Review

Using Ionic Liquids to Improve CO2 Capture

Francisco Jose Alguacil and Jose Ignacio Robla *

Centro Nacional de Investigaciones Metalurgicas (CSIC), Avda. Gregorio del Amo 8, 28040 Madrid, Spain;
fjalgua@cenim.csic.es
* Correspondence: jrobla@cenim.csic.es

Abstract: Most of our energy consumption proceeds from the use of fossil fuels and the production of
natural gas. However, the presence of impurities in this gas, like CO2 , makes treatment necessary to
avoid further concerns, such as greenhouse gas emissions, the corrosion of industrial equipment, etc.;
thus, the development of CO2 capture and storage procedures is of the utmost importance in order to
decrease CO2 production and mitigate its contribution to global warming. Among the CO2 capture
processes available, three separation technologies are being used to achieve this goal: absorption,
adsorption and membranes. To overcome some limitations of these methodologies, the joint use of
these technologies with ionic liquids is gaining interest. The present work reviewed the most recent
developments (for 2024) in CO2 capture using ionic liquids coupled to absorption-, adsorption- or
membrane-based processes.

Keywords: CO2 capture; absorption; adsorption; membranes; environment; global warming

1. Introduction
A key factor in reducing our dependency on fossil fuels and, at the same time, im-
proving/maintaining energy efficiencies is the reduction in CO2 emissions, or at least
reducing the emissions of this gas into the atmosphere using so-called carbon capture and
storage technologies.
CO2 capture, especially through chemical absorption using an aqueous amine-based
solvent, is considered the most established and effective approach for the removal of this
Citation: Alguacil, F.J.; Robla, J.I. gas [1]. However, this technology presents some drawbacks, which are normally related to
Using Ionic Liquids to Improve CO2 water content in the solvent that makes it difficult for solvent regeneration [2,3]. With their
Capture. Molecules 2024, 29, 5388. supporters and detractors, adsorption and membrane technologies are also considered as
https://doi.org/10.3390/ alternative procedures to the above in order to remove CO2 from gas streams.
molecules29225388 These three technologies have a trait in common, which is that they can use ionic
liquids (ILs) to improve their performance in the capture of CO2 . ILs are a type of chemical
Academic Editor: Angelo Nacci
that have been considered green solvents due to their properties. This consideration is due
Received: 17 September 2024 to their low vapor pressure (low volatility), high thermal stability and non-flammability.
Revised: 30 October 2024 While ILs are formed exclusively by ions in liquid form at temperatures below 100 ◦ C, one
Accepted: 4 November 2024 characteristic presented by these ILs is the possibility of tunability or modification of the
Published: 15 November 2024 cation or anion forming the salt in order to meet specific applications. In ILs, the cation
and anion can have an organic or inorganic nature, and whereas the cation is commonly
formed by an organic moiety, the anion is formed by organic or inorganic compounds. The
Copyright: © 2024 by the authors.
appealing properties of ionic liquids make them interesting eco-friendly candidates for
Licensee MDPI, Basel, Switzerland.
capturing CO2 from natural gas.
This article is an open access article Some odd points regarding ILs are related to their high viscosity; at the same time,
distributed under the terms and there is some controversy about the “green” nature of ILs [4–7].
conditions of the Creative Commons In addition to their potential uses in cleaning gases, ILs have been considered as
Attribution (CC BY) license (https:// promising solvents, with special properties in organic synthesis, catalysis, electrochemistry,
creativecommons.org/licenses/by/ separation of metals, biomass processing, pharmaceuticals, tribology and energy storage
4.0/). devices, such as batteries, supercapacitors, fuel cells, etc. [8–12].

Molecules 2024, 29, 5388. https://doi.org/10.3390/molecules29225388 https://www.mdpi.com/journal/molecules

Molecules 2024, 29, 5388 2 of 31

Aimed at CO2 capture, some of the recent literature reviewed the utilization of ionic
liquid-functionalized metal–organic frameworks [13,14], different types of ashes [15], poly-
meric ionic liquids [16], ionic liquid-membrane-based systems [17], the application of
machine learning techniques [18], ionic liquid-based advanced porous organic hyper-
crosslinked polymers [19] and the general use of ionic liquids in CO2 adsorption and
absorption procedures [20–26].
The present work presents further data (for 2024) about the applications of absorption,
adsorption and membrane technologies coupled with the use of ionic liquids in CO2
removal or capture from gas streams. Also, recent studies in the literature on the use of
ionic liquid-based aqueous biphasic solvents in this field are presented.

2. Absorption and Ionic Liquids

In absorption-based processing, CO2 is removed from the syngas stream before the
hydrogen purification stage occurs. Ionic liquids are a type of sustainable and efficient
CO2 absorbent because of their apparent advantages in providing a flexible alternative to
standard absorbents such as amine solutions.

2.1. Ionic Liquids in Monophasic Systems

Studies on the process modelling of traditional and conventional amines, i.e., mo-
noethanolamine and methyldietahanolamine, are very limited; thus, a packed column
was used to derive the profiles of the operational variables affecting CO2 loading onto
the diethylenetriamine (DETA) solution [18]. The process model was validated using
experimental data from the literature. Furthermore, the CO2 absorption efficiency of the
DETA solution was compared with that of the ionic liquid 1-n-butyl-3-methylimidazolium
hexafluorophosphate ([BMIM][PF6]). Though the CO2 absorption efficiency of the ionic
liquid was higher than that of the DETA solution, under the same operational conditions,
the apparent disadvantages of the former (higher viscosity and price) should be further
considered without compromising solvent performance.
The next work investigated the use of deep learning models for CO2 solubility pre-
diction in ionic liquids using a dataset comprising 10,116 carbon dioxide solubility data
points in 164 types of ionic liquids at various temperatures and pressures [19]. Deep neural
network models, including an artificial neural network (ANN) and long short-term mem-
ory (LSTM), were developed to predict CO2 solubility in the ionic liquids. The ANN and
LSTM models had convenient test accuracy in predicting CO2 solubility, with R2 values of
0.986 and 0.985, respectively. The ANN model presented reliable accuracy with a lower
computational time (approximately 30-times faster) than the LSTM model.
A 2D computational fluid dynamic (CFD) model in COMSOL Multiphysics® was
developed to investigate CO2 absorption into ionic liquid 1-butyl-3-methylimidazolium tri-
cyanomethanide ([BMIM][TCM]) [20]. Under various experimental conditions, a quadratic
model for absorption (p-value < 0.0001 and R2 > 0.98) was presented. The maximum CO2
concentration was obtained at a pressure of 18.26 bar, temperature of 36 ◦ C, and velocity of
0.825 m/s, whereas the sparger radius to column diameter was 0.414, and column height to
diameter was 2.5.
The next work investigated CO2 capture, storage and conversion using the integration
of plasma-ionic liquid technology [21]. 1-butyl-3-methylimidazolium chloride was utilized
to capture and store CO2 under atmospheric pressure; further, plasma was used to assist in
the reduction of removed CO2 into CO.
Since many investigations regarding CO2 absorption in ionic liquids are based on the
use of imidazolium-based reagents, there is a lack of comprehensive understanding of how
the different factors that govern the gas solubility affect the capture of this molecule onto
these chemicals. Thus, an automated high-throughput setup for the measurement of CO2
solubility in ionic liquids combining six different anions and nine different cations (Table 1),
forming up to 19 different specific ranges of compounds, was used [22]. Among all the ionic
liquids investigated, the maximum void fraction and minimum electrostatic interaction
Molecules 2024, 29, 5388 3 of 31

were for [BMIM][DCA] and [BMPYRR][Triflate], respectively, and the minimum Henry’s
constant, corresponding to maximum CO2 removal, was obtained using [BMP][NTF2 ]. CO2
solubility was better in compounds having fluorinated anions, especially when considering
identical cations.

Table 1. Cationic and anionic moieties used in the calculations.

Cation Anion
1-Allyl-3-methylimidazolium [AllylMIM]
1-Butyl-3-methylimidazolium [BMIM]
1-Butyl-3-methylpyridinium [BMP] Bis(trifluoromethylsulfonyl)imide [NTf2]
1-Butyl-1-methylpyrrolidinium [BMPYR] Dicyanimide [DCA]
1,2-Dimethyl-3-propylimidazolium Hexafluorophosphate [PF6]
[DMPIIM] Triflate [Triflate]
1-Ethyl-3-methylimidazolium [EMIM] Tetrafluoroborate [BF4]
1-Hexyl-3-methylimidazolium [HMIM] Ethyl sulphate [ESO4 ]
1-Methyl-3-octylimidazolium [OMIM]
1-Methyl-3-propylimidazolium [PMIM]
Adapted from [22].

The role of the active hydrogen atom in the ionic liquid anion is a key point to under-
stand the performance of these chemicals for CO2 capture; thus, the physical properties,
CO2 capture and conversion of three hydantoin-based anion-functionalized ionic liquids
([P4442 ][Hy], [P4442 ]2 [Hy], and [HDBU][Hy]) were investigated [23]. The results showed
that the active hydrogen atom in the anion formed anionic hydrogen bonding networks,
resulting in an increase in the melting point and viscosity and decreasing the basicity of the
ionic liquid, losing their properties for CO2 capture and conversion. Whereas [P4442 ]2 [Hy]
shows better carbon dioxide capture and conversion performance attributable to the double-
site interaction, [HDBU][Hy] presented the weakest catalytic CO2 conversion due to its
anion and cation having active hydrogen atoms. The reference reported that the active
hydrogen atom in the anion played a predominant role in the properties and potential
applications of ionic liquids than the active hydrogen atom in the cation.
The next reference investigated the geometry and structural parameters of interaction
of CO2 with several ionic liquids using state-of-the-art quantum chemical tools [24]. A
maximum of up to eight CO2 molecules were computationally found to be possible to inter-
act with the corresponding ionic liquid. The molecular electrostatic potential map (MESP)
analysis revealed that the nucleophilicity of [Suc] moiety is decreased upon an increase
in nCO2 molecules, while the electrophilicity of [P4442 ][Suc] increased with an increase in
CO2 uptake. Moreover, the nature of non-covalent interactions existing between the CO2
molecules and [P4442][Suc] anion was also investigated using non-covalent interaction
(NCI) and quantum theory of atoms in molecules (QTAIM) analysis.
The authors of [25] described the fabrication procedures of imidazolium cyanopy-
rrolide for electrochemical studies in consideration of precursor composition and reac-
tion time. The ionic liquids and different diluents (i.e., acetonitrile, dimethylformamide,
dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) were used to inves-
tigate the influence on conductivity, CO2 mass transport, and electrocatalytic reduction of
CO2 (ECO2R) activation overpotential, together with the effects of electrode materials (Sn,
Ag, Au, and glassy carbon). Acetonitrile was found to be the best diluent to decrease the
onset potential and to enhance the catalytic current density for the production of CO, which
is attributable to the increase in the ion mobility in combination with the silver electrode.
The ECO2R activity of molecular catalysts Ni(cyclam)Cl2 and iron tetraphenylsulfonato
porphyrin (FeTPPS) on the carbon cloth electrode was responsible for the high Faradaic
efficiencies for CO in the presence of the ionic liquid.
Functionalized ionic liquids (IL-Br, IL-BF4 , and IL-PF6 ) were formulated and charac-
terized with a number of analytical tools [26]. These ionic liquids presented an efficient
removal of CO2 from natural gas at ambient temperature. IL-PF6 was the formulation with
Molecules 2024, 29, 5388 4 of 31

the highest CO2 uptake capacity from the natural gas stream, with efficiencies up to 94% in
5 min. It was experimentally found that each gram of IL-PF6 , IL-BF4 , and IL-Br captured
2.02, 1.23, and 1.18 mmol of CO2 , respectively. These efficiencies depended on the flow
rate, being maximum at the lowest value (0.7 sccm). They concluded that CO2 is captured
by the ionic liquids via the amine mechanism, where the lone pair of amino groups of
the ionic liquid attacks the CO2 molecule. Another ionic liquid molecule is protonated by
attracting the proton of the amine-reacted CO2 , and a bimolecular compound of ionic liquid
containing one carbon dioxide molecule is formed. The functionalized ionic liquids utilized
in the investigation contained 3-(2-aminopropyl)-2-ethyl-1-propyl-1H-imidazol-3-ium as a
cationic moiety and bromide, tetrafluoroborate or hexafluorophosphate as anions for the
respective IL-Br, IL-BF4 and IL-PF6 ionic liquids.
Following the tendency of the formulation of new ionic liquids, three ionic liquids
formed by tailoring an imidazolium cation with amino acid anions were synthesized and
characterized [27]. The performance of propane–sultone-modified imidazolium cation
[1MeimPS]+ and amino acid anions (tryptophan ([Trp]− ), tyrosine ([Tyr]− ), and histidine
([His]− )) on CO2 uptake was investigated at 25 ◦ C and pressures up to 4 MPa. Of the
above, [1MeimPS][His] had the best results in terms of CO2 absorption (Table 2) at different
pressures. Moreover, a direct association between CO2 capacity and pressure increase was
observed. The atoms in molecules theory (QTAIM) and Interaction Region Indicator (IRI)
analysis revealed that the CO2 mainly interacted with anions through hydrogen bonding
and van der Waal forces. The natural bond orbital (NBO) analysis showed that stable
charge transfers occurred from CO2 towards the ionic liquids.

Table 2. CO2 absorption (x2 ) using different ionic liquids.

Pressure, MPa [1MeimPS][TRp] [1MeimPS][Tyr] [1MeimPS][His]

1.0 0.34 0.38 0.51
2.0 0.43 0.48 0.63
3.0 0.51 0.53 0.71
4.0 0.59 0.55 0.73

Adapted from [27]. x2 is defined as

liq
n2
x2 = liq liq
(1)
n1 + n2

where n1 liq is the number of CO2 moles in the feed gas and n2 liq is the number of moles of
CO2 adsorbed onto the ionic liquids.
A machine learning framework was developed to predict the density, viscosity, and
heat capacity of a series of anion-functionalized ionic liquids for CO2 capture, especially
those with tetraalkylphosphonium cations and aprotic N-heterocyclic anions (AHAs) [28].
Various feature sets were considered using group contribution-based (GC) descriptors
and descriptors extracted from COSMO-RS sigma profiles (SP) to build Support Vector
Regression (SVR) and Gradient-Boosted Regression (GBR) machine learning models. The
best fit for viscosity used GC-based descriptors and the SVR model, achieving a test set
%AARD of 12.5% and R2 of 0.989. Density was modeled using these same descriptors with
the SVR model framework and was fitted with a test set %AARD of 1.0%.
The absorption kinetics of CO2 into aqueous amino-acid-functionalized monoethanola-
mine glycinate ionic liquid in a stirred cell reactor was investigated [29]. The use of amino
acids was convenient because these chemicals are less volatile and present good resistance
against oxidative degradation. Experiments were carried out in a temperature range
of 25–35 ◦ C and solution concentrations ranging from 0.5 to 2.5 M in the pseudo-first-
order regime. In order to check the fast pseudo-first-order kinetic model assumption, the
dimensionless Hatta number and infinite enhancement factor were calculated. Increasing
Molecules 2024, 29, 5388 5 of 31

the ionic liquid concentration and temperature resulted in an increase in the reaction rate.
The obtained kinetic constants have the same order of magnitude as those existing for
primary amines. The reaction between the ionic liquids and CO2 is explained by the
zwitterion formation (CH2 COONH2 + COO− ), which acted as an intermediate product that
is deprotonated by a base (water, amine, hydroxyl) to form carbamate:

CH2 COONH2+ COO− + base → CH2 COONHCOO− + baseH+ (2)

The authors of [30] presented data about the absorption mechanisms of carbon dioxide
(also hydrogen sulfide and methane) for two imidazolium-based ionic liquids, 1-ethyl-
3-methylimidazolium thiocyanate ([EMIM][SCN]) and 1-ethyl-3-methylimidazolium di-
cyanamide ([EMIM][DCA]). The results reveal that CO2 presented an important affinity for
the interface over the bulk in both ionic liquids. Density profiles showed CO2 ′ s higher den-
sity in [EMIM][DCA] compared to [EMIM][SCN], demonstrating the influence of anionic
composition on CO2 solubility.
A thermodynamic model based on the cubic plus association equation of state was
utilized to calculate the contribution from the chemical reactions between various stoichio-
metric ratios of CO2 and amino acid-ionic liquid (AAIL) (Nm:n, m:n is the stoichiometric
ratio) on CO2 removal [31]. The results show that the larger contribution to the CO2 removal
in [Glu], [Tyr] and [Gln]-ionic liquids, with strong polar groups, was attributable to the
association scheme N1:2. The N1:1 association interaction was the dominant contribution
of [Gly], [Ala], [Val] and [Pro]-ionic liquids, with hydrogen atom or short alkyl side chains,
and [VBIM]-ionic liquid with multiple amino groups. The N2:1 association interaction
was primary between CO2 and [Cho][His] or [Cho][Arg]. In addition, the contributions
of these association effects were greater than that of dispersion and repulsion to CO2
solubility. More amino groups resulted in higher regeneration energy consumption and
did not increase absorbent cyclic capacity. Among the studied AAILs, [Cho][Gly], which
exhibited high cyclic capacity and low energy consumption, had the best potential towards
CO2 capture.
To operate under typical flue gas stream conditions (8–10% CO2 , 18–20% H2 O, 2–3%
O2 , and 67–72% N2 ), one study modeled the combinations of aprotic heterocyclic anion-
type ionic liquids (AHA-IL) with monoethanolamine (MEA) and investigated the carbon
capture effectiveness of these mixtures [32]. All AHA-IL/MEA mixtures exhibited 32%
lower reaction enthalpy (compared to MEA) and 64% lower viscosity (compared to AHA-
IL), improving the properties towards gas capture with respect to amines and a series of
ionic liquids. However, mixtures of the ionic liquids and non-aqueous amine presented an
outlet stream temperature exceeding the degradation temperature of the amine (>120 ◦ C)
due to the exothermic character of CO2 capture on these systems. Against this, systems
containing aqueous amine solutions did not present this characteristic, since water acted as
a coolant, absorbing the excess heat. It is concluded that only the use of solvents consisting
of the ionic liquids and aqueous amine solutions are suitable for CO2 capture operations.
A ferritin-tagged CA variant (DvCA8.0-F) was used in order to investigate its per-
formance for CO2 capture [33]. After 14 weeks of incubation in a 50% MDEA solution at
50 ◦ C, DvCA8.0-F maintained activity nearly equivalent to the initial one. The results show
that DvCA8.0-F reduced the absorption time from 70 to 50 min at 40 ◦ C and desorption
time from 40 to 25 min at 96 ◦ C in 25%MDEA+1%[N1111 ][Gly] (tetramethylammonium
glycinate) solution, with a final CO2 upload and a stripped amount of CO2 at the same
time. DvCA8.0-F exhibits the maximum reaction rate at 96 ◦ C. When the concentration of
DvCA8.0-F was 1.5 g/L, the absorption rate of CO2 reached about 90% of that of the 25%
MEA solution.
Computational frameworks can both facilitate and improve the process of finding
convenient ionic liquids via accurate property predictions in a data-driven manner. The next
reference [34] used a framework consisting of two essential steps: establishing a correlation
between the ionic liquid viscosity and CO2 solubility by joining two deep learning models
(DNN-GC and ANN-GC) and using this correlation to identify the optimal ionic liquid
Molecules 2024, 29, 5388 6 of 31

to yield maximum CO2 uptake capacity. The algorithm generated novel ionic liquids,
1-decyl-2,3-dimethylimidazolium thiocyanate, 1-nonyl-3-methylimidazolium dicyanamide,
and octyltrimethylammonium bis(trifluoromethyl sulfonyl)imide, predicting viscosity and
CO2 solubility at pre-specified conditions (20 ◦ C and 1.5 MPa).
With the goal to create new systems to be used in the removal of CO2 from gas
streams, the well-known amine extractant, MDEA, was mixed with ionic liquids in order
to formulate hybrid solvents and investigated its performance against this gas removal.
Thus, in this work, 30 wt% MDEA was mixed with imidazolium-based ionic liquids in
formulations of 5, 10 15 and 20 wt% [35]. The ILs were 1-butyl-3-methylimidazolium
dicyanamide [BMIM][DCA], 1-butyl-3-methylimidazolium acetate [BMIM][Ac] and 1-
butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][TfO]. The temperature had
a negligible influence on the viscosity above 65 ◦ C, whereas the CO2 uptake onto the
different hybrid systems and the single amine followed the order [BMIM][TfO] + MDEA >
[BMIM][DCA] + MDEA > [BMIM][Ac] + MDEA > MDEA. Experimental results indicated
that the optimum formulation for CO2 removal was 30 wt% amine and 10 wt% ionic liquid.
The system 30 wt% MDEA + 10 wt% [BMIM][TfO] presented fast CO2 absorption kinetics,
whereas the highest absorption rate was reached at 50 bar.
In the next reference [36], different advanced intelligent models, Extreme Gradient
Boosting (XGBoost), Gradient Boosting (GBoost), Light Gradient Boosting Machine (Light-
GBM), and Categorical Boosting (CatBoost) were used to predict the solubility of CO2 in
160 different ionic liquids. This prediction was based on variables such as the temperature,
pressure, and chemical structure of the ionic liquids. The results indicate that the XGBoost
model presented the most accurate results, with root mean square error (RMSE) and R2
values of 0.014 and 0.9967, respectively. It is determined that increasing pressure, decreas-
ing temperature, and lengthening the alkyl chain resulted in an increase in the solubility of
CO2 in the ionic liquids. Moreover, pressure and the number of –CH2 substituents in the
ionic liquid have the most significant impact on the CO2 capture in these compounds.
A number of dicationic ionic liquids composed of di(tetraalkylphosphonium) cations
with tributyl chains and carbon chains ranging from propyl to undecyl, with 2-cyanopyrrolide
acting as the counter-anion, presented an improved thermal stability if compared to
their monocationic aprotic-heterocyclic anion ionic liquid (AHA IL) equivalents [37].
The dicationic ionic liquids all have similar carbon dioxide loading per anion, although
they exhibit an intermediate capacity between the presented monocationic ionic liquids
and 2-cyanopyrrolide anion and that of tetraalkylphosphonium cations with longer (tri-
hexyl(tetradecyl)) and shorter (triethyloctyl) chains. The presence of oxygen resulted in
the formation of phosphine oxides (generic formulation R3 PO), both in monocationic and
dicationic ionic liquids.
An amino-functionalized ionic liquid [G1.0 PAMAM] [2-MI] combined with water
was used in CO2 capture [38]. The ionic liquid was formed by amine groups belonging
to generation 1.0 of dendrimers (G1.0 PAMAM) and 2-methylimidazole (2-MI). The ex-
perimental results showed that 42.71 wt% [G1.0 PAMAM] [2-MI]/H2 O had an uptake of
6.81 mol CO2 /mol (38.5◦ C, aeration rate 100 mL/min), which was much higher than that
of MEA/H2 O. With the combined effect of 2-MI and water, the viscosities of the solution be-
fore and after absorption at 40 ◦ C were 35.3 and 53.8 mPa·s, respectively, which were lower
than the values presented by most of the ionic liquid. The reaction mechanism of [G1.0
PAMAM] [2-MI] with CO2 was attributed to a synergistic combination of a zwitterionic
mechanism and a base-catalyzed hydration mechanism to produce carbamate (primary
and secondary amine and 2-MI) or carbonate/bicarbonate (tertiary amines).
Superbase-derived ionic liquids (SILs) are absorbents that improve the carbon chal-
lenge featured by tunable interaction strength with CO2 via structural engineering, particu-
larly the oxygenate-derived counterparts (i.e., phenolate). In spite of the above, there are
still some concerns about the usefulness of these compounds due to some issues related to
their stability. To resolve these doubts, the next reference developed pyrazolonate-derived
SILs, possessing an anti-oxidation nature, by introducing aza-fused rings in the oxygenate-
Molecules 2024, 29, 5388 7 of 31

derived anions, enhancing CO2 uptake capacity via a carbonate formation pathway (O−C
bond formation) [39].
Ionic liquids, 1-decyl-3-methylimidazolium bis(trifluromethylsulfonyl) imide [IL1],
1-hexadecyl-3-methylimidazolium bis(trifluromethylsulfonyl) imide) [IL2] and triethyte-
tradecylammonium bis(trifluromethylsulfonyl) imide [IL3], were used to investigate their
performance on CO2 capture [40]. Solubility experiments were conducted in the 30−70 ◦ C
temperature range, with pressures up to 1.5 MPa. The results show that [IL2] is the best
candidate for CO2 capture, which is attributable to its longer alkyl chain.
This reference investigates the interactions of three amino acid anions (glycine [Gly],
histidine [His], and arginine [Arg]) with the cation 1-methoxylbutyl-3-methylimidazolium
[MOBMIM] and their performance in the capture of CO2 using quantum mechanical calcu-
lations and molecular dynamics (MD) simulations [41]. The density functional theory (DFT)
calculations elucidate the reaction mechanisms explaining CO2 uptake and cycloaddition.
The cycloaddition reaction with carbon dioxide had a lower energy barrier when arginine
was involved. Results from the MD simulations highlight the higher level of electrostatic
interaction between [MOBMIM][Arg] and CO2 , if compared to the other studied molecules.
Moreover, the Lennard Jones interaction emerges as the dominant type of interaction
in these systems. The diffusion coefficient for CO2 was highest when interacting with
[MOBMIM][Gly].
Being imidazolium-based ionic liquids a popular family of these chemicals, it is not
rare that a number of hydroxyl-functionalized imidazolium ionic liquids were prepared
from the condensation of ethanolamine with glyoxal and formalin in the presence of
acetic acid as a catalyst [42]. The chemical modification of the hydroxyl groups with
epichlorohydrine added new hydroxylpropanoxychloride groups on the imidazolium
cation, which formed a quaternary compound when N-methylimidazolium chloride was
used to produce imidazolium acetate ionic liquids. The usefulness of the fabricated ionic
liquids as single or mixed solvents with saline water to capture CO2 under atmospheric or
55.2 bar pressures was evaluated at room temperature. The data indicated that CO2 uptake
depended on the ionic liquid structure (Table 3), with maximum uptake when pure DImIIL
was used. The CO2 capture efficiency increased from 6.2 (15 min) to 16.8 (30 min) mol
CO2 /kg and from 9.1 (15 min) to 20.0 (30 min) mol CO2 /kg at atmospheric and 55.2 bar
pressures, respectively. In the presence of saline water (70/30), the maximum CO2 uptake
decreases in the case of HIIL (5 mol/kg) and DImIIL (14.1 mol/kg) and increases in the
case of CPIIL (8.0 mol/kg).

Table 3. CO2 uptakes using different acetate-based ionic liquids.

Ionic Liquid CO2 Uptake, mol/kg

HIIL 6.2
CPIIL 4.5
DImIIL 16.8
Adapted from [42]. Time: 45 min. Pressure: atmospheric. HIIL: 1,3-bus(2-hydroxyethyl)-1H-imidazol-3-ium
acetate. CPIIL: 1,3-bis(2-(3-chloro-2-hydroxypropoxy)ethyl)-1H-imidazol-3-ium acetate. DImIIL: 3,3-((1H-2-(3-1-H-
imidazole-3-ium-1,3-diyl)bis(ethane-1,2-diyl))bis(2-hydroxypropane-3,1-diyl)) bis(1-methyl-1H-imidazol-3-ium)
acetate dichloride.

Utilizing monoethanol amine solutions, the catalytic effect of an imidazole series of

ionic liquids ([BMIM][PF6], [BMIM][BF4], [BMIM][HSO4], [BMIM][NO3], [BMIM][CH3COOH],
[BMIM][Cl], [BMIM] [Br], and [BMIM][I]) was evaluated with respect to the CO2 desorption
rate, amount of gas released, and heat duty [43]. The BMIM][PF6 ] catalyst shows better
catalytic activity for CO2 desorption (3.20 × 10−4 mol/L·s at 21.2 h) with respect to the
use of solutions containing only MEA (2.92 × 10−4 mol/L·s after 22.3 h), reducing the
relative heat duty by 17.59%. In addition, the catalytic applicability of [BMIM][PF6 ] for
secondary (N-methyl monoethanolamine) and tertiary amine (2-(diethylamino) ethanol))
systems was evaluated, and the results were similar to those obtained with the primary
amine. The reaction of the primary and secondary amines and CO2 is attributable to
Molecules 2024, 29, 5388 8 of 31

the zwitterion mechanism. As previously mentioned in this review, this is a two-step

mechanism, including the zwitterion formation and carbamate breakdown. In the case of
the tertiary amine, the base-catalyzed hydration mechanism is responsible for CO2 capture.
As in previous references, two imidazolium ionic liquids ([BMIM][PF6] and [BMIM][OAc])
are used for CO2 capture, in this case from biogas, in an absorption process assuming
equilibrium at each stage [44]. After the capture, three processes are investigated, (i) solute-
phase electroreduction, (ii) gas-phase electroreduction, and iii) solute-phase hydrogenation,
in order to produce formic acid as the final product. The results showed that solute-
phase electroreduction (USD 2103/ton) had the highest production cost, followed by
gas-phase electroreduction (USD 986/ton) and CO2 hydrogenation (USD 868/ton). It was
also shown that without any intervention, only hydrogenation can generate a profit. Gas-
phase electroreduction results in the lowest CO2 emissions (0.7 kg CO2 /kg HCOOH). In
terms of production costs, and to reach a convenient parity with hydrogenation, a minimum
current density of 417.3 mA/cm2 is recommended, though these costs can be reduced with
an electricity cost reduction and carbon trading mechanism.
A combination of density functional theory–infrared (IR) conductor-like screening
model for real solvents (COSMO-RS) and molecular dynamic (MD) methods was used to
investigate the impact of hydroxyl functional groups on CO2 removal within dicationic
ionic liquids (DILs) (C5 (mim)2 -(C4 )2 ][NTf2 ]2 , [C5 (mim)2 -(C2 )2 (OH)2 ][NTf2 ]2 [45]. The
latter compound exhibited stronger ion–ion interactions, higher density, and reduced free
volume, which resulted in a reduction in CO2 capture.
Tuning of azole-based ionic liquids for reversible CO2 capture from ambient air was
investigated [46]. The synthesized ionic liquids were [N2224 ] with [Tiz], [Triz], [BeNIM]
or [4-Br-Im] anions, [P4446 ] with [Im] or [BeNIM] anions and [P4442 ] with [Im] or [BeNIM]
counter-anions. Through tuning the basicity of the anion as well as the type of cation,
an ideal azole-based ionic liquid with both high CO2 capacity and good stability was
synthesized. [N2224 ][BeNIM] exhibited the highest single-component isotherm uptake
of 2.17 mmol/g at an atmospheric CO2 concentration of 0.4 mbar and 30 ◦ C and in the
presence of moisture.
A series of amino acid ionic liquids (AAILs) are fabricated via one-step hydrolysis
of lactams, which may act as messengers to facilitate aqueous solutions of multi-tertiary
amines’ fast and increasing CO2 capture [47]. The results indicated that [N1111 ][Maba]-
PMDETA-50% (PMDETA= pentamethyldiethylenetriamine) showed a greater absorption
rate constant value (0.282 min−1 ) than that of MDEA solution (0.043 min−1 ), demonstrating
the activated role of AAILs. At 1.0 bar, [N1111 ][Maba]-PMDETA-50% showed an absorption
capacity of 0.162 g/g, whereas at 0.1 bar, the uptake was 0.095 g/g; the above results were
obtained at 40 ◦ C.
Within the same type of chemical as in the previous reference, a series of protic amino
acid ionic liquids (PAAILs) were synthesized through acid–base neutralization and an
ion exchange reaction [48]. Among the synthesized PAAILs, [DBNH][Maba] (derived
from 1,5-diazabicyclo [0,3,4]non-5-ene (DBN) and meta-aminobenzoic acid (Maba)) had
the largest CO2 absorption capacity of 0.78 mol/mol (0.142 g/g) at 40 ◦ C.
Sterically hindered amines (SHAs), such as 2-amino-2-methyl-1-propanol (AMP) and
ionic liquids, are combining to form different sterically hindered amino acid ionic liquids
(SHAAILs) [49]. Aqueous solutions of these compounds are investigated for CO2 capture.
These absorbents presented remarkable physiochemical properties, CO2 upload of up to
0.92 mol/mol (40 ◦ C and 1.0 bar), and a fast absorption rate (greater than AMP). Among
them, [N1111 ][β-iPrNH-Ala] presented the best characteristics as a CO2 absorbent, which is
attributable to its convenient steric hindrance and ionic nature. Analysis confirms that the
SHAAILs undergo the carbamate-mediated rapid hydrolysis mechanism in absorbing CO2 .
Two more works related to theoretical studies are outlined next. This reference inves-
tigates the efficacy of feedforward neural network and XGBoost models to screen ionic
liquids, which can be used in CO2 capture [50]. Both models were integrated with either
group contribution (GC), molecular structure descriptors (MSD), or hybrid GC-MSD to
Molecules 2024, 29, 5388 9 of 31

give performance comparisons. It was demonstrated that the XGBoost models performed
better over feedforward neural network models, irrespective of descriptor types. Moreover,
the XGBoost-GC-MSD model outperformed the artificial neural network with the group
contribution (ANN-GC) and structure encoding multilayer perceptron (SE-MLP) models
from the previous reference. The Shapley additive explanation analysis identified the top
five influential input features: pressure, temperature, Chi2v, Chi0n, and BertzCT.
In this second work [51], three different machine learning (ML)-based models were
investigated, i.e., gaussian process regression (GPR), LightGBM, and CatBoost, for predict-
ing the solubility of CO2 in various ionic liquids. Three molecular descriptors, i.e., group
contribution (GC), molecular structure descriptors (MSDs), and hybrid GC-MSD, were
used in the three models. Overall, all models exhibited proficient CO2 solubility prediction
in the ionic liquids, with performance varying based on descriptor type. The hybrid GC-
MSD, and particularly the CatBoost-GC-MSD model, consistently outperformed others,
attributed to GC-MSD incorporating a broader array of molecular feature information. As
in the previous reference, the use of the Shapley additive explanation identified pressure,
temperature, Chi0, Kappa2, and EState_VSA10 as the top five influential input features.
The mass transfer intensification and intrinsic mechanisms of different types and
concentrations of metal salts (NaBF4 , KBF4 , KCl, and CuCl2 ) with task-specific ionic liquids
(1-aminopropyl-3-methylimidazolium tetrafluoroborate ([APMIM][BF4 ]) aqueous solutions
for CO2 removal process were investigated using a microchannel reactor [52]. The results
showed that the presence of metal salts enhanced the interaction between metal cations and
ionic liquid anions, thus decreasing the interaction between anions and cations within the
ionic liquid molecules and promoting the chemical reaction between ionic liquid cations and
CO2 . From the above salts, the presence of KBF4 in the solution produced a greater effect
for mass transfer in the CO2 absorption process. The mass transfer coefficient increases as
the gas–liquid phase flow rate rises under slug flow conditions.
Three imidazolium ionic liquids, 1-butyl-3-methylimidazolium acetate ([BMIM][OAc]),
1-butyl-3-methylimidazolium 1,2,4-triazole ([BMIM][Tz]), and 1-butyl-2,3-dimethylimidazolium
1,2,4-triazole ([BMMIM][Tz]), were synthesized to absorb carbon dioxide by the formation
of CO2 adducts [53]. These adducts can be in situ converted into dialkyl carbonates
with alcohols (ROH, R = CH3 , C2 H5 , and C4 H9 ) in a diiodomethane medium under
ambient temperature and pressure. The results indicate that [BMIM][Tz] exhibits the best
CO2 absorption capacity and dimethyl carbonate (DMC) yield, where CO2 capacity is up
to 0.22 g/g and DMC yield (based on methanol) is in the 20.2% order and 9.8% based
on CO2 . The structures of the imidazolium ionic liquids have significant effects on the
absorption of CO2 and subsequent transformation processes, because these structures
influence the binding sites for CO2 absorption, which can combine with the gas to form
CO2 adducts, zwitterion [BMIM-CO2 ], and anionic [Tz-CO2 ] species. Further analysis
shows the structural effects (binding sites and steric hindrance) of the ionic liquids on
the activation of CO2 and methanol, through the elongated C[dbnd]O bond lengths of
CO2 adducts and O-H bond lengths of methanol in ionic liquid–methanol complexes,
respectively, leading to different DMC yields.
The energy analysis and economic evaluation of CO2 capture onto ionic liquids on the
basis of thermodynamic models are of importance, and this is why they were considered in
the next reference [54]. The process simulation resulted in a chemical absorption-dominated
hybrid solvent, consisting of functional ionic liquid choline triazole ([Cho][Triz]) and
sulfolane (TMS) to separate CO2 from shale gas. The total gas capture energy consumption
of 1.65 GJ/t CO2 and the cost of 48.07 USD/t CO2 were achieved using the absorbent when
the mass fraction of the ionic liquid was 60 wt%. Compared with the commercial 30 wt%
MDEA carbon capture process, it reduced the energy consumption and economic cost by
64.16% and 45.59%, respectively.
In this reference [55], the steric effects of amino acid ionic liquid anions (based on
glycine, alanine and valine) with various chemical structures for CO2 capture were inves-
tigated. It was shown that carbamate formation was attributable to a two-step reaction
Molecules 2024, 29, 5388 10 of 31

pathway with a zwitterion intermediate undergoing dynamic proton transfer. It can be

concluded that the favored structural flexibility due to the reduced steric hindrance of the
zwitterion leads to enhanced intermolecular interactions, facilitating proton transfer to
nearby amino acid ionic liquid anions for carbamate formation. Carbamate formation is
kinetically favored, due to a lower barrier height, as the degree of steric hindrance of anions
decreases in the order valine > alanine > glycine.
Four protic ionic liquids were prepared from superbase 1,8-diazabicyclo [5.4.0]undec-
7-ene (DBU) and 1,5-diazabicyclo [4.3.0]-5-nonene (DBN) as cations, with imidazole (Im)
and pyrazole (Pyr) as anions [56]. The results showed that CO2 primarily interacted with
the anions of the protic ionic liquids through van der Waals forces, while the cations and
anions of these chemicals mainly engaged in strong hydrogen-bonding interactions. In
addition, the anions primarily serve as the absorption reaction sites for CO2 , with their
molecular centers of mass being the closest. Molecular density simulations have also shown
that CO2 molecules are preferentially accumulating at the gas/protic ionic liquid interfaces
and that chemisorption governs the gas capture at low pressures in these types of ionic
liquids. Among the studied systems, [DBUH][Pyr] was the most reacting system with CO2 ,
while [DBUH][Pyr] showed lower regeneration energy.
In this reference [57], a series of density functional theory (DFT) calculations and molec-
ular dynamics simulations were conducted to investigate the role of ethyl-3-methylimidazolium
acetate ([EMIM][OAc]) in CO2 capture by poly(ethylenimine (PEI). The results showed that
the formation of hydrogen bonds between the ionic liquid anion and the amino groups of
PEI primarily governed the addition of the ionic liquid to PEI. During the CO2 absorption
process, the ionic liquid anion absorbed CO2 but also produced a dehydrogenation effect
on the amino group of PEI, facilitating the interaction between PEI and CO2 . It was shown
that, in the presence of the ionic liquid, the viscosity of PEI was reduced, and the diffusion
of CO2 increased due to the increase in the absorption rate. CO2 capture by the mixture
ionic liquid + PEI depended on the temperature, decreasing CO2 uptake as the temperature
increased from 25 ◦ C to 60 ◦ C (Table 4).

Table 4. Approximate CO2 uptakes at various temperatures and CO2 partial pressures.

Temperature, ◦ C a mol CO2 /kg PEI + IL b mol CO2 /PEI + IL

25 4.7 5.0
40 4.4 4.6
60 4.1 4.5
Adapted from [57]. XW(PEI) :0.3. a At 0.3 bar. b At 10 bar.

Three anion-functionalized proton ionic liquids were prepared from 1,5-diazabicyclic

[4.3.0]non-5-nonene (DBN) and 2-hydroxypyridine (2-OP), 3-hydroxypyridine (3-OP) or
4-hydroxypyridine (4-OP) [58]. The results showed that [DBNH][2-OP] with an oxygen
atom located in the ortho position of the nitrogen atom presented lower viscosity and larger
free volumes as well as stronger alkalinity, which resulted in a CO2 capture capacity of
about 1.4 mol/mol ionic liquid (about 0.3 g CO2 /g) at 30 ◦ C.
Triazole anion-functionalized ionic liquids (TAFILs) were formulated by combining
low-molecular-weight cations [Cho] or [N222 ] with triazole anions containing a nitrogen-
electronegative site and further mixing with solvents to form physicochemical absorbents [59].
The results indicated that [Cho][Triz]/TMS (sulfolane) (80 wt%/20 wt%) upload 0.125 g
CO2 /g absorbent, which is equivalent to that presented by a 30 wt% MEA solution at 40 ◦ C
and 1 bar but with an enthalpy value (−35.76 kJ/mol) less than half that of 30 wt% MEA
solution. CO2 /CH4 selectivity (191.0) was obtained for the [Cho][Triz]/TMS absorbents.
The results were explained in terms of the relatively weak chemical and physical interaction
between CO2 and TAFIL absorbents.
Molecules 2024, 29, 5388 11 of 31

2.2. Ionic Liquids in Biphasic Systems

The combination of two aqueous solutions of polymer/polymer, polymer/salt or
salt/salt results in the formation of aqueous biphasic solvents [60]; moreover, about 20 years
ago, ionic liquids were introduced as a replacement for the polymer in these solvents [61].
In the CO2 capture process, the gas (or the product) accumulated in one phase (rich phase).
An ionic liquid non-aqueous biphasic absorbent ([TEPAH][CPL]/EG/DGDE)) com-
posed of tetraethylenepentamine (TEPA) caprolactam (CPL), ethylene glycol (EG), and
diethylene glycol dimethyl ether (DGDE) was proposed for CO2 capture [62]. The maxi-
mum gas uptake of the optimal absorbent reached 1.88 mol/mol, with 40% of the saturated
phase volume containing 98% of the mass percentage of CO2 products. The regeneration
energy consumption was 1.88 GJ/t CO2 , approximately 51% lower than that of 30 wt%
monoethanolamine (MEA) aqueous solution. The amino group on the cation [TEPAH]
reacted with CO2 to form carbamate, and the anion [CPL] assisted the proton transfer
during the reaction. The phase separation behavior of the absorbent was governed by the
polarity difference between the CO2 products and the solvent.
A dual-functionalized ionic liquid ([DETA][Lys]) was synthesized using neutralizing
routes from diethylenetriamine (DETA) and lysine (Lys) [63]. It could remove CO2 through
a two-stage reaction, achieving a loading capacity of up to 2.16 mol/mol. N-methyl-2-
pyrrolidone (NMP) was demonstrated to be a suitable phase splitting agent for [DETA][Lys]-
based biphasic solvent by tailoring the polarity and hydrogen bonding effect. Thus, DETA-
carbamate, Lys-carbamate, and HCO3 − /CO3 2− during CO2 absorption were formed. These
carbamate derivatives accumulated in the lower layer, while most of the NMP concentrated
in the upper layer. The CO2 -rich phase took up 53.84% of the total volume and 99.03% of
the captured gas molecule, with a gas uptake of 4.78 mol/L.
Also, the next two references used dual-functionalized ionic liquids such as T-Im
and D-Im. These were synthesized and used as promoters in low-reactive aqueous
methyldiethanolamine to fabricate a CO2 -capturing blend system [64,65]. The gas ab-
sorption kinetic performance of these blends was investigated in the 30−55 ◦ C temperature
range and different pressures (210−710 kPa). The results indicated an increase in the
initial absorption rate with the increase in the DFIL concentration (2.5–10 wt%). It was
assessed that carbamate formation increased with the increase in T-Im concentration in the
blend, whereas T-Im was more favorable towards CO2 capture than D-Im for experiments
carried out at high temperatures. Modeling of the rate kinetic using the zwitterion and
base-catalyzed hydration mechanisms was performed.
In this reference [66], simulation was carried out to model the gas–liquid equilib-
rium of CO2 in two aqueous mixtures of ionic liquids, 1-butyl-3-methyl imidazolium
acetate ([BMIM][Ac]) and amines: [BMIM][Ac] + 1-(2-aminoethyl) piperazine (AEP) and
[BMIM][Ac] + bis (3-aminopropyl) amine (APA). It was concluded that the aqueous mix-
ture (2.0 m [BMIM][Ac] +1.0 m APA) exhibited the highest CO2 removal, followed by
(2.0 m [BMIM][Ac] +1.0 m AEP) compared to the results derived from the use of all the
investigated solvent mixtures.
This reference investigated the use of an aqueous-based biphasic solvent, comprising
methyl monoethanolamine (MMEA), N-methyldiethanolamine (MDEA), and 1-butyl-3-
methylimidazolium tetrafluoroborate ([BMIM][BF4 ]), on CO2 capture from a mixture of
CO2 and CH4 [67]. In this investigation, the ionic liquid was used as a phase separator. This
phase separation is based on the incompatibility of the ionic liquid, with the carbamates
produced as a consequence of the CO2 capture by the amine mixture. The experimental
results showed that the impact of inlet flow rate, stirring rate, and initial methane con-
centration on biogas upgrading was negligible. The utilization of a mass ratio of 3:1 for
MMEA:MDEA produced the best results in terms of methane purity (>96%), CO2 saturated
uptake (0.62 mol CO2 /mol amine) (Table 5), low CO2 heat of desorption (61.45 kJ/mol
CO2 ), best CO2 /CH4 selectivity, and economic efficiency. In the original work (Section 3.6.),
the usefulness of the ionic liquid was mentioned; no further data about its utilization, i.e.,
concentration, were mentioned in the published manuscript.
Molecules 2024, 29, 5388 12 of 31

Table 5. CO2 uploading at various MMA/MDA ratios.

MMA/MDA Ratio CO2 Uploading, mol/mol

1/1 0.42
2/1 0.47
3/1 0.62
4/1 0.62
Adapted from [67]. Stirring rate: 800 min−1 . Flow: 98 L/h·kg. Temperature: 25 ◦ C.

The ionic liquid (diethylenetriamine-3-hydroxypyridine [DETA][3HPyr]) presenting

multiple active sites was combined with diethylene glycol monobutyl ether (DGME) and
water to prepare a biphasic solvent and used for CO2 absorption [68]. The results showed
that after the absorption process, the solvent changed from a single to a two-phase system,
with the presence of highly self-concentrated absorption products in the rich phase. The
volume of the rich phase was about 36.3% of the total solvent volume, whereas its viscosity
decreased to 28.1 mPa·s, with an absorption capacity of 2.67 mol/kg. The stable presence of
carbamic acid in the system was confirmed, thus promoting the absorption capacity. Den-
sity functional theory calculations revealed that DGME stabilized carbamic acid through
intermolecular hydrogen bonding interactions, and highly polar ions generated during
absorption and uneven charge distribution between ions dominated the phase-change
process and increased the water content in the rich phase.
Dual-functionalized ionic liquid [DMAPA][TZ] was synthesized as a primary ab-
sorbent and mixed with phase separation accelerators such as poly(ethylene glycol) dimethyl
ether (NHD) or propylene carbonate (PC) as biphasic solvents to achieve high efficiency,
energy savings, and corrosion inhibition of post-combustion CO2 capture [69]. The results
demonstrated a transition from a homogeneous solvent to a biphasic system upon gas
absorption, where the majority of CO2 was concentrated in the rich phase, attributed to the
formation of hydrogen bonds. Interaction between the ionic liquid and PC is significantly
stronger than that with NHD, resulting in a reduced absorption capacity of IL-PC in com-
parison to IL-NHD, while NHD effectively suppressed the formation of HCO3 − /CO3 2− .
The utilization of the ionic liquids inhibited corrosion through the adsorption–passivation
mechanism; the corrosion rate of the CO2 -rich phase in IL-NHD relative to 20# carbon
steel was 0.1896 mpy, which is 1/865 of the rate of the saturated 5 M methyl ethanol amine
(MEA) solution.
A biphasic solvent based on diethylenetriamine serine ionic liquid/polyethylene
glycol dimethyl ether/water ([DETA][SER]/NHD/H2 O) was developed [70]. The viscosity
of the ionic liquid was regulated by weakening the hydrogen bonding and van der Waals
interactions within the pure ionic liquid by adding NHD and H2 O to [DETA][SER]. The
optimal mass ratio of [DETA][SER]/NHD/H2 O was determined to be 20/40/40 wt%. The
viscosity of this solvent was found to be 7.82 mPa·s, with a total absorption uptake of
1.26 mol/mol of ionic liquid, and where the rich-phase load accounts for 99% of the total
load and occupies 37% of the volume. CO2 was captured by the formation of zwitterions
from the reaction of the primary amines on the cationic [DETA] and anionic [SER] species
with CO2 . Subsequently, proton transfer and hydrolysis of the carbamate esters were
observed. NHD was found to promote phase separation without participating in the
various chemical reactions.
A strategy for biphasic solvent preparation was investigated by combining amine
blends of 3,3′ -diaminodipropylamine (DADPA) or N-methyldiethanolamine (MDEA) and
composite agents, such as 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([BMIM][NTf2 ) and sulfolane (TMS) [71]. The ratio of DADPA:MDEA:TMS:BN:H2 O
(DMTB) used was 2:6:2:1:2. Experiments showed that the DMTB solvent exhibited a
high CO2 capacity (4.59 mol/L in the 50 vol% rich phase) and an efficient phase splitting
rate (within 3 min). The results indicated the formation of anionic DADPACOO species in
the CO2 -saturated phase in the presence of water rather than bicarbonate, while observ-
ing dissociative behaviour in MDEA and TMS. Therefore, the phase separation analysis
Molecules 2024, 29, 5388 13 of 31

revealed that the products of protonated amines and carbamic acid species were highly
polar and preferred to dissolve in the water phase.
In order to gain a better understanding about bicarbonate formation and its influence
on phase separation in the water-[N1111 ][Gly]/EtOH system, further investigations were
carried out through quantum chemical calculations employing density functional theory,
with reaction rate constants determined via transition state theory [72]. Among the various
reaction pathways, the base-catalyzed CO2 hydration reaction becomes predominant, i.e.,
one-step reaction involving anionic [Gly] species, H2 O, and CO2 . A hydrogen atom in
water was transferred to the amino group of glycine anion, forming protonated [Gly]−
and hydroxide combined with CO2 , generating bicarbonate. Furthermore, when the water
content was greater than 5 wt%, an increase in water content promoted the reduction in
hydrogen bonding among products and enhanced the hydrogen bonding of the solvent,
decreasing product self-aggregation.
Despite the fact that biphasic absorbents composed of tetraethylenepentamine, 1-
ethylimidazole, and H2 O (TEH) exhibited remarkable absorption rates and CO2 uploads,
some problems arise in relation to precipitation in the enriched phase, attributable to strong
interactions among absorption products. To avoid this issue, six amino acid ionic liquids
(AAILs) were introduced as split-phase regulators in TEH, developing a liquid–liquid
biphasic absorption system, TEH-AAILs [73]: alanine [Ala], glycine [Gly], serine [Ser],
γ-aminobutyric acid [Gaba], proline [Pro], α-aminoisobutyric acid [Aib]. The formulation
of TEH-[Ser] and TEH-[Ala] presented the best performance in terms of CO2 uptake (about
1.8 mol/kg after 40 min, 101 kPa and 40 ◦ C), though the former presented the best loading
rates at shorter times (up to 10–15 min). Bridged hydrogen bonding structures between
[Ser]–CO2 and H2 O were responsible for this efficiency. Desorption was carried out below
2.5 kPa and 85 ◦ C, with a regeneration efficiency exceeding 85%.
An amino acid-based ionic liquid ([N1111 ][Ala]) (Ala: alanine) was used as a trigger to
start the phase separation of 2-(2-aminoethylamino) ethanol (AEEA) and 1-ethylimidazole
(Eim) solutions (AEH) and to favor CO2 capture [74]. Due to the accompanying phase
change, the CO2 load of AEEA-Eim-H2 O-[N1111 ][Ala] (AEHI) is 1.47-times higher than
that of AEH. The water-shell layer around [Ala]–CO2 and hydrogen bonding were the key
reasons for the phase separation. The formation of the water-shell layer expelled Eim from
the rich phase and, thus, facilitated the proton transfer process, which not only favored the
phase separation process but also decreased the regeneration energy consumption.
An ionic liquid derived from arginine, triethylmethylammonium argininate ([N2221][Arg]),
was synthesized and used to capture CO2 in pure form and from the open air [75]. In
order to improve some drawbacks derived from the use of these AAILs (high viscosity
and low mass transfer), this ionic liquid was mixed with a binary mixture of water and
dimethyl sulfoxide (DMSO), with a variable volume ratio. Increasing the volume of DMSO
in water, the CO2 uptake gradually decreased, reaching a minimum in pure DMSO and the
maximum in an aqueous solution (Table 6). This [N2221 ][Arg] ionic liquid in the aqueous
medium was used to remove CO2 from direct air. The open-air CO2 uptake concentration
value was near 1.01 mol/mol in the aqueous solution of arginine-based ionic liquid.

Table 6. CO2 uptake at various v% DMSO/v% water ratios.

v% DMSO/v% Water Ratio CO2 Uptake, mol/mol

Pure DMSO 0.45
70/30 1.03
50/50 1.22
30/70 1.45
Pure water 1.86
Adapted from [75]. Experiments on pure CO2 .

The efficiency of CO2 absorption was investigated in aqueous MDEA solutions, and
the energy consumption of the process was reduced by designing combined absorbent
Molecules 2024, 29, 5388 14 of 31

systems [76]. For this, an ionic liquid based on the amino acid glycine, known as bis(2-
hydroxyethyl)dimethylammonium glycinate ([M2 E2 A][Gly]), was synthesized and investi-
gated as a carbon dioxide absorbent. The absorption capacity of [M2 E2 A][Gly], its aqueous
solutions and amine + ionic liquid aqueous mixtures was evaluated gravimetrically at differ-
ent temperatures and concentrations of components. The results indicated that there was an
increase in both the absorption capacity and the rate of chemical reaction with carbon diox-
ide when using this ionic liquid as an additive. The H2 O/MDEA/[M2 E2 A][Gly] formula-
tion (50/30/20 wt%) exhibited the highest absorption capacity of 2.98 mol CO2 /kg solution.
Two triazole-functionalized ionic liquids ([N2222 ][1,2,4-Triz] and [N2222 ][1,2,3-Triz])
were used and combined with imidazole organic solvents as phase separation agents to
form a series of systems aimed at CO2 capture [77]. Within a 5:4 mass ratio formulation
([N2222 ][1,2,4-Triz]:1-methylimidazole (N-MI)), CO2 loading is 0.112 g/g of solvent at 40 ◦ C
and 1 bar, in which the CO2 -rich phase accounts for 95% of the total CO2 capacity and
60% of the total volume. The results indicated that [N2222 ][1,2,4-Triz] can react with CO2
to produce carbamate that existed in the CO2 -rich phase, and, as a consequence of the gas
absorption, the original homogeneous liquid evolved into a liquid–solid phase due to the
difference in polarity between imidazole organic solvents and carbamate products and also
to strong intermolecular hydrogen bonding between carbamate products.

2.3. Remarks About Absorption and Ionic Liquids

Though it is difficult to compare results due to the different experimental conditions
used in the various investigations, Table 7 (monophasic systems) and Table 8 (biphasic
systems) summarize a number of CO2 uptake results in order to provide knowledge about
the performance of different systems used in CO2 capture.

Table 7. CO2 uptake values using ionic liquid absorption from monophasic systems.

Absorbent CO2 Uptake, mol/mol Reference

[P4442 ][Hy] 1.90 [23]
MDEA+ [BMIM][TFO] 2 < x < 2.5 [35]
[P66614 ][3-HMPz] 1.29 [39]
[N1111 ][Maba] + PMDETA 1.4 [47]
[N1111 ][Eaca] + PMDETA 1.0 [47]
[DBUH][Maba] 0.58 [48]
[DBNH][Maba] 0.78 [48]
[N1111 ][β-iPrNH-Ala] 0.78 [49]
[BMIM][Tz] 1.02 [53]
[DBNH][2-OP] 1.4 [58]

Table 8. CO2 uptake values using ionic liquid absorption from biphasic systems.

System CO2 Uptake, mol/mol Reference

[TEPAH][CPh]/EG/DGDE 1.88 (40 ◦ C) [62]
[TEPAH][CPh]/EG/DGDE 1.83 (60 ◦ C) [62]
[BMIM][NTf2 ]/MMEA/MDEA 0.62 [67]
[DMAPA][TZ]/water/NHD 1.14 [69]
[DMAPA][TZ]/water/PC 0.95 [69]
[DETA][SER]/water/NHD 1.26 [70]
[N2221 ][Arg]/water/DMSO 1.45 [75]

3. Adsorption and Ionic Liquids

When this technology is used for CO2 capture, the ionic liquid is immobilized onto
the solid material or part of the material intimate structure. The active part for CO2 capture
is not only the ionic liquid, because, very often, the characteristics of the solid material
influence this capture.
Molecules 2024, 29, 5388 15 of 31

Agave bagasse fiber-derived biochar (BCw) was impregnated with 1-butyl-3-methylim-

idazolium acetate ionic liquid. This adsorbent presented the next CO2 removal capacities at
atmospheric (1.47 mmol/g at 25 ◦ C and 1 bar) and moderately high pressure (1.32 mmol/g
at 25 ◦ C and 8.5 bar) under dynamic and static systems, respectively [78]. Biochar-IL
composites improved the CO2 capture capacity, kinetics, and selectivity (CO2 /N2 ) by
4–90% compared with the bulk adsorbents. By increasing the pressure from 1 to 8.5 bar in a
static high-pressure system, the CO2 capture capacity and kinetics of impregnated-biochar
improved two times. Additionally, the biochar-IL composites were regenerated under a
pressure swing adsorption (PSA) arrangement, where more than 70% of the desorption was
attributed to the depressurization of the system. Gas–solid physisorption and gas–liquid
chemisorption at low pressure were responsible for the CO2 loading onto the adsorbent.
Apparently, CO2 capture was not only attributed to the textural properties of the biochar
but also to its surface chemistry.
This reference was related to carbon capture and storage (CCS), in which the CO2
adsorption capacities of a series of elastomer poly(ionic liquid) (PILs) with imidazolium
cations having different alkyl chains were investigated [79]. Three PIL formulations were
investigated: PIL-Me (methyl), PIL-nBum (n-butyl), and PIL-nHex (n-hexyl). The best
results were obtained with PIL having methyl chains (Table 9).

Table 9. CO2 capture by PIL-substituted imidazolium cations at various pressures.

PIL-alkyl Pressure, bar (CO2 Uptake, mg/g)

PIL-me 1.1(9.6), 10.0(159.28)
PIL-n-butyl 0.9 (4.30), 10.1 (111.42)
PIL-n-hexyl 1.0 (4.34), 9.9 (81.81)
Adapted from [79]. Temperature: 35 ◦ C.

To overcome some negative issues (low porosity, limited batch conversion capacity,
and difficulties in reuse) relative to the utilization of poly(ionic liquids) on CO2 capture,
AEROPIL catalysts obtained from the integration of poly(ionic liquid)s in chitosan-based
aerogels were proposed to remediate the above issues [80]. Working in batch mode,
AEROPILs show moderate yields for CO2 conversion; however, high catalytic activity
was achieved when AEROPILs were used to catalyze the CO2 cycloaddition reaction to
epoxides in packed-bed reactors operating under continuous flow.
The effect of encapsulating various imidazolium ILs in porous ZIF-8 was reported to
investigate the adsorption mechanism of CO2 onto the composite adsorbents [81]. Thus, a
number of anions, including bis(trifluoromethylsulfonyl)imide [NTf2 ], methanesulfonate
[MeSO3 ], and acetate [AC], were combined with a 1-ethyl-3-methylimidazolium [EMIM]
cation. These [EMIM]-based ILs@ZIF-8 composites were computationally investigated to
identify suitable materials for CO2 capture. The results demonstrated that the incorporation
of ILs strongly affects the adsorption capability of CO2 , which is highly dependent on the
nature of the ILs inside the ZIF-8 framework, and demonstrated that the incorporation
of ILs into ZIF-8 led to better CO2 uptakes if compared to isolated ILs and pristine ZIF-8.
The [EMIM][NTf2 ]@ZIF-8 composite exhibited higher activity and stability toward the
adsorption of CO2 than the other composites, which was attributed to significant charge
transfer and strong interactions between the fluorinated IL and ZIF-8.
This investigation was performed in order to asses CO2 adsorption capacity and
the CO2 /N2 selectivity of different di-cationic ionic liquids (based on dichlorate 1,8-
diimadozole-3,6-dioxaoctane-bis-(propyl)triethoxysilane (DIL_2Cl)) immobilized in com-
mercial mesoporous silica support (SBA-15) [82]. The highest CO2 adsorption capacity
and CO2 /N2 selectivity were obtained for sample SBA@DIL_2FeCl4 (at 1 bar and 25 ◦ C,
57.31 (±0.02) mg CO2 /g, 12.27 (±0.72) mg CO2 /g). Though the results demonstrated
similar adsorption capacity between the pristine material and the IL-bearing adsorbents,
the presence of the ionic liquids improved the CO2 /N2 selectivity by approximately 3.8-
times. Compared to the results obtained with monocationic ionic liquids immobilized
Molecules 2024, 29, 5388 16 of 31

on mesoporous supports and the same percentage of ionic liquid content, these results
show that the use of dicationic-ionic liquids leads to improved CO2 selectivity due to the
increased availability of coordination sites.
Porous poly(ionic liquid)s was formed by the incorporation of dual-hydrogen-bond
donors (amide and hydroxyl groups) and nucleophiles (Br− ) as multiple effective active
sites for the cycloaddition reaction between CO2 and epoxides [83]. The presence of dual-
hydrogen-bond donors provides two active sites for synergistic catalysis with epoxides and
also increases CO2 adsorption capacity. By regulating the ratio between the ionic liquid
monomer and divinylbenzene, a hierarchical porous structure favorable for the reaction
was fabricated, resulting in optimized catalytic activity comparable to that of bulk ionic
liquid monomers. Furthermore, this catalyst exhibits structural stability exhibited after five
consecutive use adsorption cycles. Analysis of the material indicated that the –OH group
of the ionic liquid, C–O group of amides, and –CH2 produced during polymerization re-
mained unaltered. Moreover, the adsorbents retained their irregular highly dense granular
morphology after the recycling tests. It was concluded that in the catalytic mechanism, the
dual-hydrogen-bond donors and bromide anions synergistically promoted ring-opening
reactions of epoxides; at the same time, amide groups served as basic sites to favor CO2
uptake during the reaction process.
The formation of composites between metal–organic frameworks and ionic liquids
suggested the creation of new materials, amenable for use in the removal of CO2 (and other
toxic gases). On this basis, a core–shell composite utilizing ionic liquids and metal–organic
frameworks based on the dissolution–diffusion mechanism was fabricated [84]. The affinity
of ionic liquids towards various gas molecules, particularly their strong compatibility for
CO2 , allow only this gas to be loaded, while rejecting other gases. CO2 exhibits strong
interactions with the amino groups present in [TETA][Lys] (formed by reaction of tri-
ethylenetetiamine and L-lysine). The composite presented a good separation selectivity for
CO2 /C2 H2 , CO2 /CH4 and CO2 /N2 . Breakthrough experiments confirmed the effective-
ness of [TETA][Lys]@ZIF-8 in removing trace amounts of CO2 from various gas mixtures
(Table 10).

Table 10. The various gas mixtures used in the removal of CO2 by [TETA][Lys]@ZIF-8.

Mixture Gas and Elution Time

CO2 /C2 H2 (50/50) CO2 6 min, C2 H2 2.5 min
CO2 /C2 H4 (1/99) CO2 230 min, C2 H4 < 1 min
CO2 /CH4 (15/85) CO2 30 min, CH4 < 1 min
CO2 /N2 (10/90) CO2 60 min, N2 < 1 min
CO2 /CH4 /C2 H6 /C3 H8 (15/85/4/1) CO2 20 min, CH4 < 1 min, C2 H6 < 1 min, C3 H8 5 min
CO2 /N2 /O2 (1/79/20) CO2 140 min, N2 < 1 min, O2 < 1 min
Adapted from [84]. Temperature: 25 ◦ C. Pressure: 100 kPa.

Acidic and basic sites of catalysts play a key role in CO2 capture and activation. In this
reference [85], Zr, N-ZnO/ZnAl-LDH-IL composites in ionic liquid (tetraethyl ammonium-
based) and methanol systems were formulated and utilized to catalyze, from ethylene
glycol (EG) and CO2 , the synthesis of ethylene carbonate (EC). The composites showed
stronger basic sites due to the presence of reactive groups on the catalyst surface through Zr
doping, resulting in an increase in pyridinic-N groups. Carbon atoms near to pyridinic-N,
as strong basic sites, activated CO2 and EG. The replacement of Zr in the catalyst by La, Fe,
Ce or Cu did not increase EC evolution but decreased it, with the best results derived from
the use of Zr, followed by La = Ce > Fe > Cu.
Another example of the joint use of metal–organic frameworks and ionic liquid is
given. Composites for carbon dioxide separation consisting of two task-specific ionic liq-
uids, namely, tetramethylgunidinium imidazole [TMGH][IM] and tetramethylgunidinium
phenol [TMGH][PhO], impregnated in ZIF-8 were developed and compared with results
derived from the use of pristine ZIF-8 [86]. Though pristine ZIF-8 presented better CO2
Molecules 2024, 29, 5388 17 of 31

uptake concentrations (especially in the 0.4–1 bar pressure range) than the two composites,
the formulation [TMGH][IM]@ZIF-8 demonstrated better CO2 adsorption performance
if compared with [TMGH][PhO]@ZIF-8. This is attributed to its strong attraction toward
CO2 , resulting in a higher CO2 /CH4 selectivity of 110 (0.01 bar), a value which decreased
to 12 with the increase in the pressure (1 bar); in any case, these are better than the values
presented by the pristine framework. The dual-site Langmuir (DSL) model was developed
to fit experimental adsorption data:

nA bA P n b P
qe = + B B (3)
1 + bA P 1 + bB P

where qe (mmol/g) is the equilibrium uptake of the gas, P (bar) is the equilibrium pressure
and nA , bA , nB and bB are the fitting parameters. In the present case, the values for CO2 are
nA 0.6118, bA 0.4604, nB 100 and bb 0.000302 with r2 0.9998. The respective values for CH4
are 1.0, 0.0068, 1, 0.6883 and 0.9998.
The design and synthesis of improved mesoporous silica-supported ionic liquid-based
adsorbents for carbon dioxide capture are of interest. Thus, 1-ethyl-3-methylimidazolium
tetrafluoroborate, 1-ethyl-3-methylimidazolium ethyl sulfate and 1-ethyl-3-methylimidazolium
methylsulfate ionic liquids were supported on the surface of mesoporous silica to study its
performance in this capture [87]. Theoretical results show the strong interaction of molecu-
lar bodies with CO2 gas molecules, which is evident from the experimental findings. The
results demonstrate that the increase in CO2 uptake is attributed to weaker cation/anion
pair interactions, favoring lattice expansion and greater CO2 interstitial spaces.
The role of defective UiO-66-NH2 and its ionic liquid-encapsulated counterparts were
investigated by using hydrochloric acid as a defect modulator, followed by post-synthetic
ionic liquid encapsulation for CO2 capture [88]. The defective UiO-66-NH2 showed an
enhanced carbon dioxide uptake capacity compared to its non-defective counterpart be-
cause of the improved microporous structure. It was found that there exists an optimum
linker deficiency, yielding the highest CO2 capture performance due to enhanced textural
properties, overcoming the negative effect of reduced CO2 -philic amine groups. Further-
more, ionic liquid-encapsulated UiO-66-NH2 showed a slight improvement in CO2 /N2
selectivity but exhibited a notable reduction in CO2 uptake capacity because of decreased
textural properties. In the investigation, 1-methylimidazole [1-MIM] and 1-bromobutane
were used as precursors to form the ionic liquid [BMIM][Br].
Another composite was formed by incorporating magnesium and piperazinium-based
solid ionic liquids (SoILs) into HKUST-1 to favor its water stability and selective CO2
capture performance [89]. An eco-friendly process was used in the synthesis of bimetallic
Mg(x)-HKUST-1; the process used water as the unique solvent with stirring and microwave
treatment. The SoILs were incorporated into the pore structure of Mg(15)-HKUST-1 through
wet impregnation. Different ratios of Mg were used for the synthesis. Among them, 15%
Mg exhibited the highest improvement in CO2 capacity (5.32 mmol/g) and CO2 /N2 se-
lectivity (27) compared to HKUST-1 (CO2 capacity 4.2 mmol/g; CO2 /N2 selectivity 17).
Once Mg(15)-HKUST-1 was impregnated with 10% SoIL, the CO2 capture performance
was further improved. Moreover, 10% SoIL/Mg(15)-HKUST-1 and Mg(15)-HKUST-1 main-
tained, respectively, 92.4% and 85.3% CO2 adsorption capacity after 20 days of exposure to
a humid environment (60% RH) at 25 ◦ C, improving the 26% shown by HKUST-1.
Ionic liquid tetraethylammonium glycine ([N2222 ][Gly]) and a porous molecular sieve
(SBA-15) were combined to fabricate a porous amino acid ionic liquid composite 60 wt%
[N2222 ][Gly]@SBA-15 with microporous and ultra-microporous structures and used to
investigate the dynamic (fixed-bed column) CO2 adsorption breakthrough in various
conditions [90]. The results indicated that the CO2 adsorption capacity was up to 1.8 mmol
CO2 /g at 25 ◦ C, 1 bar and zero humidity. This loading capacity increases to 2.4 mmol
CO2 /g at 15% RH due to the mechanism change of the CO2 reaction with primary amine
from 2:1 under dry gas to 1: 1 stoichiometry in the presence of moisture (Table 11).
Molecules 2024, 29, 5388 18 of 31

Table 11. CO2 uptake at various relative humidities.

Relative Humidity, % CO2 Uptake, mmol/g

0 1.8
15 2.4
25 2.1
35 1.9
55 1.6
Adapted from [90]. Temperature: 25 ◦ C. 1 v% CO2 containing gas mixture balanced with N2 .

Further, CO2 adsorption breakthrough behaviors were fitted to the Avrami kinetic
model: h i
n
qt = qe 1 − e−(kA t) A (4)

where qt is the CO2 uptake at an elapsed time, qe is the gas molecule uptake at the
equilibrium (saturation) time, whereas kA and nA are the adsorption rate and constant
of the model, respectively. The CO2 adsorption rate of 60 wt% [N2222 ][Gly]@SBA-15 was
controlled by intra-particle diffusion. The temperature for CO2 desorption was 90 ◦ C.
Of the four types of porous liquids (I, II, II, and IV) [91–94], porous organic cage
(POC)-based type III porous liquids, and especially those PCOs solvated in ionic liquids,
were used less in terms of CO2 capture. Thus, this reference investigated the CO2 capac-
ity of porous liquids composed of the POC cluster and [BPy][NTf2 ] (N-butylpyridinium
bis((trifluoromethyl)sulfonyl)imide) or [BMIM][NTf2 ] (1-butyl-3-methylimidazolium bis-
(trifluoromethyl)sulfonyl)imide) [95]. The results indicated that the CO2 capacity of porous
liquids containing [BPy][NTf2 ] was higher than that of the latter POC-ionic liquid formula-
tion. Dynamical and structural analyses indicated that the CO2 diffusion rate was lowered
by the interface between the solvent and the POC cluster in both systems. In the case of the
imidazolium derivative, the lower CO2 capture was attributable to the ring part of cation
molecules being concentrated above the cage window, hindering the CO2 entering the POC
cluster inside.
A series of hydroxyl-functionalized ionic hyper-crosslinked polymers were prepared
through a one-step Friedel–Crafts reaction, involving hypoxanthine (HX) and benzimida-
zole (BI) as the monomers, along with various halohydrocarbon crosslinking agents [96].
These polymers presented a high specific surface area (558–1480 m2 /g), microporous struc-
ture, and unique ion sites. Their CO2 adsorption capacity of 157.5 mg/g at near 0 ◦ C and
1 bar is of interest. Additionally, these polymers function as recyclable catalysts in the
cycloaddition reaction of CO2 and epoxides, enabling the conversion of CO2 into cyclic
carbonates, with rates up to 99%, even without a co-catalyst. A mechanism investigation
revealed that the introduction of hydroxyl groups in the polymer is the key to improving
catalytic activity through a synergistic catalytic effect.
The functionalization of ordered mesoporous silica MCM-48 with two amino acid-
based ionic liquids (AAILs) ([Emim][Gly] and [Emim][Ala]) produced a couple of com-
posites (AAILs@MCM-48), which were used to investigate their performance on the CO2
capture and CO2 /N2 separation [97]. Under post-combustion flue gas conditions, both
composites improved CO2 capture in comparison to pristine MCM-48. Maximum CO2
uptake was yielded with the 40 wt.%-[Emim][Gly] composite, with values of 0.74 and
0.82 mmol/g at 0.1 and 0.2 bar, respectively, and 30 ◦ C. The CO2 /N2 selectivity of the
composites was also improved at 0.1 bar, with a value of 17 for the above composite
formulation, which compares very well to the value of 2 of the unmodified MCM-48.
[Emim][Gly] and [Emim][Ala] corresponded to 1-ethyl-3-methylimidazolium glycine and
1-ethyl-3-methylimidazolium alanine formulations, respectively.
The problem associated with the viscosity is always present when ionic liquids are
used, in any field. Trying to mitigate this problem, ethylene glycol, propylene glycol,
1,3-propanediol, and diethylene glycol were added to three different ionic liquids: 1-ethyl-
3-methylimidazolium 2-cyanopyrrolide ([EMIM][2-CNpyr]), 1-ethyl-3-methylimidazolium
Molecules 2024, 29, 5388 19 of 31

tetrafluoroborate ([EMIM][BF4 ]), and 1-butyl-3-methylimidazolium tetrafluoroborate

([BMIM][BF4 ]). This was to decrease (averaging 51%) the viscosity of pristine ionic
liquids [98]. Since the encapsulated mixtures [EMIM][2-CNpyr]/1,3-propanediol and
[EMIM][2-CNpyr]/diethylene glycol presented the lowest volatility (0.0019 and 0.0002 mmol/h
at 25 ◦ C, respectively), they were further investigated for CO2 capture. These results
showed that [EMIM][2-CNpyr]/diethylene glycol capsules had higher uptake capacity at
initial carbon dioxide concentrations of near 500 ppm (0.66 against 0.47 mol of CO2 /kg
when 1,3-propanediol was used). These results indicated that glycols can be effective not
only to reduce ionic liquid viscosity while increasing physisorption sites for CO2 removal
but also that encapsulation was useful to inhibit the evaporation of volatile modifiers.
Guanidine-functionalized basic binuclear poly(ionic liquid)s (P-DBTMGH) were pre-
pared via free radical copolymerization [99]. The introduction of guanidine ionic liquids
into the framework of GB-PILs improved the alkalinity in the structure, thus favoring
CO2 surface adsorption and activation ability. Bromide-containing binuclear sites help to
increase the ion density of bromide and promote the occurrence of ring opening. Using
epichlorohydrin as a probe substrate, P-DBTMGH could efficiently catalyze the cycloaddi-
tion reaction of the simulated flue gas (15 vol% CO2 + 85 vol% N2 ), without any co-catalyst
or solvent, and chloropropene carbonate (CPC) with a selectivity and yield of 99% and
96% was, respectively, obtained. Theoretical interpretations explained the synergistic
effect of guanidine basic sites and bromide-containing binuclear sites on the CO2 activa-
tion and ring opening of epoxides, which provide a choice for high-value utilization of
low-partial-pressure CO2 from flue gas.
The ionic liquid (1-carboxypropyl-3-methylimidazolium bromine (1-C-3-M)) was
grafted onto a metal–organic framework without any additives and in a single-step oper-
ation [100]. In this composite, an amine bond through reaction of the carboxyl group in
the ionic liquid with the amino group in the framework was formed. Thus, a composite
material, MIL-101-NH2 -1-carboxypropyl-3-methylimidazolium bromine (1-C-3-M@MIL-
101-NH2 ), was the result. This composite, employed as a catalyst for CO2 cycloaddition,
reached a target product PC (propylene carbonate) yield of 91.7% under the conditions
of 80 ◦ C, 1.0 MPa, and a reaction time of 4 h and without the addition of any co-catalysts
or solvents. These results improved the respective one derived from the utilization of the
pristine framework (25.6%). The catalytic activity benefitted from the synergistic effect
of Lewis acidic Cr centers and nucleophilic bromide anions, as well as the high specific
surface area and CO2 affinity of 1-C-3-M@MIL-101-NH2 .
New composites, such as ZIF-8 structures with two functionalized ionic liquids
(1-propyl-3-methylimidazole hydrochloride ([C1 MIm]Cl), and tetraethylenepentamine-
2-methylimidazole ([TEP][MIm]), were prepared and used to investigate CO2 capture [101].
The results indicated that the original [PMIm]Cl had low CO2 absorption capacity at ambi-
ent temperature and pressure, whereas the functionalized ionic liquids had a maximum
CO2 capture capacity of approximately 0.31 mol/mol. The formulation containing 20 wt%
tetraethylene pentamine-2-methylimidazole ([TEP][MIm]) exhibited the highest CO2 cap-
ture capacity of around 1.93 mol/mol. The synthesized ZIF-8-ionic liquids demonstrated a
maximum CO2 capture capacity of approximately 2.22 and 2.16 mol/mol at 20 and 10 wt%
ionic concentrations, respectively, with a porous ionic liquid addition of 1.0/100 g.
Two amino-functional ionic liquids were synthesized in deionized water: tetraethylene-
pentamine-2-methylimidazole ([TEPA][MIm]) and diethylenetriamine-2-methylimidazole
([DETA][MIm]) [102]. Two zeolite imidazolidin-8 frames (ZIF-8-W and ZIF-8-M) were
prepared in methanol and deionized water. Based on the above, the porous ionic liquid ZIF-
8-W/[TEPA][MIm] with the best performance and ZIF-8-W with the best environmental
friendships were fabricated. The difference in adsorption capacity between ZIF-8-W and
ZIF-8-M was about 36.3 mL/g; the maximum mass change rates of the two ionic liquids
after immersion in ceramic and stainless-steel tubes for seven days were 0.78% and 0.29%,
respectively. On the premise of ensuring fluidity, the maximum loading capacity of ZIF-8-
W/[TEPA][MIm] for pure CO2 reached 2.22 mol/mol, and the maximum capture capacity
Molecules 2024, 29, 5388 20 of 31

for CO2 in artificial flue gas reached 2.03 mol/mol, which was 21.9% and 31.6% higher than
the maximum capture capacity of pure ionic liquids, respectively. When [TEPA][MIm] in the
porous ionic liquid reacts with CO2 , it conforms to the characteristics of “zwitterions”. Note
the difference in the formulation of tetraethylenepentamine-2-methylimidazole between
this reference and the previous one [101].
Including the different pathways to fabricate composites, the impregnation method
was used to form a hybrid composite of 1-butyl-3-methylimidazole acetate ([BMIM][Ac])
and the molecular sieve SAPO-34 [103]. This composite was used to investigate its perfor-
mance on CO2 capture. The results showed that SAPO-34 retained its original structure after
[BMIM][Ac] impregnation. The CO2 uptake of 1.879 mmol/g at 30 ◦ C and 1 bar resulted
in a 20.6% enhancement when compared to that of the pristine SAPO-34 (1.558 mmol/g).
With an acceleration of the CO2 loading kinetics, the apparent mass transfer resistance
for CO2 capture was reduced by 11.2% compared with that of the pure [BMIM][Ac]. The
differential scanning calorimetry method revealed that the loaded sample had a lower CO2
desorption heat than that of the pure [BMIM][Ac], and the CO2 desorption heat of the
loaded samples was between 30.6 and 40.8 kJ/mol.
As is well known, graphene has multiple uses, which include the removal of gases.
Density functional theory calculations were employed to evaluate the possibility of utilizing
graphene as a carrier material to increase the CO2 adsorption uptake of tetramethylammo-
nium 2- hydroxypyridine salt ([TMA][HPy]) [104]. The results indicated that BN co-doped
fluorinated graphene represented a carrier material, which weakens the interaction between
cations and anions while enhancing the charges of oxygen and nitrogen in the anionic
species of the ionic liquid. The above resulted in an increase in the CO2 adsorption capacity.
The adsorption sites of the ionic liquids and their properties were influenced by doping
atoms in the graphene, because these atoms produced alterations in the distribution of
surface electrostatic potential. Compared to hydrogen-terminated graphene, fluorinated
graphene was a more stable carrier material due to its higher binding energy with this ionic
liquid. The higher binding energy was not derived from the direct interaction between
doped atoms and the ionic liquid but, rather, from the impact of doped atoms on the
electronic structure of graphene. With methanol acting as the solvent, the adsorption of the
ionic liquid on various graphene surfaces was a spontaneous exothermic process.
Following the concept of a one-step synthesis procedure, an amino-functionalized
imidazolium ionic liquid as an organic monodentate ligand was used in the fabrication of
microporous Cu-based I-MOFs (ionic metal–organic frameworks) [105]. Precise tuning of
the adsorption properties was obtained by incorporating aromatic anions, such as phenoxy,
benzene carboxyl, and benzene sulfonic acid group, into the I-MOFs via an ion exchange
process. The I-MOFs showed high thermal stability and uptake of 5.4 mmol/g under
atmospheric conditions for the selective adsorption of CO2 , again improving the results of
using the pristine framework. The active sites of microporous Cu-MOF are the ion basic
center and unsaturated metal, and electrostatic attraction and hydroxyl bonding between
CO2 and modified functional sulfonic groups are responsible for the adsorption.

Remarks About Adsorption and Ionic Liquids

Similar to our comment in Section 2.3, in the present case, it is also difficult, if not
unrealistic, to conduct a comparison between the different systems used to remove CO2
from gaseous streams. In any case, Table 12 presents a series of CO2 uptakes onto various
ionic liquid adsorption systems in order to see the variety of figures than one can obtain
with the different systems.
 Similar to our comment in Section 2.3, in the present case, it is also difficult, if not
unrealistic, to conduct a comparison between the different systems used to remove CO2
from gaseous streams. In any case, Table 12 presents a series of CO2 uptakes onto various
ionic liquid adsorption systems in order to see the variety of figures than one can obtain
Molecules 2024, 29, 5388 with the different systems. 21 of 31

Table 12. CO2 uptakes onto ionic liquid adsorbent systems.

Table 12. CO2 uptakes
Systemonto ionic liquid adsorbent
COsystems.
2 Uptake, mmol/g Reference
[BMIM][AC]-biochar
System 1.47
CO2 Uptake, mmol/g [78]
Reference
C:E:M1:P280% 0.53 [80]
[BMIM][AC]-biochar 1.47 [78]
SBA-15@DIL_2FeCl
C:E:M1:P280% 4 1.30
0.53 [82]
[80]
PDVN-5
SBA-15@DIL_2FeCl 4 0.22
1.30 [83]
[82]
PDVN-5
[TMGH][IM]@ZIF-8 0.22
0.40 [83]
[86]
[TMGH][IM]@ZIF-8
[H2Pi][HSO 4]2-Mg(15)-HKUST-1
0.40
6.05 [86]
[89]
[H2 Pi][HSO4 ]2 -Mg(15)-HKUST-1 6.05 [89]
[EMIM][2-CNpyr]/diethylene glycol
[EMIM][2-CNpyr]/diethylene glycol
0.66
0.66
[98]
[98]
Cu-AFIL-M-SB
Cu-AFIL-M-SB 5.40
5.40 [105]
[105]

4.4.Membranes
Membranesand andIonic
IonicLiquids
Liquids
Ionic
Ionic liquid-based membranesare
liquid-based membranes arebeing
beingconsidered
consideredas aspromising
promisingmaterials
materialsfor
forCOCO22
capture and/or separation due to their permeation and selectivity properties. Though
capture and/or separation due to their permeation and selectivity properties. Though the
investigations in this field use a number of operational devices, one useful item is
the investigations in this field use a number of operational devices, one useful item is in the
in
form of hollow fiber membrane modules (Figure 1), which allow for experiments
the form of hollow fiber membrane modules (Figure 1), which allow for experiments in ain a con-
tinuous basisbasis
continuous and and
also also
using different
using operational
different options.
operational options.

Figure 1. Commercial hollow fiber membrane module to investigate CO2 permeation phenomena.
Phases entering the module in counter-current operational form (co-current form is also possible,
and the way (tube or shell sides) in which the phases feed the module). Module length: 28 cm. Fiber
length: 15 cm. Effective membrane area: 1.4 m2 .

In these membrane systems, also in reference to mixed-matrix membranes, the ionic

liquid is supported into the micropores of the membrane or formed part of the membrane
as a consequence of the membrane casting process.
A composite membrane composed of ethanolamine-based ionic liquids and poly(vinyl
alcohol) (PVA) was developed to investigate its usefulness for CO2 capture and CO2 /CH4
separation [106]. From all the formulations investigated, the results showed that the
higher CO2 permeabilities were obtained with [m-2HEA][Pr] and [2HEA][Pr] (165 and
185 barrer, respectively). The investigation also concluded that the [BHEA][Bu] formu-
lation produced membranes with the highest CO2 /CH4 selectivity (241) and stability
(−4.2 barrer/h). The above formulations corresponded to the respective compositions of
N-methyl-2-hydroxyethylammonium propionate, 2-hydroxyethylammonium propionate
and bis-2-hydroxyethylammonium butanoate.
Supported ionic liquid membranes containing aprotic N-heterocyclic anion ionic liq-
uids in an inorganic inert support exhibit CO2 /N2 permselectivity values of 640 at 35 ◦ C
and 0.03 bar CO2 [107], which represents conditions similar to post-combustion carbon cap-
ture (PCCC) from a natural gas power plant. A Fickian model fitted to the experimental data
estimated CO2 permeability, in direct air capture conditions, of 10,400 barrer and a CO2 /N2
Molecules 2024, 29, 5388 22 of 31

permselectivity of 4000 for the best-performing ionic liquid (triethyl(octyl)phosphonium

4-bromopyrazolide ([P2228 ][4-BrPyra])). The most important criterion for high selectivity is
a large equilibrium constant for binding between the ionic liquid and CO2 , which resulted
in high carbon dioxide solubility. Ionic liquids with smaller molar volumes and with no
fluoroalkyl chains enhanced N2 rejection. Low viscosity and high ionic liquid molar density
also enhanced CO2 /N2 permselectivity and CO2 capture.
The triphenylbenzene-dimethoxyterephthaldehyde-covalent organic framework (TPB-
DMTP-COF) was modified with an imidazolium-based ionic liquid ([EMIM][NTf2 ]) to
overcome disadvantages presented by the use of COFs, and then the mixed-matrix mem-
branes were prepared by introducing IL@COF into PIM-1 (PIM: polymers of intrinsic
microporous) [108]. The ionic liquid modification resulted in a material TPB-DMTP-COF
with better CO2 affinity and narrowed pore size but also further improved the interfacial
compatibility among PIM-1 and TPB-DMTP-COF. Therefore, the introduction of IL@COF
into the PIM-1 membrane can lead to an increase in the CO2 /N2 separation properties of the
resulting membranes. Among the various formulations, 3.0 wt% IL@COF/PIM-1 mixed-
matrix membranes show CO2 permeability and CO2 /N2 selectivity of near 9138 barrer and
20.2, respectively. Such separation performance exceeds the 2008 Robeson upper bound.
Mixed-matrix membranes (MMMs) based on Pebax® 1657 were obtained utilizing
synthetic silico-metallic mineral particles (SSMMPs) functionalized with [BMIM][NTf2 ]
ionic liquid [109]. For the membrane fabrication, an ethanol/water mixture was used as
a solvent, with the SSMMP/ionic liquid content varying from 0.5 to 20% by the weight
of the polymer. Gas permeability and ideal selectivity were measured at 25 ◦ C and dif-
ferent pressures, ranging from 1 to 7 bar. The presence of SSMP/ionic liquid reduced
the flexibility of the PEO chains, resulting in better CO2 /N2 and CO2 /CH4 selectivities.
In the CO2 /N2 system, the highest selectivity was reached at lower filler concentrations,
gradually decreasing as the filler load increased. The MMM-0.5 wt% formulation resulted
in the highest selectivity of near 92. The membrane CO2 permeability increases with an
elevated filler content, from 84.21 for pure Pebax® 1657 to 1927 barrer for MMM-20 wt%
at 4 bar. The majority of the obtained MMMs have separation performances above the
2008 Robeson upper bound. In the CO2 /CH4 system, the membranes performed below
Robeson’s curve. However, the addition of 5%, 10%, and 20 wt% of SSMMP/ionic liquid
resulted in performances very close to the 1991 Robeson upper bound.
The use of double-network gels can also be used in the removal of toxic components
from gas streams. Pebax 1657, composed of a semicrystalline polyamide block, was the first
network in the ion gel membrane [110]. The usefulness of this block is that it served to form
a network to dissipate the loaded energy. In the present investigation, the polyamide block
was interpenetrated with a tetra-PEG hidden-length network, which is highly stretchable
and compatible with the ionic liquid 1-ethyl-3-methylimidazolium tricyanomethanide. This
high mechanical strength allowed researchers to develop an ion gel membrane, retaining
92.5 wt% of the ionic liquid with the convenient performance towards CO2 capture. The
as-formed ion gel membrane had a CO2 permeability and CO2 /N2 permselectivity of
3100 barrer and 43, respectively. The permeability of the toxic gas across the ion gel
membrane increased with the increase in the relative humidity without compromising the
CO2 /N2 permselectivity (Table 13). However, the increase in the temperature from 30 to
80 ◦ C increases CO2 permeability but decreases CO2 /N2 permselectivity. The stability in
the CO2 permeation was maintained for more than 10 days under a relative humidity of
80% at 80 ◦ C. The above data fulfil the requirements for the utilization of this membrane in
the capture of CO2 from flue gases released by coal-fired power plants.
Molecules 2024, 29, 5388 23 of 31

Table 13. Influence of the relative humidity on CO2 permeation and CO2 /N2 permselectivity.

Relative Humidity, % CO2 , Barrer CO2 /N2

0 1450 26
20 1600 26
40 1800 26
60 1900 26
80 2000 26
Adapted from [110]. Feed gas: 50/50 mol/mol CO2 /N2 . Temperature: 80 ◦ C. Atmospheric pressure.

A thin-film composite mixed-matrix membrane was fabricated using an ionic liq-

uid and zeolitic imidazolate framework-8 (ZIF-8) dispersed in a polymerizable ionic
liquid (PIL) matrix for CO2 separation [111]. A PIL comb copolymer, i.e., poly(1-allyl-
3-methylimidazolium bis(trifluoromethanesulfonyl)imide-co-poly(ethylene glycol) methyl
ether methacrylate) (poly(AMIM-TFSI-co-POEM), PAP), was synthesized via free radical
polymerization. The ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([EMIM][TFSI]) served to promote CO2 solubility, while 60 nm sized ZIF-8 nanoparticles
acted as a size-sieving agent. The crystalline and pore structures of ZIF-8 were maintained
in the composite membrane, with no significant PAP/ionic liquid infiltration into the pores
of ZIF-8. The 600 nm thick TFC-MMM with the PAP/IL/ZIF-8 ternary system exhibited a
CO2 permeability of 1017 GPU, CO2 /N2 selectivity of 33, and CO2 /CH4 selectivity of 13,
values which fulfilled the commercial criteria required for post-combustion CO2 capture.
Two ionic liquids were used for the preparation of cellulose acetate (CA)–ionic liquid
blend membranes. The ionic liquids were 1-butyl-3-methylimidazolium hydrogen sulfate
([BMIM][HSO4 ]) and choline glycine ([Cho][Gly]), as they present adequate CO2 dissolution
properties [112]. Several composite membranes were prepared through the solvent casting
technique, showing that the ionic liquids strongly interacted with the C=O groups of
cellulose acetate, which exhibited high affinity with CO2 . In the case of the first ionic liquid,
a reduction in the available sites that allow for strong intermolecular interactions with CO2
resulted in a decrease in the capture of this gas compared to that of pure cellulose acetate.
In the case of choline glycine, the reduction was compensated by the presence of specific
groups in the ionic liquid, which presented high affinity towards CO2 . It is concluded that
the CA-[Cho][Gly] mixed membranes had better CO2 removal capacity, in addition to other
advantages, such as non-toxicity and low cost.
In this investigation [113], 3D-printable materials based on ad hoc synthesized pho-
tocurable imidazolium ionic liquids, 1-(4-vinylbenzyl)-2-methyl-3-butylimidazolium bis-
(trifluoromethanesulfonyl)imide ([C4 vBMIM][NTf2 ]) and 1-(4-vinylbenzyl)-2-methyl-3-3,3-
dimethylbutylimidazolium bis(trifluoromethanesulfonyl)imide ([(CH3 )2 C4 vBMIM][NTf2 ]),
were examined. Polymerization was carried out on formulations containing a crosslinking
monomer (PEGDA). The investigation confirmed the reactivity of both formulations, mak-
ing them suitable for the digital light processing 3D-printing technique. Membranes were
then tested through high-pressure CO2 loading analysis to estimate their capture efficiency,
comparing the results with the standard room-temperature ionic liquid counterpart. The
results showed an increase in the gas removal when the pressure increased from 0 to
40 bar at 25 ◦ C. Complex gyroid-like structures incorporating the synthesized ionic liquids
were 3D printed, showing the ability of these materials to be processed with 3D-printing
technology while maintaining the CO2 capture performance of ionic liquids.
In order to avoid some drawbacks (poor mechanical properties, limited stability or low
gas permeability), an investigation to prepare double-network ion gel membranes with both
high strength and remarkable gas separation performance was performed [114]. Whereas
the membrane with the poly[VEIM][TFSI]:[EMIM][DCA] (70 wt%) formulation presented a
CO2 permeability of 464 barrer and CO2 /N2 separation of 63, surpassing the 2008 upper
bound, the membrane formed of poly[VEIM][TFSI]:[EMIM][TFSI] (80 wt%) did not reach
this upper bound (PCO2 = 866 barrer and CO2 /N2 separation of 31). In the above formu-
Molecules 2024, 29, 5388 24 of 31

lations, [VEIM][TFSI] and [EMIM][DCA] stand for 1-vinyl-3-ethylimidazole bis (trifluo-

romethanesulfonyl) imide and 1-ethyl-3-methylimidazolium dicyanamide, respectively.
Imidazolium-based ionic liquid monomers (IL1: 1-cyanomethyl-3-vinylimidazolium
bromide and IL2: 1-carboxymethyl-3-vinylimidazolium bromide) were co-polymerized
with two functionalized monomers of acrylamide (AM) and butyl acrylate (BA) [115], and
the influence of the chemical structures for PIL-based copolymers on their performances of
derived membranes for CO2 /N2 separation was investigated. These PIL-based composite
membranes were formed coating the copolymer solutions on the surface of a commercial
polysulfone (PSF) membrane. It was experimentally observed that the best results were
yielded from the use of the membrane containing IL-1 and acrylamide, with a CO2 perme-
ability of 76 GPU and CO2 /N2 selectivity (53), resulting in 262% and 61% increases when
compared with the use of single PSF membranes.
Two amino-functionalized PILs (1-cyanomethyl-3-vinylimidazolium bromide and
(4-aminoethyl-1-vinylimidazolium bromide) hydrobromide) were used in the fabrication
of composite membranes. In this fabrication, the formed PIL-based solutions were cast
on the superior part of polysulfone ultrafiltration membranes, aiming to investigate the
influence of the chemical structures on the separation performance of the NH2 -carrier-
based membranes [116]. The membranes presented experimental CO2 /N2 selectivity of
near 174 when the mobile carrier of 2-(1-piperazinyl) ethylamine sarcosine (PZEA-Sar)
was introduced into the amino-functionalized PIL-based membranes. The above mixture
had a synergistic influence from both fixed-site and mobile carriers and, thus, promoted
CO2 -facilitated transport.
The introduction of graphite-like phase carbon nitride (g-C3 N4 ) nanosheets and in-
teraction networks (PGCNs) built up, taking advantage of the dipole-level quadrupole
moment interactions between the ether-oxygen groups contained in polyethylene oxide
(PEO) and CO2 [117]. Membrane surface defects were compensated by coating the ionic
liquid on the surface of the membrane, creating a PEO@g-C3 N4- supported liquid mem-
brane (PGCN/ILX SILM). The results (Table 14) showed that the membrane containing
[EMIM][ACO] 30 wt% presented the best overall performance.

Table 14. Performance of supported liquid membranes (SLMs) derived from g-C3 N4 and PGCN.

SLM Ionic Liquid, wt% GPU CO2 /N2 Separation

20 1577 32
PGCN/[EMIM][AcO] 30 1396 58
40 976 50
20 990 38
PGCN/[BMIM][BF4 ] 30 937 39
40 839 34
Adapted from [117]. Temperature: 25 ◦ C. Pressure: 25 bar. [EMIM][AcO]: 1ethyl-3methylimidazole acetate.
[BMIM][BF4 ]: 1-ethyl-3-ethylimidazole tetrafluoroborate.

Remarks About Membranes and Ionic Liquids

Obviously, comparisons of the various ionic liquid–membrane system are also sub-
jective; thus, as in the above technologies, these authors opted to show (Table 15) results
derived from the investigations for the readers’ benefit. The results on CO2 /N2 selectivity
are included because this pair is the most extensively studied using this technology.
 derived from the investigations for the readers’ benefit. The results on CO2/N2 selectivity
are included because this pair is the most extensively studied using this technology.

Table 15. CO2 permeabilities and CO2/N2 selectivity using ionic liquid membranes.
Molecules 2024, 29, 5388 25 of 31
Ionic Liquid CO2 Permeation, Barrer CO2/N2 Reference
[2HEA][Pr] 185 [106]
Table 15. [P
CO 2 ][4-BrPyral]
2228permeabilities and CO2 /N2 selectivity 10,400
using ionic
a liquid 640
membranes. [107]
[EMIM][NTF
Ionic Liquid
2]
CO2 Permeation, Barrer
9138 CO2 /N2
20 [108]
Reference
[BMIM][NTf2] 192 92 [109]
[2HEA][Pr] 185 [106]
[EMIM][NTf
[P2228 ][4-BrPyral] 2] 10,400 a 610 640 33 [107] [111]
[EMIM][NTF
[VEMIM][TFSI]:[EMIM][DCA]
2 ] 9138 464 20 63 [108] [114]
[BMIM][NTf2 ] 192 92 [109]
a Modeled.
[EMIM][NTf2 ] 610 33 [111]
[VEMIM][TFSI]:[EMIM][DCA] 464 63 [114]
5. Conclusions
a Modeled.

This work reviewed the utilization of different separation technologies (absorption,

5. Conclusions
adsorption and membranes) together with the use of ionic liquids to improve CO2 capture.
This work reviewed the utilization of different separation technologies (absorption,
With the logical operational variables among these technologies, a general overview (Fig-
adsorption and membranes) together with the use of ionic liquids to improve CO2 cap-
ureture.
2) can bethe
With established. The COvariables
logical operational 2 stream feeding any of the technologies allows for the
among these technologies, a general overview
capture of this gas and the rejection
(Figure 2) can be established. The CO of2the CO2-depleted
stream feeding anygas stream
of the (containing
technologies other
allows for non-
captured toxicofgases).
the capture this gasTwo options
and the areofaccomplished:
rejection the CO2 -depletedIn gas
onestream
of them, captured
(containing CO2 is
other
desorbed from the
non-captured corresponding
toxic material
gases). Two options or solution forIneither
are accomplished: one ofcapture and storage
them, captured CO2 is(CCS)
desorbedutilization
or further from the corresponding
of the gas. In material or solution
the second for either
(or first option capture and storage
depending of the(CCS)
point of
or further
view), CO2 isutilization
convertedofinto
the agas. In the by-product
suitable second (or first option
at the timedepending
of capture.of the point of
view), CO2 is converted into a suitable by-product at the time of capture.

Figure 2. Scheme of different types of carbon dioxide capture/separation processes.

As alternatives to CCS (CO2 capture and storage), CCU (CO2 capture and utilization)
and ICCU (integrated CO2 capture and utilization) are key strategies to develop zero or
even negative carbon processes. Current investigations on CO2 capture are the first step
for its industrial applications, but to afford the scaling-up of these investigations, there are
some points that need to be resolved, i.e., the viscosity of ionic liquids and, sometimes,
relatively low mass transfer. The industrialization of these various strategies depends on
various issues: cost-effective CO2 ionic liquid adsorbents, efficient conversion protocols,
stable materials (ionic liquids, metal–organic frameworks, membranes, etc.) as well as
suitable equipment to achieve this capture in an industrialized form. Also, and no less
important, we need to investigate these systems on real gas streams to evaluate the real
performance of these proposals in real situations.
Challenges to consider (without any particular order) include the following:
- Development of polymeric membranes for CO2 capture and separation, since these
membranes present certain advantages, i.e., low energy demand and small equipment
volume.
Molecules 2024, 29, 5388 26 of 31

- Enhancement of CO2 separation through the development of poly(ionic liquids) con-

taining amino groups due to the tunability of the cation and anion, as well as the high
CO2 affinity towards the amino groups.
- Development of ionic metal–organic frameworks (I-MOFs) and other materials of
interest, like graphene and ionic liquids.
- Development of porous ionic liquids, formed of an ionic liquid and a suitable solid
porous material, which can improve CO2 capture and storage.
- The use of 3D-printing technology in the development of complex gyroid-like struc-
tures, incorporating ionic liquids.
- Usage of highly efficient catalysts for the conversion of low-partial-pressure CO2
under mild conditions.
- Development of materials to improve low-concentration CO2 capture.
- Replacement of aqueous amine solutions for the capture of CO2 in post-combustion
technologies. The application of functionalized ionic liquids, i.e., amino acid ionic
liquids, in carbon dioxide (CO2 ) capture seemed to be promising; however, some ques-
tions needed further investigations, like analysis of the interaction of amino groups
in these amino acid ionic liquids with CO2 , evaluation of the energy consumption of
CO2 capture, improvement in their (solvents) high viscosity and low mass transfer.
- Improvements in amine solvent regeneration and decrease in degradation of the
amines with absorption/regeneration cycles.
- Development of functionalized solvents with improved characteristics: low volatility,
high mass capacity, and low energy consumption for CO2 capture.
- Utilization of chemisorption with biphasic solvents, being this a low-energy strategy
for separating CO2 from industrial flue gas. Investigation of the solvent degrada-
tion and changes in water content can be difficult in terms of the phase-splitting
performance.

Author Contributions: Conceptualization, F.J.A. and J.I.R.; methodology, F.J.A. and J.I.R.; investiga-
tion, F.J.A. and J.I.R.; writing—original draft preparation, F.J.A.; writing—review and editing, F.J.A.
and J.I.R.; funding acquisition, J.I.R. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by CSIC, grant number 202250E019.
Informed Consent Statement: Not applicable.
Acknowledgments: To the CSIC (Spain) for support. To M.I. Maher for checking the English.
Conflicts of Interest: The authors declare no conflicts of interest.

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