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

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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
REVIEW
Abstract: High cost and high energy penalty for carbon
dioxide (CO2) uptake from flue gases are important
obstacles in large-scale industrial applications, and
developing efficient technology for CO2 capture from
technic and economic points is crucial. Ionic liquids (ILs)
show the potential for CO 2 separation due to their inherent
advantages and have been proposed as alternatives in
order to overcome the drawbacks of conventional sorbents.
Chemical modification of ILs to improve their performance
in CO2 absorption has received more attention. Deep
eutectic solvents (DESs) as a new generation of ILs are
considered as more economical alternatives to cope with
the deficiencies of high cost and high viscosity of
conventional ILs. This review discusses the potential of the
functionalized ILs and DESs as CO2 sorbents. Incorporation
of CO2-philic functional groups like amine in cation and/or
anion moiety of ILs can be promoted their absorption
capacity. In general, the functionalization of anion part of
ILs is more effective than cation part. DESs represent
favourable solvent properties and are capable of capturing
CO2, but the research work is scarce and undeveloped
compared to the studies conducted on ILs. It is possible to
develop novel DESs with promising absorption capacity.
However, more investigation needs to be carried out on the
mechanism of CO2 sorption of DESs to clarify how these
novel sorbents can be adjusted and fine-tuned to best
tailored as optimized media for CO2 capture.
1. Introduction
Nowadays, the threat of global warming attracts ever more
attention. The exponential increase in the concentration of
greenhouse gases in the atmosphere is considered as one
of the most important reasons for climate change. Carbon
dioxide (CO2) is the most significant anthropogenic
greenhouse gas and thus makes a major contribution in
global warming. Naturally, CO2 exists in the atmosphere as
part of the earths carbon cycle, but human activities are
influencing the carbon cycle by emitting more CO 2 to the
atmosphere.[1-3]
The main source of CO2 emission is the combustion of
fossil fuels for transportation or production of electricity;
meanwhile, the industrial processes such as cement
manufacturing, natural gas processing, iron smelters, and
[a] Dr. Shokat Sarmad, Department of Engineering Science and
Mathematics, Devision of Energy Science, Lule University of
Thechnology, 971 87 Lule Sweden
E-mail: shokat.sarmad@ltu.se
Professor Xiaoyan Ji, xiaoyan.ji@ltu.se
[b] Professor Jyri-Pekka Mikkola, Technical Chemistry, Department of
Chemistry, Chemical-Biological Centre, Ume University, SE-90871,
Ume, Sweden
E-mail: jyri-Pekka.Mikkola@umu.se
[c] Industrial Chemistry & Reaction Engineering, John Gadolin Process
Chemistry Centre, bo Akademi University, Biskopsgatan 8, Fl-
20500, bo-Turku, Finland
E-mail: jpmikkol@abo.fi
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
ammonia production also emit significant amounts of CO2.
The greatest anthropogenic portion of CO2 emitted to the
environment is from the flue gases in power plants.
Therefore, decreasing CO2 emissions from flue gases is
very important.[4]
CO2 capture and storage (CCS) has been proposed as one
of the most important inventions to mitigate CO 2
emissions.[5] The process of CCS includes capturing waste
CO2, transporting the captured CO 2 to a storage site and
depositing it in a safe place. Due to the high cost of
separating CO2 in CCS, comprehensive efforts have been
put to develop efficient technologies to capture and
separate CO2 from flue gas, atmospheric air, and synthesis
gas.[6,7]
One of the most common techniques to remove CO 2 from
gas streams is the absorption by liquid solvents. In the
absorption cycle, the CO2-rich solution from the absorber is
transferred to the regenerator to release CO2 typically by
increasing the temperature and/or decreasing pressure.
The regenerated solution is recirculated to the top of the
absorber, thus completing the cycle. The gas from the
regenerator is concentrated in CO2 and ready for
dehydration and compression to a liquid phase for the
purpose of storage. The absorption can be either a physical
or chemical absorption process. In a physical absorption
process, CO2 is physically absorbed into the solvent and
removed in the absorber column via the rich solvent. The
CO2 solubility in the physical absorption process follows the
Henrys Law, and the process favours high-pressure and
low-temperature operations. This technology is mature and
has been widely applied to treat both natural- and synthesis
gas streams.[8] In a chemical absorption process, the
chemical reagents capture CO2 by a reversible chemical
reaction, and weakly bonded intermediates are formed.
Consequently, the intermediate compounds upon heating
are broken down into streams of solvent and CO 2 in the
regenerator. The chemical absorption process is more
suitable for the gas streams with a low partial pressure of
CO2, and it has been widely developed and
commercialized.[9-11] Traditionally, aqueous amine solutions
have been used as chemical solvents upon trapping CO 2 by
chemical absorption since they exhibit excellent absorption
capacity, high reactivity, high selectivity and low price. The
main disadvantages associated with these solutions are the
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
on developing more efficient solvents for CO2 separation.
During the last decades, ionic liquids (ILs) have received
great attention as potential alternatives to common amine
solutions due to their almost unlimited tunability in terms of
the chemical properties, e.g. the low melting point and
negligible vapour pressure.[13, 14] They belong to a class of
organic salts with lattice energies lower than those of
common inorganic salts like NaCl, and they are highly
affected by their asymmetric structure. Hence, it is possible
for them to exist in the liquid state at room temperature.
ChemSusChem
REVIEW
Since CO2 is more soluble in ILs than other common gases
(N2, CH4, etc.), ILs are capable to selectively separate CO2
from gas streams.[15,16]
In many common ILs, CO2 is physically absorbed, so that
the removal of CO2 requires less energy in comparison to
amine solutions. However, the absorption capacity is lower
than that of commercial amine solutions. It is important to
improve the absorption capacity by altering their structures
or mixing with other solvents. Meanwhile, another important
disadvantage of ILs that has been widely discussed is their
high viscosity, and how to adjust their viscosity to an
acceptable range is crucial.
Dr. Shokat Sarmad received her PhD in
physical chemistry from the University of
Tabriz, Tabriz-Iran in 2011. Her principle
areas of interest are synthesis,
characterization of ILs, DESs, and polymeric
materials; thermodynamics and transport
properties of IL solutions. She has co-
authored 10 publications in peer-reviewed
scientific journals and one book chapter. She
has worked at Lule University of Technology
as a postdoctoral fellow in a research group which focuses on CO 2
separation/capture and storage using the novel ionic
technology.
Prof. Jyri-Pekka Mikkola, born in Nousiainen,
Finland in 1966 received his M.Sc. in
chemical engineering from bo Akademi
Univ., bo-Turku, Finland in 1992. After
spending a few years at the industry he
returned to the academia to complete his
PhD in chemical engineering from bo
Akademi Univ., bo-Turku, Finland, 1999.
Since 2008 he is a professor (Sustainable
Chemical technology) at both Ume Univ.,
Sweden and bo Akademi, Finland. He has
co-authored >200 papers and holds a number of patents. The principal
areas of interest are green chemistry, IL technologies; chemical kinetics;
and novel materials.
Xiaoyan Ji was born in Jiangsu, China in
1971. She got PhD in Chemical Engineering
in 2000. She has more than 20 years
experiences of research and development in
the area of Chemical Engineering and
Energy Engineering. Her expertise is on
applied thermodynamics focused on
fundamental theoretical modelling and
experimental measurements for the complex
fluids (ionic liquids) with interface (confined).
Up to now, as a first author or main contributor, she has published 70+
journal articles, 5 books/book-chapters and 30+ conference contributions.
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
This can be targeted by choosing appropriate anion and/or
cation. Besides, the toxicity and low biodegradability of ILs
have been discussed, and the presence of impurities may
also affect their properties.[17,18] These aforementioned
drawbacks combined with the high price of ILs restrict their
industrial applications. To cope with the deficiencies of
conventional ILs, such as their potential toxicity and low
biodegradability as well as often high-cost, more recently,
deep eutectic solvents (DESs) have been introduced. [19] In
fact, DESs possess analogous properties to ILs and share
many common properties with them. Importantly, the
synthesis of DESs is simple, and almost all DESs can be
prepared by mixing a hydrogen bond donor (HBD) with a
hydrogen bond acceptor (HBA) in appropriate molar ratios.
The properties of these solvents can be rendered for CO 2
separation, as well generally, they are green and
biodegradable. However, compared to conventional ILs, the
research work on DESs is still in its infancy and
undeveloped, and the performance of these solvents on
CO2 separation needs to be improved. Since DESs are
similar to conventional ILs, it will be of importance to gain
the experiences from ILs on how to improve their
performance.
The research work on developing conventional ILs for CO2
separation has been reviewed. Hasib et al. discussed
liquid-based recent progress and development in using ILs in CO 2
capture, and the room temperature ILs, task-specific ILs,
supported IL membranes and polymerized ILs were
included in this review.[20] Yu and coworkers investigated
CO2 capture by absorption and adsorption technologies. [11]
Zhao et al. reviewed progress in CO2 trapping using
conventional ILs, functionalized ILs, supported IL
membranes, polymerized ILs and the mixtures of ILs with
molecular solvents, and they also suggested further
developments.[21] In another work, Privalova et al. reviewed
conventional and IL-based technologies particularly
including switchable ILs (SILs) for CO2 separation. They
focused on both traditional solvents and different advanced
systems, meanwhile, the comparison of these technologies
from the aspects of environment, technology, and
economics was provided. The suitability of different ILs as
promising gas separation solvents, their synthesis and
properties were also discussed.[22] Torralba et al. discussed
CO2 capturing using ILs based on the solubility measured
experimentally. They reviewed the CO2 solubility in the ILs
based on imidazolium, pyrrolidinium, pyridinium and other
common cations. Different experimental techniques like
gravimetric analysis, the pressure drop, and the view-cell
methods were also described.[23] Zhang et al. reviewed the
research progress on CO2 capture using ILs with a specific
attention to potential industrial applications. They discussed
and compared the CO2 absorption capacities of pure ILs
(conventional and task-specific ILs) and mixtures of ILs,
and the mechanisms of chemisorption and physisorption
were explained with experimental characteristics and
molecular simulation.[24] Yang et al. discussed applications
of task-specific ILs for CO2 capture activation and
ChemSusChem
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subsequent conversion of CO2, targeting catalytic
transformation of CO2 under low pressures (preferably at 1
atm). The motivation is that the ammonium alkylcarbonate
salt formed during the CO2 uptake exhibited excellent
reactivity in terms of catalytically converting the captured
CO2 into organic molecules under low pressures.[25] Kumar
and coworkers reviewed applications of aqueous amines,
ILs and IL-amine blends for natural gas sweetening and
their healthy/environmental effects. They discussed that the
combination of ILs with secondary, tertiary and sterically
hindered amines were highly efficient in CO2 capturing, and
the stripping of CO2 from the so-called CO2BOLs (CO2-
binding organic liquids) was less energy consuming. For
example, by modest heating or inert gas bubbling, CO 2
could be stripped.[26] Zhang et al. provided a short
summary regarding the development of CO2 separation and
conversion using ILs.[27]
Bara et al. reviewed the research work using imidazolium-based
room temperature ILs as CO2 separation media. The role of
these ILs as physical solvents or that of supported ionic liquid
membranes (SILMs) as highly permeable and selective transport
medium was investigated.[28] Room temperature ILs by the
combination with amine groups in anion or cation part exhibit
great potential to chemically capture CO2.[28] Karadas and
coworkers discussed the use of ILs as alternative fluids for CO2
capture and natural gas sweetening as well analyzed the state-
of-the-art results to deduce the possibility of ILs as appropriate
alternatives to conventional amine-based absorbents.[29]
Shannon et al. reviewed the differences between the reactive
and reversible ILs and conventional ILs reported in the
literature.[30] They introduced imidazolium and imidazolium-
amine hybrid solvents as an adjustable approach for removal of
CO2, H2S, or SO2. Ramdins group discussed state-of-the-art of
CO2 capture using ILs.[31] They provided an overview of the
achievements and difficulties that have been faced in
discovering a proper IL for CO2 capture with the consideration of
economical and envionmental issue.[31]
Carvalho et al. very recently discussed some myths about the
CO2 solubility in ILs.[32] They used CO2 solubility in eicosane as
a references, explained that Ils did not exhibit higher physical
sorption of CO2 compared to the n-alkanes and stated that the
fluorination of the ions had no influence on CO 2 solubility while
the existence of the oxygenation slightly decreased the CO 2
solubility.[32] The heavy alkanes possess very low vapor
pressure and thus are similar to IL solutions. Alkanes are
chemically and thermally stable, biodegradable, and can be
prepared as very low-cost solutions as well. They have
moderately high molecular weight. The effect of the alkyl chain
length on the CO2 solubility was also investigated.[32]
However, to our best knowledge, no work has been carried
out to summarize how to functionalize the conventional ILs
in order to optimize their performance for CO2 separation as
well as the underlying mechanisms.
For deep eutectic solvents, three review papers were found
with the focus on their properties. Smith et al. discussed the
properties of DESs and their applications in different areas,
whereas Zhang et al. reviewed the syntheses, properties,
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
and applications of DESs.[33,34] Garcia et al. recently
provided a summary of physicochemical properties of DESs
and their applications in gas separation.[35] Therefore, the
review on how to functionalize DESs is still unavailable.
The goal of this work was to review the influence of different
functional groups on improving the performance of ILs and
DESs to achieve an efficient CO2 capture as well as on the
interaction between CO2 and IL. To achieve this, the
research work on CO2 capture with ILs was surveyed, and
the effect of CO2-philic functional groups on physical
properties and CO2 absorption capacity of ILs was
reviewed. The research work on DESs was also reviewed
from the aspect of functional groups. The experiences on
ILs and the requirements of CO2 uptake will provide
knowledge on improving DESs for CO2 capture.
2. Ionic liquids (ILs)
Obviously, ILs belong to one of the potential alternatives for CO2
capture owing to their specific characteristics. They are organic
salts, a class of novel solvents typically made up of asymmetric
bulky cations and organic/inorganic anions, to render solvents
with a polar (even as a non-aqueous solution) nature. ILs exhibit
unique properties such as low melting point (often near room
temperature), frequently negligible vapor pressures as well as
high thermal and chemical stabilities, non-flammability and so
forth. The most predominant advantage is that their
physicochemical properties are tunable via a myriad of structural
modifications of cation or anion, and they thus can be called as
designer solvents.[36-38]
ILs since several years back are known as potent CO 2
absorbents. During the past decade, IL-CO2 systems have been
investigated in detail. The studies indicate that the supercritical
CO2 is highly soluble in ILs (almost up to 0.75 mole fraction), but
the normal volume expansion is not observed in the liquid due to
the strong Coulombic forces between the ions. ILs do not
dissolve in supercritical CO2 (e.g. 510-7 mole fraction of
[C4MIM][PF6] in CO2-rich phase), which is associated with the
low vapor pressure of ILs and the incapacity of CO2 to
sufficiently solvate ions in the supercritical phase.[13, 39]
Meanwhile, CO2 is more soluble in ILs than in common organic
solvents.[40, 41] All this renders ILs promising for CO2 separation.
In principle, ILs are capable of CO2 sorption either by physical or
chemical absorption. Conventional ILs are defined as the ILs
that do not possess any functional groups and thus, CO2
absorption occurs via a physical absorption mechanism. The
CO2 absorption capacity of ILs can be improved by
functionalization of ILs or using binary mixtures of ILs or mixing
ILs with selected organic solvents. In this section, the ILs as
physical absorbents for CO2 separation were tackled at first, and
then it was followed by a review of the functionalized varieties.
2.1. ILs as physical absorbents for CO2 separation
ILs have been recognized as potential sorbents for CO2
separation, and a lot of research work has been carried out. In
ChemSusChem
REVIEW
addition, several review articles have been published with the
focus on summarizing the experimental findings. The focus of
this part was to investigate how to improve the performance of
ILs to achieve an efficient separation and the mechanism behind
the experimental findings was analyzed as well.
2.1.1. Physical absorption and Coulombic interactions
In common ILs, the CO2 separation takes place via physical
absorption mechanism, which can be explained by the concept
of free volume.
Fractional free volume (FFV) is attributed to the ratio of empty
space to occupied space in a material. It can be concluded that
with increasing alkyl chain length, free volume increases that
resulting in providing more free space for gas molecules. Based
on classical thermodynamics, FFV can be defined as the
difference between the molar volume and Van der Waals
volume of a component as bellow:
Vm 1.3Vvdw
FFV (1)
Vm
Van der Waals volume of the ILs calculated using methods
proposed by Bondi.[42, 43]
Shannon et al. revealed that CO2 solubility and selectivity in ILs
were controlled by the free volume of the IL.[44, 45] They used the
COSMOtherm program to calculate the free volume of several
imidazolium-based ILs and demonstrated that the volume-
normalized solubility of CO2 was proportional to the free volume
to the power 0.5.[31, 44] According to free volume theory, the CO2
solubility in ILs increases by increasing pressure at a constant
temperature but at very high pressures reaches to a steady level
because there is no free volume occupied by CO2 molecules.
This indicates that addition of further CO 2 molecules is
impossible unless the structure of ILs broken. In summary, by
increasing the molar volume and free volume of ILs, CO2
solubility increases. This result approved the idea that entropic
effects had a more dominant contribution in CO2 solubility in ILs
than solutesolvent interactions as claimed by Carvalho and
Coutinho.[46]
Due to Coulombic interactions between the ions of ILs, only a
small volume expansion is observed in ILs upon dissolution of
CO2. It has been stated that both the cation and the anion of an
IL participate in Coulombic interactions and form a rigid packing.
Further, the thermal expansion coefficients of ILs are small in
comparison to organic solvents.[47] The rigid network of cations
and anions in ILs potentially includes a large amount of free
volume; as a consequence, these free spaces can be occupied
by the CO2 molecules. The molecular dynamics simulations
carried out by Cadena et al. also showed that the arrangement
of ions was not disturbed by the addition of CO 2 into IL
solutions.[48]
Furthermore, Huang et al. reported that the size of the originally
available free spaces in [C4MIM][PF6] was not big enough to
incorporate CO2.[49] Their molecular dynamics simulations
indicated that after introducing CO2, the [PF6] anions were
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. All rights reserved.
10.1002/cssc.201600987
hold CO2 molecules, while the rearrangement of the initially
available spaces would not result in a great volumetric
expansion during CO2 dissolution even at high concentrations.
This also indicated that due to the finite free volume that was
originally available, just a certain amount of CO 2 molecules
could be associated even at high pressures.
Meanwhile, in the work by Huang et al., the diffusion coefficients
for [C4MIM]+, [PF6] and CO2 molecules were calculated with
molecular dynamics simulations, and the results demonstrated
that the CO2 molecules were five times more mobile than the
ions of the IL.[49] These results further confirm the hypothesis
that the cations and anions of ILs form a rigid network with
Coulombic interactions and thus they are less mobile.
2.1.2. CO2 solubility
Importantly, CO2 capture using ILs through physical absorption
is favorable as they consume less energy upon solvent
regeneration compared to chemical absorption, e.g. in the case
of amine solutions. The high CO2 solubility is needed to achieve
a cost-effective process. Upon the physical absorption of CO2
using ILs, the size of anions is the main factor influencing the
CO2 solubility. This could be inferred on the basis of the
observation of the solubility measurements and the results from
molecular dynamics simulations. The structure of the cation of
an IL also influences the CO2 solubility. The full name and
structure of investigated ILs in this paper are represented in
Table 1.
a) The influence of anion
The influence of the anion on the CO2 solubility was also studied
by Aki et al. in which seven ILs with the same [C4MIM] cation
and different anions were examined. It was revealed that the
CO2 solubility in the ILs with fluorinated anions was higher than
those with non-fluorinated anions ([CF3SO3] [(CF3SO2)2N]
[(CF3SO2)3C]).[50] It was believed that the fluorination of the anion
was the main reason for the increased CO2 solubility. This
observation was further confirmed by Pringle et al. who studied
the CO2 absorption capacity in [C2MIM][Tf2N] and
[C2MIM][Mes2N].[51] The high CO2 solubility in the ILs containing
fluorinated anions (e.g. [Tf2N]) may be due to the presence of a
S=O group (referred the Henrys Law constants listed in Table
2). On the basis of ab initio calculations, it was found the S=O
group increased the CO2-philicity of molecules due to Lewis
acid-base interactions between the S=O group and the carbon
atom of CO2.[52]
The non-fluorinated nature and low viscosity of
tetracyanoborate-based ILs rendered them as an attractive
sorbent for the CO2 separation process. Mota-Martinez and
coworkers studied the physicochemical properties and CO 2
solubility of 1-hexyl-3-methylimidazolium tetracyanoborate
[C6MIM][TCB] up to 12.34 MPa at 283.56-364.04 K.[53] The
results were compared with C6MIM-based ILs in order to
investigate the effect of the anion.
ChemSusChem 10.1002/cssc.201600987

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Table 1. 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-2,3-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
- 1-butyl-3-methylimidazolium isobutyrate
+
N N
O [C4MIM][LEV]
1-butyl-3-methylimidazolium levulinate
N + O-
N O

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ChemSusChem 10.1002/cssc.201600987

REVIEW

O O 1-butyl-3- [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- 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]
+ - 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- 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 1,3-dimethylimidazolium dimethylphosphate [DMIM][Me2PO4]

OH
+ N P
N O
O
O- 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

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ChemSusChem 10.1002/cssc.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- 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-
+ -
[1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2- [MTBDH ][Im ]

N N a]pyrimidine][imidazole]
(Z)
HN N
N
1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2- [MTBDH+][TFE-]

N N F a]pyrimidine][2,2,2-Trifluoroethanol]
(Z)
OH
N F
F
F F [1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2- [MTBDH+]2[HFPD2-
F F ]
N N a]pyrimidine]-[2,2,3,3,4,4-hexafluoropentan-1,5-diol]
(Z)
HO F
N F OH
(S) O tetraethylammonium -alanine [N2222][L-Ala]
+
N
H2N OH
Triethylbutylammonium acetate [N2224][CH3COO]
+ -
N O
O
O O N-propyl-N-methyl-N,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,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

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ChemSusChem 10.1002/cssc.201600987

REVIEW

tetrabutylphosphonium benzimidazolide [P4444][BnIm]

N
+
P
N
-
trihexyltetradecylphosphonium,2-cyanopyrrolide [P66614][2-CNPyr]

-
N
P+ N

trihexyltetradecyphosphonium 4-Hydroxybenza ldehyde [P66614][4-CHO-

PhO]

P+ HO
O
O- 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- 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- N
+
N N
[Tf2N]--based ILs as attractive solvents for CO2 capture.[58] They
The Comparison revealed that at 333 K, [C6MIM][TCB] exhibited reported that [C2MIM][TCB] showed superior transport
higher solubility than [C6MIM][PF6] or [C6MIM][BF4], and almost properties, as well as lower viscosity and higher electrical
the same as [C6MIM][Tf2N].[54-56] conductivity compared to [C2MIM][Tf2N]. Due to the smaller
Nevertheless, [C6MIM][eFAP], which is known as one of the molar volume, [C2MIM][TCB] exhibited higher solubility in
most CO2-philic ILs, represented a bit higher solubility than molality scale under the studied condition. The standard
[C6MIM][TCB].[57] Moreover, 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- dilution revealed that the [TCB]- anion interacted with CO2 as
biodegradable, and the viscosity is more than twice of the strongly as [Tf2N]-.[58]
viscosity of [C6MIM][TCB]. Therefore, this IL was considered
unsuitable for sustainable applications. b) The influence of cation
Recently, Makino et al. investigated the performance of
tetracyanoborate [TCB]- and bis(trifluoromethanesulfonyl) amide

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ChemSusChem 10.1002/cssc.201600987

REVIEW

[62]
The experimental and molecular modeling studies by Cadena et [C4MIM][PRO] 0.000229 298.15
al.[48] were focused on investigating the factors that control the [C4MIM][IBS] 0.00137 298.15 [62]

CO2 solubility in imidazolium-based ILs.[48] According to literature, [62]

[C4MIM][TMA] 0.00286 298.15
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] 0.00993 298.15
position rather than a methyl group.[48, 50, 59] In order to prove [C4MIM][PF6] 5.34 298.15 [48]

this, Cadena et al.[48] examined three different ILs and [48]

[C4MIM][BF4] 5.65 298.15
investigated how the replacement by a methyl group against a
[48]
hydrogen atom at the C2 position of the imidazolium ring would [C4MMIM][BF4] 6.10 298.15
influence the CO2 solubility. The investigation revealed that the [C4MMIM][PF6] 6.18 298.15 [48]

presence of hydrogen on the C2 position only slightly influenced [60]

[C4MMIM][Tf2N] 3.50 298.15
the CO2 solubility, which can be inferred by comparison of the
[57]
Henrys Law constants listed in Table 2. [C5MIM][bFAP] 2.02 298.15
The influence of the cation on the CO2 solubility was also [C6MIM][Tf2N] 3.16 298.15 [57]

studied by Aki et al.[50] and Anthony et al.[60] An increase in the [57]

[C6MIM][eFAP] 2.52 298.15
length of the alkyl chain appended into the cation resulted in an
[57]
increase in CO2 solubility, particularly at higher pressures (as [C6MIM][pFAP] 2.16 298.15
can be seen from Table 2). As mentioned above, physical [C6MIM][Tf2N] 2.57 298.15
[62]

absorption was triggered by the interaction between ILs and CO2 [62]
[C6MIM][FAP] 2.28 298.15
molecules, in which the CO2 molecules occupied the free space
[57]
within the IL structure via Van der Waals forces and a large [C6MIM][ACE] 3.29 333.15
quadrapole moment. By increasing the alkyl chain length of ILs, [C6MIM][SAC] 11.30 333.15 [57]

the density increases, and thus, more free volume within the [57]
[C6H4F9MIM][Tf2N] 2.84 298.15
longer chain is available for a CO2 molecule to vacate this
[66]
space. [C8MIM][Tf2N] 3.29 313.2
[57]
[C8H4F13MIM][Tf2N] 2.73 298.15
Table 2. Henrys Law constants for some ILs
[60]
[p(5)mpyrr][Tf2N] 3.10 298.15
Ionic liquid HCO2 [MPa] T [K] References [60]
[P4441][Tf2N] 3.30 298.15
[61] [57]
[C2MIM][eFAP] 1.62 303.15 [hmpy][Tf2N] 3.28 298.15
[62] [57]
[C2MIM][TFA] 5.20 298.15 [Et3NBH2MIM][Tf2N] 3.31 298.15
[63] [67]
[C2MIM][BF4] 2.35 303.20 [mp(3)pip][FSI] 4.10 298.15
[51] [67]
[C2MIM][Nmes2] 7.70 293.15 [mp(3)pyrr][FSI] 4.00 298.15
[51] [67]
[C2MIM][Tf2N] 4.70 293.15 [N1223][FSI] 3.80 298.15
[62]
[C2MIM][Ac] 0.00512 298.15
[62]
[C2MIM][Tf2N] 3.18 298.15 Recently, Gupta et al. investigated mainly the cation effect of
[C2MIM][Tf2N] 3.56 298.15
[48] five tetracyanoborate ([TCB]) based ILs by integrating ab
[48]
initio calculations and molecular simulations. [68] The ILs studied
[C2MMIM][Tf2N] 3.96 298.15
were those with the cations namely 1-butyl-3-methylimidazolium
[C4MIM][Bu2PO4] 4.98 313.15
[64]
[C4MIM]+, 1-propargyl-3-methylimidazolium [HCC-C1MIM]+, 1-
[C4MIM][PF6] 5.34 298.15
[61] ethanenitrile-3-methylimidazolium [NC-C1MIM]+, 1-
+
[60]
butylpyridinium [C4Py] , and N-((dimethyl-amino) methylene)-N-
[C4MIM][Tf2N] 3.30 298.15
methylmethanaminium [(N11)2CH]+.[68] The results revealed that
[62]
[C4MIM][IAAC] 15.10 298.15 the binding energy of anion-cation followed the order:
[C4MIM][SUC] 7.08 298.15
[62] [NC-C1MIM]+>[(N11)2CH]+> [HCC-C1MIM]+> [C4MIM]+ >[C4Py]+.
[62]
The decrease in the fractional free volume, the percentage of
[C4MIM][TFES] 6.09 298.15
CO2 regeneration in the ILs, and the CO2 solubility and diffusivity
[62]
[C4MIM][BF4] 5.29 298.15 followed this trend too. [C4Py][TCB] with the lowest cation-anion
[C4MIM][PF4] 5.26 298.15
[62] binding energy was predicted to exhibit the highest
[62]
CO2 solubility and possess the largest fractional free volume.
[C4MIM][TFA] 4.94 298.15
Their studies suggested that low cation-anion interactions
[62]
[C4MIM]2[IDA] 2.10 298.15 played the key role in their high CO2 solvation ability and
[C4MIM][CF3CF2CF2COO] 1.84 303.15 [65] [C4Py][TCB] could be considered as a promising candidate for
[62]
CO2 capture.[68]
[C4MIM][Ac] 0.00222 298.15

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ChemSusChem
REVIEW
c) Novel ILs developed recently
In the case of physical absorption of CO2, most of the studied
ILs were based on imidazolium cations. Similar performance
was reported in the case of pyridinium-based ILs which are
cheaper and more easily biodegradable compared to
imidazolium ones.
Recently, Tagiuri et al. compared the CO2 solubility in three ILs
based on bis(fluorosulfonyl)imide [FSI] ([p(3)mpip][FSI],
[p(3)mpyrr][FSI], [N4441][FSI]).[67] They observed that the
solubility of CO2 in the ILs containing [FSI]- anion was almost an
par compared with those containing more fluorinated anion like
[Tf2N], meanwhile, a negligible effect of the cation on the CO2
solubility was reported as well. Their Henrys law constants are
also listed in Table 2.
In the work reported by Tagiuri et al., the CO2 solubility in three
[Tf2N]-based ILs with pyrrolidinium, phosphonium, and methyl
substituted at the C2 position of the imidazolium cations was
studied. It was observed that the CO2 solubility in molality scale
followed the trend of pyrrolidinium > methyl substituted
imidazolium > phosphonium.[69]
Carvalho and coworkers examined the CO 2 solubility of two
phosphonium-based ILs: namely [P66614][Tf2N] and [P66614][Cl].[70]
They reported the highest recorded solubility observed without
chemically binding in terms of CO2 absorption. Their results
showed that phosphonium-based ILs dissolved more CO2 than
imidazolium-based ILs with the same anion. The higher partial
molar entropy of CO2 in [P66614][Cl] observed in their study
indicated stronger structural solvation in [P66614][Cl]-based ILs,
and the observed higher partial molar enthalpy for the case of
[P66614][Tf2N] indicated a stronger interaction between CO2 and
[P66614][Cl].
Chen et al. compared the CO2 solubility in [C4MIM][MDEGSO4]
and [P66614][C12H25PhSO3].[71] The results indicated that
phosphonium-based ILs (e.g. [P66614][C12H25PhSO3]) could
dissolve more CO2 than the respective imidazolium-based ILs
([C4MIM][MDEGSO4]). In fact, they reported the largest observed
CO2 solubility in the ILs when concerning physical absorption
(95 g CO2 per kg of ILs). [P66614][C12H25PhSO3] even exhibited a
higher CO2 absorption capacity in comparison to [ P66614][Tf2N] or
[P66614][Cl].
d) Summary
In summary, compared to the cation, the anion is more
important in order to improve the CO 2 absorption capacity
of ILs. Among the studied ILs, those that contain the anion
with fluoroalkyl group exhibited a high CO2 absorption
capacity, and they followed the order suggested by Aki et
al.:[50]
[NO3]- [DCA]- [BF4]- [PF6]- [TfO]- [Tf2N]- [Tf3C]-
where TfO-, Tf2N- and Tf3C- contain one, two and three CF 3
groups, respectively.
For the case of cations, among the studied ILs, those
contain imidazolium cation with longer alkyl chain exhibited
a higher CO2 absorption capacity, and phosphonium
cations could dissolve more CO2 compared to imidazolium-
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
based ILs. Zhangs group proposed the following trend for
the CO2 solubility in the ILs with different cations:
thiouronium > guanidinium > pyridinium > imidazolium.[72]
2.2. Functionalization of ILs
To improve the performance of ILs, one method is to
introduce CO2-philic groups in the cation and/or anion of
ILs. The literature survey indicates that the presence of
functional groups, such as amine groups, fluorine atoms
and carbonyl groups, is capable of improving the CO 2
absorption capacity of ILs.
One useful method to increase CO2 solubility is the
replacement of the hydrogen atoms of common solvents
with fluorine atoms. Furthermore, the CO2-philicity of
fluorinated hydrocarbons must be proportional to the
density of fluorine atoms. Since fluorine atoms have a
higher electronegativity than hydrogen atoms, it is preferred
to carry out a stepwise fluorination of hydrocarbons leading
to weak Lewis-base units. The weak Lewis-base units can
interact with the carbon atom of CO2 due to the generation
of polar C-F bonds. Further, fluorination may result in a
rivalry among the neighbouring electronegative fluorine
atoms and thus result in worse Lewis-base potential. In the
case of partially fluorinated compounds, the electron
deficient hydrogen atoms can interact with oxygen atoms of
CO2 through weak C-HO interactions, and this mode of
interactions can be identified as a stabilizing force upon the
interaction between an aldehyde or acetate group and
CO2.[52, 73, 74] Although, CO2 was considered as a nonpolar
solvent due to its low dielectric constant, the solvent
property of this supercritical CO2 is anyhow similar to the
alkane of hexane. In fact, the large quadrupole moment of
CO2 explains its solvation power of other molecules.
Raveendran et al. have performed quantum chemical
calculations to figure out the specific interactions between
CO2 and fluorine atom of fluorinated organic materials by
comparing the reaction of methane and perfluoromethane
with CO2.[75] The result indicated that the nature of
interactions between CO 2 and fluorocarbons and those
between CO2 and hydrocarbons was completely different,
although being energetically similar. The results also
observed clear and specific interactions in the case of
partially fluorinated compounds. The dissociation energies
as a function of the number of fluorine atoms replaced on
the hydrocarbon chain demonstrated that there might be an
optimal density of fluorine atoms that resulted in a
maximum CO2-philicity.
Carbonyl groups are commonly used to improve the CO2
solubility in ILs. From the interaction viewpoint, CO 2 can be
considered as a Lewis acid, and the electron deficient
carbon atom can interact with carbonyl groups. Meanwhile,
the interactions between CO2 and a carbonyl functional
group (e.g. an acetate group) indicated that CO 2 can
simultaneously act as a Lewis acid and a Lewis base, i.e.
the carbon atom of CO2 interacts as a Lewis acid with the
carbonyl group of the acetate moiety, and one oxygen atom
ChemSusChem 10.1002/cssc.201600987

REVIEW

of CO2 can interact as a Lewis-base with one of the R- 2.2.1. Cation functionalization
hydrogen atoms via cooperative C-HO hydrogen bond.
Due to the quadrupolar charge separation in CO 2, a partial Amination:
positive charge can be generated on the carbon atom, and
a partial negative charge can then reside on the oxygen Bates group functionalized the cation moiety with a primary
atoms. Thus, CO2 can act as either an electron acceptor or amine in an imidazolium-based IL. The CO2 capture process
an electron donor. In addition, the double bonds of CO 2 can carried out via the formation of ammonium carbamate. After
be easily polarized and thus CO2 can take part in relatively almost 3 hours exposure, the molar uptake of CO2 reached 0.5
strong Lewis acid-base interactions with stronger Lewis mol CO2 per mol of the IL (i.e. theoretical maximum CO2 capture
base groups. Consequently, this kind of strong Lewis acid- capacity for ammonium carbamate). This amount was
base interactions will render the oxygen atoms of CO 2 comparable with amine solutions like mono-ethanol amine, di-
better Lewis-base groups. The quantum chemical iso-propanol amine, and so forth. For this IL, each CO2 reacted
calculations of Raveendran et al. 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.[80]
fluorination. 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, consequently rendering the carbonyl
Scheme 1. Reaction between CO2 and amine group (adapted with
groups to be weaker Lewis-bases.[75]
permission)[80]
Amine functional groups can be added to IL structure to
insert specific chemical reactivity with CO2. Amine
The process was completely reversible. After five cycles there
functional groups absorbed CO2 via two different paths:
was no loss of efficiency. Also, the formation of ammonium
formation of carbamate and formation of carbonate. Based
carbamate was confirmed by FTIR and NMR spectroscopy.
on the literature, the formation of carbonate and carbamate
Sanchez et al. functionalized the imidazolium-based cations
generally, contributes to the reaction between amine
paired with [DCA] and [BF4] with both a hydroxyl group and a
aqueous solutions and CO2.[76] Reaction of primary and
primary or tertiary amine.[81] These types of functionalized ILs
secondary amines with CO2 consists of two steps: formation
were capable of chemical absorption of CO2. They observed that
of the zwitterion and base-catalyzed deprotonation of the
the CO2 loading of ILs increased almost three-folds by
zwitterion. The unhindered (primary or secondary) amines
introducing the functional groups in their structures, whilst for the
form a stable carbamate, and only half a mol of CO2 is
traditional amine solutions the maximum gas loadings were
absorbed per mol of amine. Upon heating, the carbamate
stoichiometrically restricted. Their results also revealed that for
dissociates to produce CO2 and amine. Since the formed
ILs at low pressures (below 0.1 MPa) the chemical absorption
carbamate during absorption is completely stable, it
took place, similar to aqueous amine solutions. At high
requires a lot of heat energy to break the bonds and to
pressures (above 0.2 MPa), the amine solutions achieved the
regenerate the absorbent.[77] The primary amine
maximum capacity and further increasing the CO2 loading was
functionalized ILs uptake CO2 via formation of particular
not feasible; whereas, in the case of functionalized ILs, the gas
carbamate salt.
loading could be continuously boosted by ascending pressure
Tertiary amines in reaction with CO2 form an unstable
because of physical absorption. This reflected a fact that the
carbamate, and the reaction leads to the formation of
task-specific ILs were capable of both chemical and physical
bicarbonate ions. Tertiary amines have a high theoretical
absorptions of CO2.
capacity to absorb CO2 (one mol of CO2 per mol of amine).
Regeneration of tertiary amines requires less heat energy
Fluorination:
than for unhindered amines. However, 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.[57] They
Secondary > Tertiary). 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.[78, 79]
[C6H4F9MIM][Tf2N] (as can be seen in Table 2). Since
As a conclusion, it is evident that CO 2 can act as a weak
fluorinated molecules are expensive and lead to potential
Lewis acid and Lewis base, and the fluorine atom, amine
environment challenges, non-fluorous CO2-philic groups
group, and the C-H bond (via C-HO interactions) can
were studied further.
promote the CO2-philicity. These functional groups can be
either in cation or in anion of ILs. Besides, other functional
Carbonylation:
groups have also been proposed, and some for the cation
and some for the anion of ILs. In the next section, examples
The carbonyl group belongs to one of the promising candidates
of functionalization of ILs were reviewed.
to improve the CO2-philicity of ILs because they are capable of

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ChemSusChem
REVIEW
participating in Lewis acid-Lewis base interactions.[82, 83] Muldoon
et al. reported that introducing a butyl ester group in pyridinium
based ILs [b2-Nic][Tf2N] led to a negligible influence on the CO2
solubility at low pressures.[57] At high pressures, [b2-Nic][Tf2N]
exhibited a slightly higher CO2 solubility due to the secondary
interactions between the cation and CO2 molecules. The very
similar behavior was reported for [C2MIM][Tf2N] and
[C2MMIM][Tf2N].[48] The cation functionalization with ester groups
did not provide a good performance as expected, and it could be
attributed to the change of the electronegativity for oxygen atom
directly attached to the pyridinium cation. Molecular simulations
by Pensado et al. revealed that introducing ester functional
groups in the side chain of imidazolium cation increased the
biodegradability of these ILs but did not affect the solvation of
CO2 considerably.[84]
Etherification:
Another recognized option was the addition of ether functionality
into the alkyl chains of ILs. The ether groups increased the
flexibility of the alkyl chain, thus leading to increased free
volumes; meanwhile, the oxygen of ether could interact with the
carbon atom of CO2. All this could improve the CO2 absorption
capacity. To illustrate the influence of ether groups, the CO2
solubility in two ILs with ether groups (Ecoeng 500, Ecoeng
41M) was studied.[57] The performance of Ecoeng 500 was
similar to that of [C6MIM][Tf2N], and the good performance of
Ecoeng 500 was connected to its large free volume induced by
the long alkyl chain. It should be mentioned that the ions in
Ecoeng 500 are not environmentally detrimental, and the
dissolution of CO2 in this IL resulted in a reduced viscosity
thereby facilitating faster sorption rates under good mixing. [57] In
contrast, Ecoeng 41M which contained C4MIM cation paired with
ether functionalized alkyl sulfate anion did not give rise to a very
impressive performance.
Ether functionalization of ILs led to the formation of 1:1 van der
Waals complex due to the reaction of ether oxygen atoms as the
Lewis-base with the carbon atoms of CO2 as the Lewis acid.[85]
Baras group synthesized imidazolium-based ILs with oligo-
(ethylene glycol) functional groups.[86] Due to the presence of
polar ether linkages, these PEG-based ILs (e.g. 1-(2-
Methoxyethyl)-3-methylimidazolium bis(trifluoromethane)
sulfonimide) demonstrated a higher CO2 solubility than the
corresponding alkyl polyethylene analogues. These ILs were
capable of dissolving the same amount of CO 2 as their alkyl
functionalized analogues [C4MIM][Tf2N]. In addition, the
solubilities of N2 and CH4 in these ILs were lower, leading to 30-
75% higher selectivity than their alkyl functionalized
analogues.[87]
Sharma et al. reported the CO2 solubility in a series of ether
functionalized imidazolium-based ILs [C2OMIM][X].[88] These ILs
showed high absorption capacity (almost 0.9 mol CO2 per mol of
IL at 30 C). The observations based on FTIR and 13CNMR
spectroscopy confirmed that one mol of these ILs chemically
reacted with one mol of CO2 to form a carbamic acid. The CO2
absorption capacity of the studied ILs followed the trend: BF 4 <
DCA PF6 TfO < Tf2N.
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10.1002/cssc.201600987
Alcoholation:
Wang et al. introduced an equimolar (1:1) mixture of an alcohol
functionalized IL and superbase to achieve a rapid and
reversibly chemical absorption of CO2 at the ambient
pressure.[89] The system consisted of [heMIM][Tf2N] or
[Nip,211OH][Tf2N] as the IL and DBU, MTBD, BEMP or
EtP2(dma) as the superbase. The CO2 absorption capacity was
almost one mol CO2 per mol of superbase, and the absorbed
CO2 could be released by bubbling of an inert gas or mild
heating. For example, for the system composed of [heMIM][Tf2N]
and DBU, the molar ratio of 1.04 (CO2:DBU) was reached, a
value higher than that for pure [heMIM][Tf2N].[38] The formation of
amidinium alkylcarbonate due to the reaction of CO2 with an IL
and a superbase was confirmed by NMR spectroscopy. The
molar ratio of CO2 to DBU surpassed the theoretical maximum
for chemical absorption (1.0 mol per mol of DBU), demonstrating
that both chemical and physical absorptions took place. The
absorption process of the IL-superbase systems was gently
exothermic and resulted in a rapid uptake of CO2.
Hydroxylation:
Jalilis group synthesized hydroxyl-functionalized ILs by
introducing hydroxyl groups in the imidazolium cations. They
measured the CO2 solubility in [heMIM]+-based ILs with different
anions ([PF6], [Tf2N], [TfO]).[90, 91] The results indicated that the
CO2 solubility in hydroxy-functionalized imidazolium-based ILs
was higher than [C2MIM]+-based ILs containing the same anions.
This could be inferred that the introduction of hydroxyl functional
groups was a good tactic for improving CO2 absorption. The CO2
absorption capacity in the studied systems followed the trend:
[heMIM][Tf2N] > [heMIM][TfO] > [heMIM][PF6] > [heMIM][BF4].
Yuan et al. reported that the CO2 solubility in a series of
hydroxyl-functionalized ILs (hydroxylammonium) is higher than
[C2MIM][EtSO4] but lower than [C4MIM][PF6], and the highest
capacity was exhibited by the IL with THEAL (tri-(2-hydroxy
ethyl)-ammonium lactate) species.[92] In comparison to aqueous
amine solutions, these hydroxyl functionalized ILs exhibited
much lower CO2 solubility. The results of Deng and coworkers
revealed that the hydroxyl functionalization of ammonium-based
ILs did not considerably affect the CO2 absorption capacity while
the hydroxyl functionalization of pyridinium-based ILs led to a
decreased CO2 solubility.[93] This behavior could be attributed to
the undesirable entropic contribution to the Gibbs energy of
solvation. The similar behavior was shown in [heMIM][BF4]
system which exhibited a lower CO2 solubility than the
conventional IL of [C2MIM][BF4].[91] Huang et al. proposed
equimolar mixtures of hydroxyl-functionalized imidazolium-based
ILs and monoethanolamine (MEA) for CO2 uptake.[94] They
studied a mixture of [C3OHMIM][BF4] and MEA and compared to
the mixture of the conventional IL [C4MIM][BF4] and MEA. The
bubbling CO2 in the conventional ILs resulted in precipitating of
the MEA-carbamate salts. In both cases ([C3OHMIM][BF4]/MEA
and [C4MIM][BF4]/MEA), the absorption took place very quickly
and resulted in almost 0.378 mol CO2/mol MEA. It is known that
halide ions are capable of interacting with amines in organic
ChemSusChem
REVIEW
solutions via hydrogen bonding. When the amine was
protonated, the interaction between halide ion and amines could
be strengthened. Therefore, the effect of Cl - on the absorption
capacity was also studied. The results indicated that even
partially replacing BF4- ions with Cl- increased the thermal
stability and absorption capacity of the hydroxylated IL/MEA
system and prevented the precipitation of carbamate salts. The
hydrogen bonding and electrostatic attraction forces between Cl -
and protonated amine (MEAH+) or cation (C3OHMIM+) resulted
in the advantages mentioned above, which was confirmed by
spectroscopy and cyclic voltammetry. Vafaeezadeh et al.
introduced hydroxyl functionalized phenolic-based IL, 1-(2-
hydroxyethyl)-2,3-dimethyl- imidazolium phenoxide, and it is
capable of 1.5 molar CO2 absorption under ambient
conditions.[95] In addition, the phenolic ILs are cheap and thus
can be practical compounds with improved absorption capacity
almost up to 1 mol CO2/mol IL.
2.2.2. Anion functionalization
Fluorination:
Muldoon and coworkers investigated the effect of anion-
fluorination and introducing other CO2-philic groups to enhance
the solubility of CO2 in ILs.[57] To investigate the influence of
fluorinating anions, they compared the CO2 solubility in
[C6MIM][eFAP], [C6MIM][pFAP] and [C5MIM][bFAP]. The positive
effect of fluorine was observed by comparing the results with
those in [C6MIM][PF6] (it was shown in Table 2).[54] This
confirmed that the replacement of three fluorine atoms with
fluoroethyl groups significantly increased the CO 2 solubility. By
increasing the length of the fluoroalkyl chain on the anion, a
further increase in CO2 solubility was observed. For example,
the highest value was reported for [C5MIM][bFAP] by physical
absorption (kH= 2.02 MPa at 298.15 K as can be seen in Table
2). They also examined the fluorinated carboxylate anions and
observed a lower CO2 solubility in [C4MIM][TFA] as expected.
This is because the electronegative fluorine atoms reduced the
advantage of the carbonyl in interaction with CO 2. Combined
with other studies, it was concluded that there was an optimal
number of fluorine atoms to reach the maximum CO2-philicity,
and further increasing the number of fluorine atoms led to a
decrease of CO2-philicity.[75] The CO2 solubility in [N4444][doc]
was reported as high as in the case of [C6MIM][eFAP] that is one
of the best performings fluorinated ILs reported until today. The
carbonyl functionality, the long branched alkyl chain as well as
the low toxicity render the docusate anion as one of the
promising candidates among fluorinate anions. [57] The results
indicated that the CO2 solubility increased by introducing
fluoroalkyl group; nevertheless, Bara et al. reported that
fluoroalkyl-functionalized ILs exhibited almost 10% increase
in CO2 capture over their analogues.[96]
Similar to [Tf2N]-, the anions [SAC]- and [ACE]- contain sulfonyl
and carbonyl groups neighboring to the nitrogen atom. As can
be seen from Table 2, it was clear that the introducing sulfonyl
and carbonyl groups were not enough to increase the CO 2
solubility in [SAC]- or [ACE]- and the fluoroalkyl groups in [Tf2N]-
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
played an important role to enhance the dissolution of CO 2.[57]
Shiflett et al. compared the CO2 solubility in [C2MIM][Ac]
(chemically absorbing) with [C2MIM][TFA] (physically
absorbing).[97] The mixture of two ILs showed a combination of
physical and chemical absorption. The research showed that the
CO2 solubility in [C2MIM][Ac] was reduced when a methyl group
in the acetate anion was replaced with a fluorinated methyl
group (replacing CH3-COO- with CF3-COO-). The plausible
reason is that the CF3 group weakened the Lewis basicity of the
anion by decreasing the electron density.
Besnard et al. proposed that fluorinated aromatic rings provide a
positive effect on the CO2 solubility, but unfortunately, this idea
has never been used to design the functionalized ILs in order to
enhance the CO2 affinity.[32, 98]
Carbonylation:
Carbonyl groups are known as one of the promising CO 2-philic
groups and could interact with the acidic carbon of CO2 through
the free electrons on the oxygen atoms.[82, 83] Meanwhile, several
studies have shown that the oxygen atoms of CO2 could interact
with the acidic hydrogens on the methyl group of acetate,[74] and
the addition of acetate group was expected to be an efficient
method to improve the CO2 solubility. Yokozeki et al. evaluated
the CO2 solubility in 18 different ILs and reported that the high
CO2 solubility with a strong chemical absorption was only
observed in the ILs with [X-COO], such as [C4MIM][Ac],
[C2MIM][Ac], [C4MIM][PRO], [C4MIM][IBS], [C4MIM][TMA] and
[C4MIM][LEV].[62] The X group (e.g. CH3, CH3CH2, CH(CH3)2,
C(CH3)3 and CH2CH2C=OCH3) also showed a powerful influence
on the formation of complexes with CO2, thus resulting in a
strong chemical absorption. These ILs showed a large negative
deviation from Raoults law, therefore justifying the assumption
that both chemical absorption and chemical complex formation
took place. This behavior was also explained with
thermodynamic excess functions, i.e. the negative values of GE
implied that the heat of mixing HE was more negative than that
of TSE, and the presence of a minimum in GE at around 33
mol% suggested the formation of 1:2 (CO2:IL) complex, i.e. one
CO2 molecule was sandwiched by two ILs. A new strategy was
proposed by Ding et al. to develop ILs via the non-covalent
interaction.[99] The developed ILs exhibited extremely high
absorption capacities up to 1.24 mol CO2 per mol of IL and great
reversibility because of the Lewis acid-base and cooperative C-
HO hydrogen bonding interaction. The C-HO hydrogen
bonding interaction itself is weak, and the strength of this
interaction affects the CO2 absorption capacity. Introducing
carbonyl groups to the anion strengthened the C-HO
hydrogen bonding interaction. Among the carbonyl groups
studied, the aldehyde carbonyl group was the most promising
one with a high CO2 absorption capacity. For example, the CO 2
absorption capacities for [P66614][4-CHO-PhO] and [P66614][PhO]
could be 1.01 and 0.81 mol CO2 per mol of IL, respectively. In
the case that the ILs contained carbonyl groups with stronger
basicity (e.g. [P66614][4-CHO-Im]), the capacity could be
increased to 1.24 mol CO2 per mol of ILs. These ILs exhibited
high stability. Therefore, the electron-withdrawing nature of the
ChemSusChem
REVIEW
carbonyl group resulted in a great reversibility, and attaching the
carbonyl group to anion was more efficient than to cation. For
comparison, the carbonyl group to cation can only give rise to
ILs with a capacity of 0.06 mol per mol of IL.
Carvalho et al. investigated the specific interactions of
[C4MIM][Ac] and [C4MIM][TFA] with CO2.[100] The results
revealed that CO2 solubility in [C4MIM][Ac] due to the differences
in enthalpies of solvation was spontaneous unlike in
[C4MIM][TFA].[100] An acid-base type of solvation mechanism in
acetate-based ILs was proved using ab initio calculations and
high resolution spectroscopy.
Gurau et al. confirmed the chemically absorption of CO2 in 1,3-
dialkylimidazolium acetate ILs using X-ray diffraction and NMR
spectroscopy.[101] They examined the reactivity of CO2 with
[C2MIM][Ac] by bubbling CO2 through the acetate-based IL at
atmospheric and ambient temperature conditions. After 24 hours
bubbling, the formation of 1-ethyl-3-methylimidazolium-2-
carboxylate was observed using NMR spectroscopy. As well, X-
ray diffraction analysis exhibited that imidazolium carboxylate
and acetic acid were formed in the absence of water. Indeed
water was shown to inhibit the interaction of acetate with the
proton at the C2 position of the imidazolium ring, so preventing
the CO2 reaction.[101]
Besnard et al. also using Raman, infrared, NMR spectroscopy
and DFT calculations demonstrated that CO2 reacted with
[C4MIM][Ac] to form an imidazolium carboxylate and acetic acid
via the deprotonation of the C2 of the imidazolium ring. [102]
Amination:
Amino acids exhibited potential benefits over amines due to their
considerably lower vapor pressure. In addition, they were more
tolerant to oxidative degradation and less toxic than common
alkanol amine solvents.[103, 104] Amino acids were used to
functionalize common ILs in either anion or cation. [105, 106] One
should point out that these ILs are high-quality functional
solvents; moreover, they are biodegradable and biocompatible
as well as equipped with chiral centers. However, their
viscosities are high and thus limit their applications. Jiang et al.
synthesized low-viscosity amino acid ILs (AAILs) using
symmetric tetra alkyl ammonium species as the cation
precursors and amino acids as the anions.[107] They found that
the tetraethylammonium cations resulted in solvents with lower
viscosity, especially in the case of alanine as the anion. They
proposed that the amino acid functionalized ILs composed of
[N2222][L-Ala] exhibited lower viscosities than amino acids and
contributed to a high CO2 absorption potential (0.5 mol per mol
of IL). According to the 13CNMR results, the studied ILs
chemically reacted with CO2.
Guo et al. studied the reaction of glycine with CO2 and provided
insight into how functional groups could affect the amine
reactivity of amino acids in terms of CO2 capture.[108] In aqueous
media, amino acids can exist as protonated, neutral or
deprotonated basic form, and the deprotonated basic form was
more reactive than the neutral form. This information was
valuable for determining the operation conditions, especially the
pH of the medium in the case of employing amino acid as liquid
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10.1002/cssc.201600987
absorption solvents or designing novel amino acid-based
solvents for CO2 uptake.
Gurkan et al. functionalized the anion with amine groups.[109]
They realized that, by introducing amine functional group to the
anion, the stoichiometry of the reaction could be increased from
one CO2 for every two amine molecules (1:2) to one for each
amine molecule (1:1). On the basis of the calculations,
introducing an amine group to the anion of ILs favored the
formation of carbamic acid, thus reflecting the instability of the
product di-anion. The influence was most noticeable when the
charge center and amine were close enough to each other. In
contrast, introducing an amine to the cation of ILs favors the
formation of the carbamate, indicating that the electrostatic
stability of the zwitterion product is favored. The 1:1
stoichiometry of the reaction of CO2 with the studied ILs was
characterized by FTIR spectroscopy at 298 K. Specifically, in the
FTIR spectrum of [P66614][Pro], before reaction with CO2, the
peak at 3290 cm-1 was assigned to [prolinate] N-H stretch bond.
The peak disappeared after reaction with CO2. The intensity of
the N-H bending was decreased after reacting with CO2. No
evidence confirmed the formation of ammonium in the case of
1:1, while in the case of 1:2, the ammonium formation was
observed. Their results also revealed that the anion-
functionalized ILs exhibited higher CO2 absorption capacities
than cation-functionalized ILs, and the location of the functional
groups (anion or cation) was another important factor upon the
design of functionalized ILs for specific applications.
Goodrich et al. introduced new amine-functionalized anion-
tethered ILs as CO2 absorbents with the trihexyl
(tetradecyl)phosphonium cation (P66614) due to its low price, high
thermal stability, and availability.[110] All the studied ILs exhibited
the capacities higher than 0.5 mol CO2 per mol of ILs at low
pressures (below 1 bar). The chemical absorption of CO2
resulted in an increase in viscosity due to the formation of a
hydrogen bond network. Decreasing the number of hydrogen
atoms on anion available for hydrogen bonding can reduce the
viscosity, and the presence of water can decrease the viscosity
significantly.
Protic ILs:
Wang et al. introduced an efficient system for CO2 capture
based on anion functionalized protic ILs (PILs). [111] They
used very strong superbases to deprotonate weak proton
donors of imidazole, pyrrolidinone, phenol or fluorinated
alcohols directly. The properties of PILs could be easily
adjusted because a variety of organic superbases and
weak proton donors are available. The studied PILs
exhibited low melting points and were capable of rapidly
and reversibly capture CO2 with high capacity (more than 1
mol per mol of ILs). The superbase played the decisive role
upon the formation of reactive PILs as strong proton
acceptors. Wang et al. also investigated the performance of
different superbase-derived PILs on the absorption of CO2.
Most of the studied PILs showed high absorption capacity
at atmospheric pressure. For example, [MTBDH +][TFE-]
resulted in 1.13 (mol CO 2 per mol PIL) and [MTBDH+]2
ChemSusChem
REVIEW
[HFPD2-] showed even higher capacity (2 mol per mol PIL)
due to the presence of two reactive groups. The rapid
absorption process was attributed to the low viscosity of the
PILs (e.g. 8.63 mPas for [MTBDH+][TFE-] and 31.85 mPas
for [MTBDH+][Im-]). During the reaction of CO 2 with PILs,
liquid carbonates, as well as carbamate or phenolate salts,
were formed as characterized by NMR and IR
spectroscopy.
Basic ILs:
Wang and coworkers developed a new anion-functionalized IL
that is capable of reversible, rapid, highly stable, energy-saving
and equimolar chemisorption of CO2 due to the reactivity of the
anions.[112] Indeed, the basicity of the ILs influenced the
absorption capacity, e.g. the absorption capacity increased from
0.17 to 0.95 mol CO2 per mol of IL by increasing the pKa of the
anion from 11.9 to 13.9 in DMSO (Dimethyl sulfoxide) and,
consequently, an equimolar absorption process could be
demonstrated by tuning the pKa values of the anion in basic ILs.
During the absorption process with these basic ILs, a carbamate
or carbonate salt was formed based on the observations from
NMR and IR spectroscopy. Furthermore, the increase of the
viscosity was not observed upon the functionalization and the
viscosity of [P66614][Im] was even decreased with the dissolution
of CO2. As mentioned in the former text, for amine-functionalized
ILs, the viscosity was increased considerably and resulted in the
formation of viscous or solid like gels. Therefore, these basic ILs
are promising in CO2 separation.
Phase-change ionic liquids (PCILs):
PCILs are attributed to salts that are solid at temperatures 313-
353 K and have a high CO2 absorption capacity due to the
chemical reaction. They are capable of reversibly and
stoichiometrically reacting (one mol CO2 per mol of salt) with
CO2, and the phase was changed from solid to liquid during the
reaction with CO2. The generated heat during the phase
transition was used to reduce the parasitic power consumption.
The melting point of the complex formed with CO2 (PCIL-CO2)
was below that of the pure PCIL.
Seo et al. investigated the CO2 solubility in PCILs based on tetra
butyl phosphonium salts with aprotic heterocyclic anions
(AHAs).[113] For these AHAs, their viscosities do not increase
upon the reaction with CO2 and they can bind with CO2 in the
range of reaction enthalpies that are suitable for gas separation.
Taking these advantages into consideration, AHA ILs are
promising candidates as efficient and environmental-friendly
absorbents in post-combustion CO2 capture. In fact, by using
AHAs, the enthalpy of reaction with CO2 could be easily
adjusted, and the melting point could be tuned by changing the
alkyl chain length of the corresponding phosphonium salt.
The CO2 solubility in four different PCILs composed of tetrabutyl
phosphonium salt as cations and AHAs as anions was studied.
At 333 K, these ILs were solid, but they transformed to liquid
quickly upon reaction with CO2. After cooling down to ambient
temperature, these CO2 saturated ILs remain liquid. This
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10.1002/cssc.201600987
indicated a considerable difference between the melting point of
pure PCIL and PCIL-CO2 complex. The studied PCILs exhibited
the following trend in CO2 solubility: [P4444][BnIm] > [P4444][6-
BrBnIm] > [P4444][2-CNPyr] > [P4444][3-CF3Pyra]. This order was
compatible with the decreasing enthalpies of anion-CO2 reaction
as reported earlier.[114]
The CO2 solubility measurements in [P2222][BnIm] were carried
out at various temperatures. At 323 K and below, the IL did not
fully liquidize but could dissolve a considerable amount of CO 2.
At 333 K and over, the IL became a liquid by introducing CO2
into the reaction cell, and the sample initially formed a slurry at
low pressures ( 0.1 bar). By increasing the pressure (almost
above 0.15 bar), most of the sample transformed to liquid and
saturated with CO2. The CO2 solubility in [P2222][BnIm] reached
to 1 mol CO2 per IL at 333 K and 0.1 MPa, but it reduced slightly
at high temperatures due to the exothermic nature of the CO 2
absorption reaction. CO2 was fully desorbed from [P2222][BnIm]
at 343 K by using a vacuum and the sample was fully back to
pure [P2222][BnIm] as dry solid, indicating the fully reversibility of
the reaction between IL and CO2. Thus, it could be concluded
that the PCILs were more energy-efficient candidates than the
aqueous amine solutions. Among the studied PCILs,
[P2222][BnIm] was the most promising candidate in the CO2
capture.[113, 115]
Seo et al. also, synthesized a family of ILs containing the alkyl-
phosphonium cation with AHA-based anions (pyrrolide,
pyrazolide, triazolide, imidazolide, and indazolide).[114] The
results revealed that cations had just minor effect on absorption;
they affected the physical properties of AHA ILs like viscosity.
The AHA-derived ILs remain liquid under ambient conditions due
to the presence of bulky and unsymmetrical alkyl chains coupled
to the phosphonium groups. The anions in the studied ILs are
composed of a tertiary amine that is associated with a
heterocyclic ring. Hence, each mol of IL was capable of binding
one mol of CO2 to form stable carbamate ions through Lewis
acid-base interactions. In addition, the water effect was further
studied. It was expected that the water in solutions would
decrease the CO2 molar capacity due to reprotonation of the
anion.[116] However, for [P66614][2-CNPyr], no capacity reduction
was observed at all, while the CO2 solubility was slightly
increased with the addition of water.[117] For phenolate ILs, the
CO2 absorption capacity increased due to the formation of
bicarbonate with the addition of water.[118, 119]
Reversible ILs:
Reversible ILs were considered as an alternative and highly
promising material that exhibited tunable properties and
chemistries.[30] In fact, the synthesis of an IL did not require,
starting with one or more neutral organic molecules that can
react with acid gas to form an IL or IL-like product in situ. By
tuning the chemical structures of these molecules the physical,
chemical or thermodynamic properties such as viscosity,
stability, heat of absorption can be controlled.[30]
Reversible ILs are considered as a special group of ILs based
on substituted cyclic and acyclic guanidine or amidine
derivatives and phosphonium cations.[120] This class of ILs can
ChemSusChem
REVIEW
also be described as organosuperbase ILs. Cyclic guanidinium
and amidinium derivatives were widely used as basic catalysts
due to their strong basicity. However, the main drawback was on
the difficult recovery from the reaction mixture. To cope with this,
one strategy was to convert these superbases into IL, which was
helpful in recycling the salt.[120]
This approach was introduced by Jessop et al. for the first
time.[121] They showed that introducing CO2 into a nonionic
liquid like alcohol or amine resulted in the formation a salt (IL)
which can be converted to its nonionic initial state by exposing it
to an inert gas.[121] Since the polarity of these solvents can be
tuned upon reaction with CO2 they considered as switchable
solvents.[122] Heldebrant and coworkers studied the reaction of
DBU (amidine) with CO2 in presence and absence of water. [123]
Their spectroscopic results revealed that an IL [DBUH]+[HCO3]-
was formed via the reaction of DBU and CO2 in the presence of
water but no reaction was observed in the absence of water. [123]
Blasucci et al. described two-component, reversible IL systems
based on amidines or guanidines and alcohols as well as one-
component, reversible IL generated from silylated amines.[124]
Scheme 2 depicted the mentioned systems. In both systems, the
molecular liquids reacted with CO2 at 1 atm to form ILs which
was able to be reversed upon heating or sparging with nitrogen
to release CO2.[124]
Two-component
N + CO2 N
+ ROH O
- CO2 C OR
(Z) N N
O O
H
H
N N
+ CO2 O
+ ROH C OR
N N N N
- CO2 O [129]
One-component
+ CO2
R1 R1
2 Si NH2 Si NH3 + O N
R2 R2
R3 - CO2 R3
O results indicated a value around 1.05 mol CO2 per mol of IL that
Scheme 2. Schemes for one- and two-component reversible ILs
The studies of Heldebrant et al. revealed that when
alkanolamidines, alkanolguanidines and diamines reacted with
CO2 to form reversible ILs, a considerably better CO2
chemisorption capacity was achieved.[125] CO2 chemically bound
to the alcohol on alkanolamidines and alkanolguanidines as
zwitterionic alkylcarbonates while on diamines as zwitterionic
carbamates. All the mentioned reversible ILs can be reverted to
their non-ionic forms by thermally stripping CO2 at temperatures
around 50 C.[125, 126] As reported by Hildebrant et al., for
hydroxyalkyl guanidine which containing short hydroxyalkyl
substituents (n<3), the chemisorption of CO2 was irreversible.[125]
Therefore, the CO2 addition product easily cyclized to stable
carbonate and did not release the chemically bound CO 2 even
by heating around 100 C.[125] Therefore, the CO2 addition
product easily cyclized to stable carbonate and did not release
the chemically bound CO2 even by heating to around 100 C.[125]
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10.1002/cssc.201600987
In contrast, in longer substituents (n>4), the chemisorption of
CO2 was reversible. Instead of a stable cyclic carbonate, an
unstable carbonate was formed that could easily release CO 2.
1,1,3,3-tetramethylguanidine-alcohol mixtures can be used as
more industrially feasible and practical alternative for the
chemisorption of CO2 since 1,1,3,3-tetramethylguanidine was
easily available and manufactured on an industrial scale. Cyclic
guanidine derivatives 1,3,5-triazabicyclo[4.4.0]dec-5-ene (TBD)
and its methyl analogue (MTBD) can be used as cation
precursors of reversible ILs.[127]
2.2.3. Dual functionalization of ILs
Zhang et al. reported a series of dual amino-functionalized ILs
based on (3-aminopropyl) tributyl phosphonium amino acid salts
([aP4443][AA]), where [AA] is represented by the natural amino
acids. The chemical absorption capacities of CO 2 were almost 1
mol CO2 per mol IL for both [aP4443][Gly] and [aP4443][Ala], and
this kind of ILs could be used in the reversible uptake of CO2.[128]
For the dual amino-functionalized ILs investigated by Zhang et
al., the cation (1,3-di(2-aminoethylene)-2-methylimidazolium
bromide) was bound with two primary amine groups. The
mechanism of reaction (scheme 3) was investigated by both
FTIR and NMR spectroscopy before and after CO2 exposure.[129]
According to the spectroscopic analysis, the absorption
mechanism included the formation of carbamate as shown
below in scheme 3.
O
H2N N NH2 + CO2 H2N N N N
N H
Scheme 3. CO2 absorption mechanism with dual amino-functionalized IL
(adapted with permission)
H Two amine groups bind to the cation and thus the maximum
R
Si 1 absorption capacity can reach 1 mol of CO2 per mol of IL. The
R
R3 2
was close to the theoretical absorption capacity. It could be
deduced that each primary amine group of the IL reacted with a
[124] CO2 molecule. The studied IL was capable of rapid and
reversible absorption of CO2.
Xue et al. synthesized dual amino IL with amino functionalized
imidazolium cation and taurine anioin [aeMMIM][Tau] that was
capable of absorbing CO2 up to 0.9 mol per mol of IL at ambient
pressure. NMR and FTIR spectroscopy verified a chemical
process. Additionally, the synthesized IL could be recycled
under vacuum or at a higher temperature.[130]
2.2.4. IL-IL or IL-small organic molecules mixtures
Double salt ionic liquids (DSILs) are considered as salts which
composed of more than two types of ions. DSILs are in liquid
form at low temperatures (lower than 373 K), and they can
exhibit unique glass transition temperature and melting point or
can act as a single set of ions. Chatel et al. recently reviewed
the physical properties, thermal behavior, solvent properties,
and applications of DSILs.[131] Due to the high CO2 solubility,
DSILs have gained more interest to use as liquid sorbents. The
ChemSusChem
REVIEW
CO2 solubility in DSILs is lower than the corresponding ILs, but it
is possible to adjust physical properties and solubility according
to the nature of ions.[131]
Using DSILs provides the opportunity to adjust the selectivity
and solubility upon capturing CO2. The IL [C2MIM][Tf2N] has
demonstrated one of the highest physical absorption capacities
for CO2 although it is to some extent toxic and expensive. Mixing
this IL with a cheaper, less toxic and non-fluorinated IL could be
a plausible compromise, giving the possibility to maintain almost
the same CO2 absorption capacity. Pinto et al. studied the CO2
absorption in a mixture of [C2MIM][Tf2N] and a non-fluorinated
pyridinium-based IL [C2py][EtSO4] in order to find an optimal
balance of the preferred properties. [132] The Henrys constant
decreased as the molar ratio of [C2MIM][Tf2N] increased, and
thus the absorption capacity increased by increasing the content
of the fluorinated IL. Almost the same behavior was observed for
the binary mixtures of imidazolium-based ILs such as
[C2MIM][Tf2N]+[C2MIM][EtSO4] and [C2MIM][Tf2N]+[C4MIM]
[EtSO4].[133] The CO2 solubility increased by increasing the
content of [C2MIM][Tf2N]. However, the capacity of the mixtures
was not higher than that of the pure fluorinated ILs.
Finotello et al. studied the solubility and selectivity of the binary
mixtures of ILs with imidazolium cations ([C2MIM][Tf2N] and
[C2MIM][BF4]).[134] Their results revealed that the solubilities of
CO2 and CH4 decreased with increasing the concentration of
[C2MIM][BF4]. The selectivity for CO2 with respect to CH4 and N2
in pure [C2MIM][BF4] was improved by the addition of 5 mol%
[C2MIM][Tf2N].
Lei and coworkers examined the CO2 solubility in binary
mixtures of imidazolium-based ILs.[66] The [C8MIM][Tf2N] with a
fluoroalkyl group and long alkyl chain length was chosen to
achieve high CO2 solubility, and the other IL was [C2MIM][BF4]
or [C4MIM][BF4] because of the high selectivity. The results
indicated that the solubility in all IL mixtures increased with
increasing pressure and decreasing temperature. The solubility
increased with increasing the amount of [C8MIM][Tf2N], and the
Henrys Law constant at the same content of [C8MIM][Tf2N]
followed the trend of: [C8MIM][Tf2N]+[C4MIM][BF4] >
[C8MIM][Tf2N]+[C2MIM][BF4]. It was also observed that at high
pressures the mixed ILs provided the probability of adjusting the
selectivity and solubility for physical absorption of CO2.
Functional ILs have great potential to apply as CO2 absorbent,
however, their high viscosity considerably influence CO2
absorption process. Wang et al. improved the performance of
amine functionalized imidazolium-based IL [NH2e-mim][BF4] by
mixing with low viscosity conventional ILs [C2MIM][BF4]/
[C4MIM][BF4].[135] The best performance achieved when the mole
fraction of [NH2e-mim][BF4] was 0.4 and the mixed system
exhibited an effective regeneration performance.[135]
Recently, Zhang et al. introduced a new kind of CO2 absorbent
with high efficiency and low cost.[136] They used a mixture of
imidazolium-based ILs mixed with an aqueous solution of a non-
ionic surfactant. Low viscosity and low cost of the sorption media
together with low IL consumption and good reproducibility were
achieved, thus rendering this system fascinating as a new kind
of absorbent for CO2. The results indicated that the absorption
capacity increased with increasing pressure and concentration
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
of ILs. The best result was shown in [8% Tween 80 (surfactant)
+ 10% [C2MIM][TfO] + water], which was capable to capture
0.798 mol/L CO2 at ambient temperature and low pressure (0.6
MPa). This renders the solvent system equivalent in terms of the
performance to alkanolamine solutions.
Li et al. reported that both the pure [Choline][Pro] and its mixture
with [Choline][Pro]/PEG200 could capture CO2 efficiently and be
easily regenerated by introducing N2 through the solution.[137]
The gas was mainly absorbed by [Choline][Pro] due to a very
strong interaction between the basic groups in [Choline][Pro]
and CO2. By increasing the amount of PEG200, the CO2
solubility decreased, but the viscosity was also decreased, thus
improving the kinetics of absorption and desorption of the CO 2.
The results illustrated that both chemical and physical
absorptions occurred in this solution.
Camper and coworkers used a mixed solution of a room
temperature IL and an alkanol amine the IL-amine combinations
are shown in Scheme 4.[138] The absorbed CO2 could be
released by increasing the temperature or decreasing the
pressure. This mixture combined the advantages of ILs such as
low heat capacity, high CO2 solubility, low vapor pressure and
high thermal stability with those of low viscosity and fast capture
performance of alkanol amines. This IL-alkanolamine solution
behaved similarly to aqueous amine solution but offered the
advantages of increased energy efficiency and diminished
corrosion of the equipment. Increasing the IL concentration led
to an increase in viscosity of the solution and a decrease in the
energy consumption for the solvent regeneration, and
particularly, the amine loss per ton of CO2 was remarkably lower
than in the case of aqueous amine solutions. The best result
was obtained with 30%wt MEA + 40%wt [C4MIM][BF4] + 30%wt
H2O, and the viscosity of this mixture was close to the viscosity
of a traditional amine solution.[139] For imidazolium-based ILs,
due to the acidity of hydrogen at the C2 position, they were not
completely inert under most conditions. Wang et al. took
advantage of the inherent acidity of imidazolium cations and
mixed with an organic superbase for CO2 capture at atmospheric
pressure.[127] The superbase reacted with CO2 to form
carboxylate salt, and equimolar CO2 capture was attained. The
results indicated that the C2 proton of an imidazolium cation
improved the CO2 capture capability, and by replacing the
imidazolium cation with pyridinium, only 0.25 mol CO 2 per mol of
IL could be captured.
H
H2N N
N N OH HO OH
N N OH
O O O O
F3C S N S CF3
F3C S N S CF3
O O (b)
O O
(a)
Scheme 4. IL-amine combination used for CO 2 capture, (a)
[C6MIM][Tf2N] with monoethanol amine and (b) hydroxyl-terminated IL
[140]
with diethanolamine
Triethylbutylammonium acetate and its water complexes
([N2224][CH3COO]-H2O) are fascinating as CO2 absorbents due
to their high CO2 absorption capacity and low viscosity. Wang
and coworkers used these solutions for reversible CO 2
absorption.[141] The good performance was from the large free
ChemSusChem
REVIEW
volume and basicity of the triethylbutylammonium cation and
acetate anion. The main drawback was the low thermal stability.
Quinn et al. proposed that the water molecules were connected
with the acetate anion through hydrogen bond which was
confirmed by NMR and FTIR spectroscopy.[142] The analytical
results along with the proposed mechanism indicated that by
reacting CO2 with IL, bicarbonate, and acetic acid were formed.
The chemical reaction proceeded to equilibrium. Once the
acetate anion lost its basicity, the absorption process was then
controlled by the physical mechanism via hydrogen bonding or
van der Waals forces. It is clear that by increasing the amount of
water, the combination of water molecules with acetate anion
and the affinity between CO2 and acetate anion were decreased.
The CO2 absorption in [C2MIM][Ac] (chemically absorbed CO2)
and [C2MIM][EtSO4] (physically absorbed CO2) and their binary
mixtures was studied by Pintos group.[143] In the binary mixture,
a combination of chemical and physical absorptions took place
and the addition of [C2MIM][EtSO4] to [C2MIM][Ac] restricted the
solidification due to the chemical reaction between [C 2MIM][Ac]
and CO2. Therefore, the absorption capacity for the mixture
containing (0.75 molar fraction) [C2MIM][Ac] + (0.25 molar
fraction) [C2MIM][EtSO4] at higher pressures was almost the
same as that of pure [C2MIM][Ac].[89]
3. Deep Eutectic Solvents (DESs)
Generally, the synthesis of ILs is complicated and requires a
large amount of expensive raw materials. The process of IL
synthesis is seldom environmentally friendly. All these problems
restrict their industrial applications. To cope with the high price
and toxicity of common ILs, recently Deep Eutectic Solvents
(DESs), a new generation of green solvents, have been
developed.[144]
DESs were obtained by mixing two components with an
appropriate molar ratio to form an eutectic solution with a
melting point lower than each individual component. The
decrease in the freezing point of the resulting DES is related to
the strength of interactions between the two components. In
general, DESs exhibit desirable properties, such as availability,
low-price, biodegradability, recyclability, non-flammability,
biocompatibility, non-toxicity, high thermal stability and non-
volatility. DESs are considered as economical alternatives to
common ILs since they can be prepared simply with high-purity
and low-cost on a large-scale.[145, 146]
The first generation of DESs has been based on the mixture of
quaternary ammonium or phosphonium salts with hydrogen
bond donors (HBD). The properties of the resulting solvent can
be considerably changed by altering HBD. Considering that
quaternary salts are generally inexpensive, non-toxic and
biodegradable as well as a wide array of amides, carboxylic
acids, alcohols, amines and metal salts can be used as
complexing agents, it is possible to obtain task-specific and
inexpensive eutectic ILs.[147-151] Low-cost and environmental
compatibility are crucial factors in developing new solvents for
CO2 separation, and eutectic-based IL analogues are thus more
promising than the conventional ILs.
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
2-hydroxy-N,N,N-trimethylethanaminium chloride (choline
chloride) is the most prevalent chemical used upon the design of
DESs. Choline chloride (ChCl) is non-toxic, biocompatible,
biodegradable and inexpensive. This quaternary ammonium salt
can be produced as an important additive used in animal feed.
Meanwhile, ChCl and protic ammonium salts with hydroxyl,
formyl, thiol and carboxyl are capable of forming DES upon
mixing with a common HBD, and the physicochemical properties
of the resulting DES can be altered by changing the HBD or
modifying the relative ratios of ChCl/HBD.[152, 153]
3.1. Functional groups for adjusting the properties of DESs
DESs can be designed by combining different components, and
task-specific DESs with specific physicochemical properties can
be prepared. Many DESs have been synthesized, and their
physicochemical properties have been reported. [27, 154, 155]
Physicochemical properties are determined by the structure of
DESs, and how the properties are affected will be essential to
design a task-specific DES.
The application of DESs in CO2 separation requires sufficient
information about their thermodynamic, physical, or chemical
properties. These properties are influenced by the temperature,
pH value, composition, and water content. In this section, we
discussed the factors that affect the physicochemical properties
of DESs such as freezing point, density, viscosity and surface
tension. In addition, how the CO2 absorption depends on the
strength of inter-intramolecular interactions or the free volume as
well as how much CO2 absorption capacity in DESs can be
adjusted were also reviewed.
Freezing point:
Eutectic mixtures are composed of at least two solid
components and the freezing point of the mixture is lower than
the freezing points of the individual components. The depression
of freezing point appears from the establishment of strong
intermolecular interactions between the HBD-HBA pairs and is
optimal for any eutectic mixture composition. Formation of a
liquid phase in DESs is controlled by the freezing point of ionic
species, and freezing temperature is influenced by the lattice
energy of salt and HBD as well as the entropy changes
occurring upon formation of a liquid. Consequently, DESs which
are constituted of larger ions with smaller charges are needed
less energy to break the bonds then caused to a depression in
the freezing point.[156]
Amide functional groups exhibit a great ability to form hydrogen
bonds with ChCl. Meanwhile, the halide salts with a low freezing
point can form complexes with HBDs to achieve a DES with a
low freezing point. For example, a mixture of ChCl and urea can
form an eutectic being a liquid at room temperature, and the
freezing point of the mixture can be as low as 285 K. This is
significantly lower than those of the constituents (mp are 575 K
for ChCl and 406 K for urea). This noticeable depression of the
freezing point was attributed to the interaction between the urea
and chloride ions.[157] Other functional groups that are capable of
hydrogen bond formation could also be used in the preparation
ChemSusChem
REVIEW
of eutectic mixtures with low freezing points. [34] The freezing
point depression of choline salts with urea exhibit the following
order: F-> NO3->Cl->BF4-
In addition, ChCl and D-glucose mixtures also exhibit eutectic
point at 2:1 molar ratio (288.15 K). D-glucose contains 5
hydroxyl groups in a cyclic form and the angle of the interaction
between hydroxyl groups and chloride anion is more desirable to
permit two ChCl molecules to form hydrogen bonds. [158]
Density:
The type of the salts in DESs has a strong effect on the density
and volumetric properties. For example, the density of
ammonium-based DESs is lower than that of phosphonium-
based DESs with a fixed HBD such as ethylene glycol. [159-161]
The density of DESs relates to the functional groups and the
chain length. For the DESs formed by HBDs with the hydroxyl
groups, their density increases with increasing the number of
hydroxyl groups.[162]According to the hole theory,[34] the average
hole radius or free volume increases with increasing the chain
length of HBD and leads to a decrease in density. For example,
among the DESs of ethylene glycol, 1,3-propanediol, glycerol
and 1,5-pentandiol, the DES with the longest chain in 1,5-
pentandiol presented the lowest density.[161] Therefore, the
density decreases with increasing chain length of HBDs.
Similarly, for the DESs containing dicarboxylic acids, the density
decreases with increasing chain length (oxalic acids > malonic
acid > glutaric acid > levulinic acid). Meanwhile, the addition of
the number of carboxylic groups also leads to an increase in
density (oxalic acids > glycolic acid). [163] However, for the
tetraalkylammonium bromide, the increase in the alkyl chain
length of the cation resulted in decreasing density. [164]
Moreover, the addition of water to DES mixtures significantly
decreases the density.[165-168] Interestingly, the introduction of an
aromatic group in HBDs (phenol, o-cresol) also decreases the
density of DESs, and the density of the DESs with o-cresol is
lower than those with phenol. This may attribute to the smaller
steric hindrances induced by phenol because the phenol
molecules are smaller than o-cresol.[169]
Viscosity:
The viscosities of DESs are generally high compared to other
organic solvents and thus give rise to problems in applications.
The mass and heat transfer ability and the conductivity of
solvent are strongly affected by their viscosity, and the high
viscosity of DESs hinders the mobility of any dissolved species.
Principally, the viscosity of DESs is related to the temperature,
the type of salt, the type of HBDs, the water content and the
molar ratio of salt:HBD. The involvement of water will
significantly decrease the viscosity of DESs. For example, the
viscosity of water saturated ChCl-oxalic acid system at 293.15 K
was 200 times lower than the case of dried sample. By
increasing the amount of water, the viscosity of DESs
decreased.[163, 165-168, 170]
The temperature dependency of viscosity can be explained
using Arrhenius equation, and the activation energies can be
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10.1002/cssc.201600987
used to evaluate the strength of the intermolecular forces in the
DES as well as their connection with viscosity. The higher
activation energy indicated it is more difficult for the ions to move
past each other.[147, 158-160, 163] Therefore, intermolecular
interactions between ions-HBDs have a key role in DESs
viscosity. For example, for ChCl-phenol, ChCl-o-cresol and
ChCl-ethylene glycol, their viscosities and activation energies
are low, whilst for ChCl-glucose and ChCl-sorbitol, their
viscosities and activation energies are high.
The addition of NiCl26H2O to ChCl-urea mixture considerably
reduced the viscosity of the resulting DES, and it appeared that
the water of hydration plays an important role in this case.
However, by increasing the mole fraction of NiCl26H2O, the
number of hydrogen bonds between ChCl and NiCl 2 increased
and resulted in an increase in viscosity. [170-172]
A comparison of the viscosity of DESs containing carboxylic
acids showed that the influence of HBDs on viscosity was
minimal. The presence of one extra carboxylic group (e.g. oxalic
acid, glycolic acid) or a hydroxyl group (e.g. glutaric acid,
levulinic acid) resulted in increased viscosity. This is because
the existence of extra carboxylic or hydroxyl groups creates
additional hydrogen bonds, thus leading to increase viscosity.[163]
Meanwhile, a comparison of the viscosity of DESs based on
ChCl and carboxylic acids with those of cholinium-based ILs
showed that the viscosity of these DESs was lower than those of
ILs.[161]
Based on the hole theory,[173, 174] the viscosity of DESs
corresponds to the holes available in the fluid which allows
appropriate ionic motions. On the basis of this theory, the
volumetric factors are more effective than interactions between a
salt and a HBD. Moreover, the distribution of the hole sizes is
dependent on the HBD and salt type.[35, 158, 159]
Surface tension:
Surface tension is one of the most important properties that
influence the mass transfer. The surface tension of DESs is
sensitive to the nature of salt and HBD, the temperature
and the molar ratio of a salt to a HBD. A temperature
increase leads to a decrease of surface tension. This is
because the high temperature increases the kinetic energy
and reduces the cohesion forces between molecules,
therefore weakening the interactions among the solvent
components.[160] Compared to conventional ILs, the surface
tension of DESs is higher, which indicates the stronger hydrogen
bonds formed between a salt and a HBD.[175]
Since surface tension is a measure of the strength of
intermolecular forces, it is expected to follow the same trend as
the viscosity. Interestingly, the addition of 30 mol % ChCl
decreased the surface tension of glycerol. This is because that
ChCl assists in breaking the intermolecular forces in glycerol.[176]
In general, the type of salt has a strong effect on surface
tension, and the presence of hydroxyl groups in a salt resulted in
a high surface tension due to their hydrogen bonding ability.
Increasing the alkyl chain length of salt also leads to an increase
in surface tension. Increasing the amount of salt decreases the
surface tension because it will lead to a weakened hydrogen
ChemSusChem
REVIEW
bond network whereupon the dissociated cations and anions
occupy the free spaces between HBD molecules and weaken
the attractive forces on the surface.[176]
Generally, surface tension is controlled by London forces, and
these forces depend on the diameter of molecules and the
potential of ionization instead of the permanent dipole moments
of molecules. For example, in tetrabutylammonium DESs, the
glycerol-based DESs exhibited higher surface tensions than
corresponding ethylene glycol DESs.[160] Similarly, replacing
glycerol with ethylene glycol as the HBD in the K 2CO3-based
DESs decreased the surface tension, which is attributed to the
lower number of hydrogen bonding sites found in ethylene
glycol.[172]
For the DESs based on ChCl and D-glucose, those with mole
ratios of 2:1 exhibited the lowest surface tensions [158] whereas
the ratio of 2.5:1 resulted in the highest. Surface tensions of
these DESs were higher compared to ILs such as [C4MIM][BF4]
[177]
or the DESs based on carboxylic acids.[147] Abbott et al.
reported that the surface tension of the DESs composed of ChCl
and carboxylic acids was higher than those of common
molecular solvents but similar to imidazolium-based ILs and
high-temperature molten salts.[147]
3.2. CO2 capture using DESs
As environmentally friendly solvents suitable for large scale
industrial applications, DESs have gained great interests in
CO2 separation due to their unique characteristics. Although
the viscosity of DESs is generally high, it can be overcome
by mixing DES with common solvents, such as water or
PEG200. Meanwhile, Abbott et al. reported that by adding
ChCl to glycerol, the viscosity of the resulting solution
decreased remarkably.[176] Similarly, Maugeris group found
that the addition of glycerol as the second HBD to the DES
composed of ChCl-sugar based polyols resulted in a
formation of solution with a low viscosity and melting point;
for example, the viscosity of ChCl:glucose:glycerol
(1:0.5:0.5) at 323.15 K decreased to mPas compared to
the viscosity of ChCl:glucose (1:1) with a value of 34400
mPas.[178]
To use DESs for CO2 separation, the CO2 absorption
capacity is another important factor. Generally, the CO 2
solubility in DESs depends on pressure, temperature and
the molar ratio of HBD, and it increases with increasing
pressure and decreasing temperature.
ChCl-based DESs:
Li et al. investigated the DES composed of ChCl and urea
(1:1.5, 1:2, and 1:2.5) at pressures up to 13 MPa. The highest
CO2 solubility values were obtained for ChCl/urea (1:2) with a
value of 0.301 mol CO2/mol DES at 12.5 MPa and 313.2 K.[179]
Leron et al. investigated the CO2 solubility in the DES based on
ChCl and urea (1:2).[180] The CO2 solubility in the DES was
comparable with C4MIM-based ILs.[50, 181] The CO2 absorption
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
capacity of ChCl-urea is higher than ChCl-glycerol and ChCl-
ethylene glycol.[182, 183]
The solubility of CO2 in ChCl/glycerol (1:2) was investigated by
Leron et al. The CO2 solubility in these DESs was comparable
with that of [C4MIM]-based ILs (e.g. [C4MIM][PF6], [C4MIM][PF6])
but higher than [C2MIM]-based ILs (e.g. [C2MIM][BF4] or
[C2MIM][C2N3]).[183]
Chen et al. studied the solubility of CO2 in the DESs composed
of ChCl and dihydric alcohols (1,4-butanediol, 2,3-butanediol
and 1,2-propanediol) with a molar ratio of ChCl to HBD (1:3 and
1:4).[184] The DESs containing 2,3-butanediol with a ratio of 1:4
showed the highest CO2 absorption capacity. The CO2 solubility
in these DESs was similar to those in ammonium-based ILs
([hhemel], [bheal], [hhemeal]) but slightly lower than
imidazolium- and phosphonium-based ILs ([DMIM][Me2PO4],
[C4MIM][Bu2PO4], [C2MIM][Et2PO4], [C6MIM][BF4], [C4MIM][Tf2N]
or [P6,6,6,14][C12H25PhSO3]).[55, 64, 185-187]
The CO2 solubility in the DESs of ChCl-phenol (1:2, 1:3, 1:4);
ChCl-diethylene glycol (1:3 and 1:4) and ChCl-triethylene glycol
(1:3 and 1:4) was studied by Li et al. The results revealed that
the ChCl-triethylene glycol (1:4) possessed the highest CO 2
absorption capacity.[188]
Considering the hygroscopic nature of ChCl, almost all ChCl-
based DESs contain at least a small amount of water. Water
acts as an anti-solvent, thus decreasing the solubility of CO2. Su
et al. investigated the influence of water on the CO 2 solubility in
reline (ChCl-urea 1:2)/water solution.[189] The results indicated
that the CO2 solubility in DES decreased with an increase in
water content. Consequently, they plotted the enthalpy of the
CO2 absorption versus the mole fraction of reline. It was shown
that a crossover point occurred at the mole fraction of 0.231.
Above this mole fraction (at high water content), the absorption
of CO2 was endothermic. Below that (at low water content), the
absorption was exothermic. These results were very useful
when attempting to develop new technologies for CO2
separation.
The CO2 solubility in a binary aqueous solution of reline (ChCl-
urea 1:2) (50, 60, 70 wt%) and its ternary solutions with
monoethanolamine were investigated by Hsu et al. The results
demonstrated that the low CO2 solubility in aqueous reline
solutions could be greatly improved by the addition of
monoethanolamine.[190]
Recently, Ullah et al. investigated the DES composed of ChCl
and levulinic acid (1:2) for CO2 capture and with the focus on the
characterization of the DES and the CO2 solubility
measurements at high pressures.[191] The recorded CO2
absorption capacity was 2.3 mmol of CO2 per gram of DES at
293.15 K and 5 MPa, and none of the measurements indicated
that chemical absorption of CO2 would have occurred.
Meanwhile, the corrosion was greatly reduced (0.027 mm per
year), whilst MEA solution exhibited a corrosion rate of 0.54 mm
per year.
Lin et al. presented Henrys constants of CO2 in aqueous DES
solution at 303.15-313.15 K with different DES compositions
(20-80 wt-%).[165] The investigated systems included ChCl as
ammonium salt and ethylene glycol, glycerol as well as malonic
acid as the alternative HBDs. Their results indicated that by
ChemSusChem
REVIEW
increasing the amount of water in solution, Henrys constants
increased (CO2 solubility decreased) as mentioned by Su et
al.[189] The same behavior was reported by Xie et al. for ChCl-
urea (1:2) system.[167]
Thermodynamic properties are useful for quantitative
explanation of CO2 dissolution into DESs and for the design CO 2
capture process. Moreover, the dissolution enthalpy is correlated
to the strength of interactions between the DES and CO2
whereas the dissolution entropy reflects the order degree of
intermolecular structures in the solution of CO2 and DES. The
Gibbs free energy, enthalpy and entropy of dissolution were also
calculated by correlating the values of Henrys constants. For
CO2 solvation in DESs under all reported conditions, the
dissolution enthalpy was always negative, thus indicating that
the absorption process was exothermic and the dissolution of
CO2 in DESs was favorable from the point of enthalpy.
Moreover, the dissolution entropy was typically negative, and the
negative entropy reflected the high ordering degree when CO 2
dissolved in the DESs. The positive Gibbs free energy revealed
that the dissolution of CO2 into DES was not spontaneous.
Garcia et al. reported a theoretical study to characterize the
mechanism of CO2 capture in DESs.[192] They chose three DESs
based on ChCl with different HBDs and molar ratios. Their
results indicated that there is a direct relation between the
freezing point of the DESs and its topological properties. The
released energy for CO2 capture using DESs was found to be
higher than those of common ILs, and then the studied DESs
were suitable for CO2 uptake purposes. Due to the hydrophilic
nature of ChCl, the effect of water on the absorption capacity of
DESs was analyzed. DESs with a molar ratio of 1:2 and 1:3
contained two active sites, and the water did not affect the CO2
capture performance due to the equivalent affinity of CO2
molecules with two active sites and the water molecules with
one active site. In the case of 1:1 DESs, only one active site is
present, and both CO2 and H2O can be mutually captured by the
DESs. Also, the presence of both molecules did not cause any
rivalry between them. The investigation of the water effect on the
physicochemical properties of DESs was very important
because of the infeasibility to work with anhydrous mediums in
industrial scale. The study of the water-effect is helpful for
adjusting the physicochemical properties of the solvents without
preventing their CO2 uptake ability.
Recently, Lu et al.[193] studied the CO2 solubility in the DES
solutions composed of levulinic acid or furfuryl alcohol as HBD.
The molar ratios of ChCl:HBD were 1:3, 1:4, and 1:5,
respectively. The mixture of ChCl:Lev (1:5) represented the
highest solubility, and the capacity was higher than furfuryl
alcohol. The CO2 solubility in these DESs was higher than those
in ammonium-based ILs (e.g. [hhemel] and [hhemea]) [185] but
slightly lower than those in imidazolium-based ILs (e.g.
[DMIM][Me2PO4], [C2MIM][Et2PO4], [C6MIM][BF4], and
[C4MIM][Tf2N]).[55,64,186] The CO2 solubility in the studied DESs
was higher than those of the DESs containing di-hydric alcohols
or lactic acid as the HBD[184,194] but lower than those containing
urea and glycerol as HBDs.[179,180,183]
Lactate-based DESs:
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
Zubeir et al. studied the DESs based on lactic acid as an
environmentally friendly and biodegradable solvent and
tetramethylammonium chloride with the molar ratio (2:1). [164] The
CO2 solubility increased with increasing alkyl chain length of
ammonium salt. Among the studied systems, the
tetrabutylammonium chloride exhibited the highest CO 2
solubility. The absorption capacity of these DESs was similar to
other studied DESs [194, 195] but lower than fluorinated-ILs (e.g.
[C4MIM][PF6]).[39] The similar study was conducted for the DESs
composed of ChCl and lactic acid (1:2) by Francisco et al.,[194]
and the DESs exhibited excellent thermophysical properties
although their CO2 absorption capacity was lower than the
common ILs.[195]
Phosphonium- and ammonium-based DESs:
Ali et al. synthesized phosphonium- and ammonium-based
DESs from glycerol, ethylene glycol, triethylene glycol, 2,2,2-
triflouroacetamide, and 1,4-butanediol.[196] The results showed
that the CO2 solubility in glycerol and ethylene glycol was lower
than aqueous monoethanolamine solutions. The type of salt and
the molar ratio of salt:HBD highly affected the CO2 absorption
capacity. Additionally, using monoethanolamine as the HBD
could improve the CO2 solubility and provide the highest
solubility; however, increasing its concentration decreased the
CO2 solubility.
Task-specific DESs:
Sze et al. introduced the first task-specific DES capable of
chemically binding CO2 with high capacity.[197] The DES
composed of ChCl, glycerol, and a superbase. The superbase
was used to deprotonate the OH groups of ChCl and glycerol,
thus resulting in alkoxide anions capable of reacting with CO 2 to
reversibly form an alkylcarbonate salt under ambient conditions.
The general reaction of CO2 capture is shown in Scheme 5.
To prove that for the observed DES the mass increase during
the exposure to CO2 was due to the formation of alkylcarbonate
salt, the 13C-NMR, and FTIR analysis was performed before and
after CO2 bubbling.
H
CO2 N O
N O N+
HO N +
+
N
+
O -
, N2 Cl
Cl- (Z) N
Scheme 5. Mechanism for superbase-promoted CO2 capture using a
task-specific DES (adapted with permission)
[197]
After CO2 bubbling, the appearance of a new peak near 160
ppm was completely consistent with the alkyl carbonate
formation, whereupon the other two new peaks in the 1600-1650
and 1300-1350 cm-1 ranges were assigned to the asymmetric
and symmetric stretches for the monodentate bond between
CO2 and ChCl. Therefore, both 13C-NMR and FTIR analysis
confirmed the presence of chemically bound CO2.
ChemSusChem 10.1002/cssc.201600987

REVIEW

Table 3. CO2 solubility values in different DESs

Salt HBD Molar solubility temperature pressure References

ratio [K] [MPa]
-1 [184]
ChCl 1,4-butanediol 1:3 0.1624 / molkg 293.15 0.5097
ChCl 1,4-butanediol 1:4 0.1560 / molkg-1 293.15 0.5134 [184]
-1 [184]
ChCl 2,3-butanediol 1:3 0.1501/ molkg 293.15 0.5113
-1 [184]
ChCl 2,3-butanediol 1:4 0.1915 / molkg 293.15 0.5085
-1 [184]
ChCl 1,2-butanediol 1:3 0.1827 / molkg 293.15 0.5145
-1 [184]
ChCl 1,2-butanediol 1:4 0.1884/ molkg 293.15 0.5015
ChCl Levulinic acid 1:3 0.2549 / molkg-1 303.15 0.5700 [193]
-1 [193]
ChCl Levulinic acid 1:4 0.2700 / molkg 303.15 0.5749
-1 [193]
ChCl Levulinic acid 1:5 0.2869 / molkg 303.15 0.5667
-1 [193]
ChCl Furfuryl alcohol 1:3 0.1856 / molkg 303.15 0.5828
-1 [193]
ChCl Furfuryl alcohol 1:4 0.2196 / molkg 303.15 0.5815
ChCl Furfuryl alcohol 1:5 0.2276 / molkg-1 303.15 0.5774 [193]
-1 [182]
ChCl Ethylene glycol 1:2 3.1265 / molkg 303.15 5.8630
ChCl Phenol 1:2 0.1945 / molkg-1 293.15 0.4945 [188]
-1 [188]
ChCl Phenol 1:3 0.2052 / molkg 293.15 0.5085
-1 [188]
ChCl Phenol 1:4 0.2108 / molkg 293.15 0.5092
-1 [188]
ChCl Diethylene glycol 1:3 0.1687 / molkg 293.15 0.5129
0.1852 / molkg-1
[188]
ChCl Diethylene glycol 1:4 293.15 0.5088
ChCl Triethylene glycol 1:3 0.1909 / molkg-1 293.15 0.5040 [188]

0.1941/ molkg-1
[188]
ChCl Triethylene glycol 1:4 293.15 0.5135
ChCl Urea 1:2 3.5592 / molkg-1 303.15 5.6540 [180]

3.6929 / molkg-1
[183]
ChCl Glycerol 1:2 303.15 5.8630
0.2010 / molmol-1
[179]
ChCl Urea 1:1.5 313.15 11.8400
0.3090 / molmol-1
[179]
ChCl Urea 1:2 313.15 12.5000
0.2030 / molmol-1
[179]
ChCl Urea 1:2.5 313.15 12.4500
0.0419 / molmol-1
[196]
ChCl Triethylene glycol 1:4 298.15 1.0000
ChCl Ethylene glycol 1:4 0.0230 / molmol-1 298.15 1.0000 [196]

0.0262 / molmol-1
[196]
ChCl Ethylene glycol 1:8 298.15 1.0000
0.0240 / molmol-1
[196]
ChCl Urea 1:4 298.15 1.0000
0.0211 / molmol-1
[196]
ChCl Urea 1:2.5 298.15 1.0000
ChCl Glycerol 1:3 0.0454 / molmol-1 298.15 1.0000 [196]

ChCl Glycerol 1:8 0.0306 / molmol-1 298.15 1.0000 [196]

0.1096 / molmol-1
[196]
ChCl Eethanol amine 1:6 298.15 1.0000
0.0925 / molmol-1
[196]
ChCl Diethanol amine 1:6 298.15 1.0000
0.0511 / molmol-1
[196]
ChCl Glycerol 1:12 298.15 1.0000
BTPPC Ethylene glycol 1:12 0.0503 / molmol-1 298.15 1.0000 [196]

0.1441 / molmol-1
[196]
BTPPB Ethanol amine 1:6 298.15 1.0000
0.1254 / molmol-1
[196]
MTPPB Ethanol amine 1:7 298.15 1.0000
0.1189 / molmol-1
[196]
MTPPB Ethanol amine 1:8 298.15 1.0000
0.1168 / molmol-1
[196]
MTPPB Ethanol amine 1:6 298.15 1.0000
0.1036 / molmol-1
[196]
TBAB Diethanol amine 1:6 298.15 1.0000
0.0830 / molmol-1
[196]
TBAB Triethanol amine 1:3 298.15 1.0000
TMACl Lactic acid 1:2 0.0588 / molmol-1 308.15 1.9920 [164]
-1 [164]
TEACl Lactic acid 1:2 0.0725 / molmol 308.15 1.9930
TBACl Lactic acid 1:2 0.1272 / molmol-1 308.15 1.9920 [164]

DESs depended on temperature, pressure and the molar ratio of

For all ternary DES systems (ChCl-HBD-superbase), the
viscosity increased over time after capturing CO 2, and the
increase in viscosity negatively affected the mass transfer and
capture kinetics.
Among all the studied DESs, the one containing DBU showed
only a slightly increase in viscosity and the lowest CO2
absorption capacity was associated with this DESs. The CO2
absorption capacity influenced by the molar ratio of superbase to
HBD, and the DESs with 1:2:7 molar ratio provided the highest
CO2 absorption capacity (105 mg per gram of DES). This
capacity is comparable with those reported for task-specific ILs
and supported amine polymers.[24, 198] In addition, the studied
DESs could be almost fully regenerated by heating to 333 K and
introducing N2 (50 mL/min) within 35 min. For these DESs,
although their viscosities are generally high, their CO 2 capture
capacities are remarkable (2.4 mmol of CO2 per gram of DES).
Summary:
salt:HBD. The CO2 solubility increased with increasing pressure
and decreasing temperature. For the DESs based on
monocarboxylate, the CO2 solubility increased by increasing the
alkyl chain length of HBD. In ammonium-based DESs,
increasing the length of ammonium salt resulted in increasing
CO2 absorption capacity. The water content of DESs highly
influenced the CO2 solubility because it acted as anti-solvent
and the CO2 affinity decreased by increasing the amount of
water.
The type of salt and the molar ratio of salt:HBD highly affected
the CO2 absorption capacity. For example, the absorption
capacities of ChCl-diethanolamine (1:6) and
tetrabutylammonium bromide-diethanolamine (1:6) at 298 K and
1 MPa were 0.0408 and 0.0373 (gCO2/gDES), respectively.[199]
Among the studied DESs up to date, DES composed of ChCl-
Glycerol (1:2) exhibited the best performance (3.692 mol/kg) at
303 K and 5.863 MPa.

Considering all above discussions and based on the information

presented in Table 3, it can be inferred that the CO2 solubility in

This article is protected by copyright. All rights reserved.

ChemSusChem
REVIEW
Conclusions
This review summarized the application of ILs and DESs as a
new generation of solvents to capture CO2 with a special focus
on improving the performance by functionalization. Due to the
designer nature of ILs, it is attainable to incorporate CO 2-philic
functional groups to promote the CO2 absorption capacity of ILs.
Functionalized ILs are as efficient as the alkanolamine solvents
in terms of CO2 absorption capacity. Among the functional
groups fluorine atoms, amine and carbonyl groups are
considered as the primary CO2-phile functional groups. These
functional groups can introduce to cation and/or anion parts of
ILs. The affinity of CO2 with the ILs depends on the IL structure
associated with the type of anion of ILs; consequently,
functionalization of anion part of ILs is more effective than cation
part. In the case of fluorine atoms or carbonyl groups, the best
result has been obtained when the functional groups incorporate
to the anion of the ILs, in contrast, amine groups are better to
introduce in the cation of the common ILs.
We believe that ILs display certain technical advantages over
other traditional amine solutions. These advantages relate to
tunable physicochemical properties and designer nature of this
solvent. The CO2 working capacities of ILs are still somewhat
low as compared with a state-of-the-art amine solution but can
be partly balanced by chemical modification of them to prepare
task-specific ILs. Selection of cation and anions with appropriate
functional groups can improve the interactions of CO 2 with ILs
and result in new sorbents as effective as amine or
alkanolamine solutions. ILs containing amine or carboxylate
moiety can be considered as chemical scrubbing solvent also
have advantages for CO2 separation under low pressure, and
amine-functionalized ILs exhibit better selectivity.
The main tasks of future work are to design new IL or DES with
high CO2 affinity and low viscosity to compete with commercial
amine solutions in industrial scale. To achieve this goal two main
methods can be carried out. First, functionalization of
conventional IL, indeed by introducing CO 2-philic functional
groups in the structure of ILs, the CO2 solubility of them can be
improved. It is expected the ILs that contain a level of
fluorination have improved CO2 solubility. The high stability and
low reactivity of the fluorinated compounds give them many
excellent properties, but these also result in being poorly
biodegradable and persistent in the environment. Using
fluorinated aromatic rings either in anion or cation of ILs to
improve the CO2 affinity seems to work well based on the results
revealed by Besnard et al. but up to now, there is no report
regarding the functionalization of ILs using fluorinated aromatic
rings. Tetracyanoborate-based ILs can be considered as a very
promising sorbent for the industrial gas separation process due
to their high CO2 solubility, low viscosity, low eco-toxicity, and
faster CO2 mass transfer kinetics compared to highly fluorinated
CO2-philic IL. Second, mixtures of ILs with organic solvents to
decrease their viscosity and enhance reactivity and CO2 affinity
are of great importance. As another alternative, reversible ILs
are highly promising approach since their tunable properties
allow for tailor-made properties, according to the specific
demands, but do not need any specific synthesis.
This article is protected by copyright. All rights reserved.
10.1002/cssc.201600987
Furthermore, there are a few studies on physical properties and
the influence of salt, HBD and their molar ratio on the solvent
properties of DESs. Systematic studies in this field are in
demand. The studies carried out so far indicated that these
solvents might represent an acceptable alternative to common
solvents of today as CO2 sorbents. It would be possible to
develop a large amount of DESs with low cost and excellent
properties by sensible selection of the salt and HBD, provided
that appropriate molar ratios are chosen among them.
Comparison of the CO2 absorption capacity of DESs with that of
ILs clearly highlighted that DESs are capable of absorbing CO 2
even more than ILs due to their tunable physicochemical
properties. However, the mechanism of CO2 sorption with DESs
needs to be investigated in detailed to clarify how to adjust and
fine-tune these novel sorbents to achieve a high CO2 absorption
capacity.
Acknowledgements
Kempe Foundations is gratefully acknowledged for funding of
this research. The Bio4Energy program and Wallenberg Wood
Science Center under auspices of Knut and Alice Wallenberg
foundation are acknowledged. This work is also a part of the
activities of the Johan Gadolin Process Chemistry Centre at bo
Akademi University.
Keywords: CO2 capture Ionic liquids Deep eutectic solvents
Task-specific ionic liquid Green sorbent
Abbreviations
AHA: aprotic heterocyclic anion
ATR-IR: Attenuated total reflectance- Infrared
BEMP: 2-tert-butylimino-2-diethylamino-1,3-dimethyperhydro-
1,3,2-diaza-phosphorane
[bheal]: bis(2-hydroxyethyl)ammonium lactate
BTPPB: n-Butyltriphenylphosphonium bromide
BTPPC: Benzyltriphenylphosphonium chloride
CCS: Carbon dioxide Capture and Storage
CO2BOLs: Carbon Dioxide-Binding Organic Liquids
DBU: 1,8-Diazabicyclo[5.4.0]undec-7-ene
DMSO: Dimethyl sulfoxide
EtP2(dma):
Tetramethyl(tris(dimethylamino)phosphoranylidene)phosphorictri
amid-Et-imin
FTIR: Fourier Transform Infrared
IL: Ionic Liquid
MEA: monoethanolamine
MTBD: 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene
MTPPB: Methyltriphenylphosphonium bromide
NMR: Nuclear Magnetic Resonance
PCIL: Phase-change ionic liquids
PEG200: poly ethylene glycol 200
TBAB: tetrabutylammonium bromide
TWEEN 80: Polyethylene glycol sorbitan monooleate
ChemSusChem
REVIEW
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REVIEW
Shokat Sarmad,* Jyri-Pekka Mikkola,
Xiaoyan Ji

1 32.

CO2 capture with Ionic Liquids (ILs)

and Deep Eutectic Solvents (DESs): a
new generation of sorbents

Contents
2. Ionic liquids (ILs)................................................................................................................................................................................ 4
2.1.1. Physical absorption and Coulombic interactions ..................................................................................................................... 5
2.1.2. CO2 solubility .......................................................................................................................................................................... 5
a) The influence of anion ............................................................................................................................................................. 5
b) The influence of cation ............................................................................................................................................................ 9
c) Novel ILs developed recently................................................................................................................................................. 11
d) Summary ............................................................................................................................................................................... 11
2.2. Functionalization of ILs ............................................................................................................................................................ 11
2.2.1. Cation functionalization ......................................................................................................................................................... 12
Amination: ................................................................................................................................................................................. 12
Fluorination:............................................................................................................................................................................... 12
Carbonylation: ........................................................................................................................................................................... 12
Etherification:............................................................................................................................................................................. 13
Alcoholation: .............................................................................................................................................................................. 13
Hydroxylation: ............................................................................................................................................................................ 13
2.2.2. Anion functionalization .......................................................................................................................................................... 14
Fluorination:............................................................................................................................................................................... 14
Carbonylation: ........................................................................................................................................................................... 14
Amination: ................................................................................................................................................................................. 15
Protic ILs: .................................................................................................................................................................................. 15
Basic ILs: ................................................................................................................................................................................... 16
Phase-change ionic liquids (PCILs): .......................................................................................................................................... 16
Reversible ILs:........................................................................................................................................................................... 16
2.2.3. Dual functionalization of ILs .................................................................................................................................................. 17
2.2.4. IL-IL or IL-small organic molecules mixtures ......................................................................................................................... 17
3. Deep Eutectic Solvents (DESs) ....................................................................................................................................................... 19
3.1. Functional groups for adjusting the properties of DESs ........................................................................................................... 19
Freezing point: ........................................................................................................................................................................... 19
Density: ..................................................................................................................................................................................... 20
Viscosity: ................................................................................................................................................................................... 20

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ChemSusChem 10.1002/cssc.201600987

REVIEW
Surface tension: ...................................................................................................................................................................... 20
3.2. CO2 capture using DESs ......................................................................................................................................................... 21
ChCl-based DESs: .................................................................................................................................................................... 21
Lactate-based DESs:................................................................................................................................................................. 22
Phosphonium- and ammonium-based DESs: ............................................................................................................................ 22
Task-specific DESs: .................................................................................................................................................................. 22
Summary: .................................................................................................................................................................................. 23
Conclusions ......................................................................................................................................................................................... 24
Acknowledgements ............................................................................................................................................................................. 24
References .......................................................................................................................................................................................... 25

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