Basic ILs: .................................................................3..............................2.........* Jyri-Pekka Mikkola.................................................................................................................................................................................................................................................................................... Ionic liquids (ILs)......................... Anion functionalization ................................................... 16 2............................................................................................................................................1002/cssc..............................................................4.............................................................2........... 13 2........................................................................................................ Deep Eutectic Solvents (DESs) ................................................................................. 14 Amination: .................................................................................................................................................... IL-IL or IL-small organic molecules mixtures ........................................................................................ 12 Etherification:..............................................................................................................................................................................................1.................................................................................. 12 Carbonylation: ............................................................................................................................... Cation functionalization ............................................. Functionalization of ILs ............................................................................................................... 16 Reversible ILs:.............................................................................................................................................................................................................................

........................................................................................ .........................................................................................................................................................................................................................................................................................................................................2................... 21 Lactate-based DESs:... 23 Conclusions ..........................................................................................................................201600987 REVIEW Surface tension: ..................................... 22 Phosphonium.................................................................... 25 This article is protected by copyright...................................................................................................1002/cssc..............and ammonium-based DESs: ....................................................................................................................................... 24 References .................................................................................................................................................................................................................................................................................................................ChemSusChem 10......................................... CO2 capture using DESs ....................................................................................................... 22 Task-specific DESs: ........................................................ 24 Acknowledgements ....................................................................................... 20 3.................................................................................................................. 22 Summary: .......... All rights reserved....... 21 ChCl-based DESs: .......................