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Review 1

Muhammad Zia ul Mustafa1

Recent Developments and Applications of
Hilmi bin Mukhtar1,*
Nik Abdul Hadi Md Nordin1 Ionic Liquids in Gas Separation Membranes
Hafiz Abdul Mannan1
Rizwan Nasir2 Flue gas emissions and the harmful effects of these gases urge to separate and cap-
Nabilah Fazil1 ture these unwanted gases. Ionic liquids due to negligible vapor pressure, thermal
stability, and wide electrochemical stability have expanded its application in gas
separations. A comprehensive overview of the recent developments and applica-
tions of ionic liquid membranes (ILMs) for gas separation is given. The three gen-
eral classifications of ILMs, such as supported ionic liquid membranes (SILMs),
ionic liquid polymeric membranes (ILPMs), and ionic liquid mixed-matrix mem-
branes (ILMMMs) along with their applications, for the separation of various
mixed gases systems is discussed in detail. Furthermore, issues, challenges, com-
putational study, and future perspectives for ILMs are also considered.

Keywords: Gas separation membranes, Ionic liquids, Ionic liquid membranes,

Ionic liquid polymeric membranes
Received: October 01, 2018; revised: July 07, 2019; accepted: September 06, 2019
DOI: 10.1002/ceat.201800519

1 Introduction Polymers such as polyethersulfone (PES), polyacrylonitrile

1.1 General Aspects
An enormous amount of gases emitted by industries lead to
global warming [1, 2] resulting in CO2 emission, acid rain [3],
fog, and haze [4]. These emissions are severely affecting human
beings. Moreover, fossil fuels will be the primary source of elec-
trical power generation and main manufacturing processes.
The international energy agency has reported that the emission
of greenhouse gas is increasing by 6 % per annum due to the
usage of fossil fuels as an energy source [5].
Other relevant sources of CO2 emissions are manufacturing
and construction sectors such as cement, iron, and steel indus-
try, as well as ammonia production and fermentation [6]. How-
ever, the rapid progress of human civilization demands taking
control of these emissions to provide a healthy living environ-
ment for human beings. So, it inevitable to capture harmful gas
emissions with suitable techniques. There are many processes
available to treat industrial trail gases or process gases such as
physical and chemical solvents scrubbing, pressure swing
adsorption (PSA), cryogenic distillation, amine absorption, and
membrane separation. However, most of the technologies are
suffering from high energy consumption and high cost. Hence,
designing a new process, new solvents or materials has become
necessary in the gas separation area.
1.2 Background
Membrane technology has numerous advantages over other
separation techniques due to lower energy requirements, com-
pacted size, lower investment cost, and eco-friendly separation.
(PAN), polysulfone (PSF), and polyamide are prominent poly-
mers, contributing effectively in gas separation membranes.
Adding an inorganic filler in the polymer matrix gives rise to
mixed-matrix membranes, with improved permeability and
selectivity well above the upper bound limit [7]. Several studies
state that the addition of an inorganic filler into a polymer
could improve the gas separation performance of the mem-
branes.
Inorganic fillers such as metal-organic framework (MOF),
silica, and multiwall carbon nanotubes (MWCNTs) facilitate
the gas separation performance [7, 8]. Mixed-matrix mem-
branes (MMMs) are considered a revolutionary method to
enhance permeability and selectivity. In these membranes, the
gas separation performance is contributed by an inorganic filler
having molecular sieving ability. These fillers may be porous or
nonporous. However, there is a limitation in polymer and inor-
ganic filler-based MMMs. Researchers have reported that a fill-
er dispersed non-uniformly in a polymer can produce a noni-
deal filler-polymer interfacial morphology, e.g., interface voids
[9].
Moreover, when glassy polymers are used as matrix material,
a poor polymer-filler contact arises, which leads to the develop-
–
1
Muhammad Zia ul Mustafa, Prof. Dr. Hilmi bin Mukhtar, Dr. Nik Ab-
dul Hadi Md Nordin, Dr. Hafiz Abdul Mannan, Nabilah Fazil
hilmi_mukhtar@utp.edu.my
Universiti Teknologi PETRONAS, Chemical Engineering Department,
Bandar Seri Iskandar, 32610 Perak, Malaysia.
2
Dr. Rizwan Nasir
University of Jeddah, Department of Chemical Engineering, Jeddah,
Saudi Arabia.

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ment of leaky interfacial voids and results in poor selectivity.
Another big problem faced during membrane synthesis is filler
agglomeration, because it creates phase separation between fill-
er and polymer, leading to weakening of the composite and
forming non-selective defects [10]. So, the addition of the ter-
nary component can help minimize the polymer and inorganic
interfacial voids issues. Literature has reported that the pres-
ence of ionic liquids (ILs) helps to CO2 absorption in a poly-
mer, resulting in an increase in CO2 permeance and CO2/CH4
selectivity [11]. The presence of ILs helps to form defect-free
interfacial morphology. It functionalizes the fillers present, im-
proving the interfacial morphology issue.
Li et al. [8] reported that an MOF-polymer interfaces by
incorporating an ionic liquid (IL)[bmim][Tf2N] into ZIF-8
cages. It was determined that the incorporation of MOF into
polymers gives weak adhesion and non-selective interfacial
voids. However, the addition of 15 wt % IL@ZIF-8 improved
the CO2 permeability and CO2/N2 selectivity by 45 % and 74 %,
respectively, and 92 % enhancement in CO2/CH4 selectivity
concerning the pure polymeric membrane was achieved. The
results showed that IL@MOFs are favorable fillers of MMMs
for gas separation. Both the MOFs and ILs are easily tunable.
MMMs based on IL@MOFs can be designed to achieve better
gas separation performance for desired tasks. Ban et al. [12]
also described a five times rise of CO2/CH4 ideal selectivity in
IL@ZIF-8 membranes. The sections below provide comprehen-
sive information about ILs and their applications in gas separa-
tion membranes.
2 Ionic Liquids (ILs)
ILs are organic salts that exist in liquid form at or below 25 °C.
They remain fluids at such a low temperature because of con-
siderable size and irregularity of the cation, attached with reso-
nance-stabilized anions. ILs are characterized by negligible
vapor pressure, nonflammability, and high thermal stability,
which make them suitable for different gas separation process-
es.
The first IL reported was ethyl ammonium nitrate by Paul
Walden in 1914, and now ILs have become a major scientific
area. More specifically, ILs were suggested as a CO2 separation
medium by Blanchard et al. in 2001 [13]. Currently, in the last
two decades, ILs have gained tremendous popularity covering
multidisciplinary fields such as chemistry, material science,
chemical engineering, and environmental science [14]. How-
ever, the use of ILs is also limited because of high cost, unclear
toxicities, and potential environmental effects.
ILs are classified into few categories, such as room-tempera-
ture ILs (RTILs) [11], task-specific ILs (TSILs) [15], and poly-
ionic liquids (PILs) [16]. They are recommended as solvents,
catalysts, and reagents in many chemical reactions. Properties
of ILs can be modified with alternation of cations or anions for
specific applications [17]. The cations or anions via functional-
ization can change the properties of the materials such as
hydrophobicity/hydrophilicity and specific chemical interac-
tions. In polymers, ILs can act as wetting agents and these fea-
tures open applications of ILs as solvents in membranes. ILs
have also been reported by Zhang et al. [18], who described
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that ILs act as a solvent and catalyst which controls a catalytic
conversion of cellulose, hemicellulose, lignin, and lignocellulos-
ic biomass into useful chemical products and fuel. Dai et al.
[19] published a comprehensive review of ILs in numerous
important selective oxidation reactions. ILs were found to be
highly efficient catalysts and solvents in these reactions.
In separation processes, the choice of appropriate solvents is
challenging. Ventura et al. [20] reported a detailed review on
the ILs in the extraction of bioactive compounds as a solvent.
The use of ILs provides higher extraction yields compared to
conventional solvents.
Different ILs are under study in membrane synthesis, e.g.,
emim dca, emim tf2n, and emim tcb have been reported by
J. Grunauer et al. [21] in supported liquid membranes for gas
separation. Mannan et al. [22] applied emim tf2n and polye-
thersulfone-based membranes for gas separation. ILs have
shown good potential for gas separations [23]. Important cat-
ions and anions used in gas separation membranes are summa-
rized in Figs. 1 and 2, respectively.
2.1 Types of ILs
TSILs act as a complexing agent which can be used for maxi-
mum loading in the base materials. In this way, these ILs can
absorb high quantities of gas. Davis et al. reported the develop-
ment of an IL-based amine functionality, capable of absorbing
0.5 mole of CO2 per mole of IL [25]. Moreover, complexing
agents are also doped in ILs to increase the solubility uptake of
many solutes [26, 27].
Comparatively, RTILs, more specifically, imidazolium-based
ILs due to the modular nature, are polymerized. Applications
of RTILs cover broad aspects such as green solvents for reac-
tions, bulk fluids, membrane separations, and electrochemical
systems [17]. Imidazolium- and pyridinium-based ILs are
reported as feasible solvents for CO2 separation due to tunable
cation or anion properties to meet the system requirements
[28].
Furthermore, polymeric ILs exhibit higher CO2 absorption
and high mechanical strength [29] values compared to straight
RTILs [30]. Polymerization of the RTIL monomer by changing
the n-alkyl length is helpful to increase the permeability of tar-
get gases, i.e., CO2, N2, and methane (CH4) [31].
2.2 Applications of ILs in Separation Processes
ILs in separation processes cover a wide range, such as electro-
chemical applications, extractive separation [32, 33], and also
membrane gas separations [34]. Membranes based on ILs
exhibit significant benefits for separation of gas mixtures com-
pared to conventional solvent-based membranes because ILs
have much higher solubility values for different gaseous species
[34–36]. Furthermore, IL gas separation membranes work by
gas solubility in the IL comparison to diffusivity [37]. A
detailed description of properties and applications of IL mem-
branes is presented in Fig. 3.
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Review 3

Figure 1. Different cations

used for gas separation
membranes [24].

tial pressure difference of the gas

between the two sides of the mem-
brane. Permeation is related to rate
control and the separation degree
is calculated by the selectivity of
the membrane at a specific pres-
sure, temperature, and flow rate
[38]. Gas separation happens only
if a component passes via the
membrane more quickly than
others. Based on pore sizes of the
membrane matrix, four fundamen-
tal transport mechanisms in gas
separation membranes are report-
ed, namely, Poiseuille flow, Knud-
sen diffusion, molecular sieving,
and solution diffusion. Porous
membranes involve Poiseuille flow,
Knudsen diffusion, and molecular
sieving, in which the separation
process is based on the molecular
size through the small pores in the
membrane matrix. Most commer-
cial applications are based on a
Figure 2. Different anions used for gas separation membranes [24]. nonporous process via solution-dif-
fusion mechanism.
2.2.1 Separation of Gas Mixtures Global warming issues are a crucial factor for CO2 removal
from industrial gas mixtures. RTILs provide easily adaptable
Separation of gas mixtures is performed using porous and non- and tunable properties for the creation of new processes and
porous membranes. The driving force for separation is the par- materials designed to capture CO2 from industrial flue gases

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Figure 3. Properties and applications of IL membranes [45].
[39]. Membrane technology is a fascinating approach to CO2
separation from N2 and CH4 in industrial processes. Polymer
membranes are reported as a long-term substitute to other sep-
aration processes for certain CO2 separation processes [40],
and IL membranes are also recognized to be highly capable of
selective CO2 separation from gas mixtures. For example,
anodic alumina membranes with a definite pore geometry
showed CO2 permeabilities > 1000 Barrer, greater than perme-
abilities reported by others for similar supported ionic liquid
membrane (SILM) systems [41]. The membranes are well-
suited to separate desired gases from unwanted gaseous mix-
tures.
2.2.2 Separation of Sulfur Compounds
Sulfur compounds are also soluble in ILs in
the form of SO2 and H2S. However, a
limited part of sulfur compound removal is
reported in this review paper. Literature
has shown that IL membranes are helpful
in the separation of sulfur compounds. For
example, Jalili et al. reported that the
solubility of H2S in ILs was determined
with the solubility in the sequence as
[bmim][Tf2N] > [bmim][BF4] > [bmim][PF6]
[42]. These IL membranes have the poten-
tial to remove sulfur compounds from the
mixtures.
Figure 4. Polymeric membrane fabrication.
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2.2.3 Separation of Metal Ions
Separation of metal ions is performed using differ-
ent separation techniques such as adsorption of
metal ions on resins, liquid-liquid extraction, or
using membranes such as SILMs and polymeric IL
membranes (PILMs). Liquid-liquid extraction is
considered a conventional technique involving an
aqueous and organic phase; however, the drawback
is the use of the organic phase, which is usually
flammable and toxic [43]. ILs having environmen-
tally friendly properties are reported as promising
green extracting agents, for extracting different
metals such as alkali, alkaline earth, heavy metals,
and radioactive metals [43].
An IL based on the hydrophobic fatty acid is em-
ployed for continuous metal ion extraction of co-
balt ions from Co(II)/Na(I) and Ca(II)/Co(II)/K(I)
mixtures [44]. However, the IL-based metal separa-
tion process is more expensive compared to ion-
exchange resins, because the ILs need higher
volumes of stripping solution. Consequently,
immobilized membranes have been developed as
an effective method of separation. Two types of
membranes, i.e, SILMs and ILPMs, are applied to
remove metal ions with lower IL loss. In SILMs,
ILs are incorporated into the porous support while
in ILPMs the ILs are doped into a dense polymer support.
These types of membranes are mechanically stable. Fig. 3 indi-
cated the properties and applications of IL membranes.
3 Synthesis of Gas Separation
Membranes
3.1 Polymeric Membranes
The synthesis of a pure polymeric dense membrane runs in
three steps: (1) dispersion of the polymer into a solvent, (2)
casting of the dope solution, and (3) drying of the casted mem-
brane. The polymeric membrane fabrication is explained in
Fig. 4.
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3.2 Ionic Liquid Mixed-Matrix Membranes (ILMMMs)
Generally, the ILMMM synthesis involves several additional
steps compared to the synthesis of pure polymeric membranes:
(1) Dispersion of inorganic particles in the solvent, (2) sonica-
tion of the solution to keep particles in suspension, (3) priming
of the polymer with the inorganic particles, (4) casting of the
solution, (5) drying of the membranes. The fabrication of
ILMMMs is illustrated in Fig. 5. Fig. 6 presents schematically
the ILMMMs synthesis.
4 Applications of ILs in Gas Separation
Membranes
4.1 Polymeric Membranes
Membrane technology is applied since 1980 [46]. Commercial-
scale CO2 separation from natural gas is installed at Kvaerner-
GSM. Many polymeric materials have been reported for the
synthesis of dense polymeric membranes. Initially, DuPont
(USA) and Ube Industries Ltd. (Japan) [47] used membranes
Figure 6. Schematic representation for ILMMM synthesis.
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based on polyamides. Polyamide and cellulose acetate were
reported for gas separation membranes for CO2 and CH4 sepa-
ration [48]. Fluorinated polyimides comprising 2,2-bis(3,4-
dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) are
described as attractive membrane materials because of their
remarkable gas permeability and selectivity compared to non-
fluoropolyimides [49–51]. Similarly, improved CO2/CH4 selec-
tivity was found using a 6FDA-based co-PI membrane cross-
linked by ethylene glycerol [52].
The recent gas separation membrane technologies are lead-
ing by polymeric materials due to low cost, excellent mechani-
cal stability at higher pressure, and easy synthesis ability. Poly-
mer-polymer blending is also reported by many authors
[53, 54]. However, these membranes suffer from low perme-
ability or selectivity. There is an inverse relationship between
permeability and selectivity stated by many authors [55–57].
Moreover, plasticization is an issue which arises in dense
polymeric membranes when CO2 concentration in the feed
stream rises. CO2-induced plasticization is a phenomenon
where the permeability of CO2 increases as a function of pres-
sure, whereas selectivity decreases [58]. The presence of CO2
acts as a plasticizer, and dissolved CO2 in polymer causes
Figure 5. ILMMMs.
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swelling in the interstitial place within the chains of the poly-
mer matrix resulting in a transformation in the polymer struc-
ture [59]. Furthermore, polymeric material membranes are
limited by the tradeoff between permeability and selectivity.
These membranes dramatically reduce gas separation perfor-
mance at higher pressure stream of gases due to plasticization.
The morphology of a pure polyethersulfone membrane is illus-
trated in Fig. 7.
Figure 7. FESEM image of a pure PES polymeric membrane
(cross-sectional view) [60].
The image above represents a pure PES polymeric mem-
brane having a smooth, dense, and homogeneous morphology.
However, the plasticization issue in dense polymeric mem-
branes has been reported in which as CO2 concentration in the
feed stream rises, leading to permeant deformation of polymer
chains, thus resulting in selectivity loss at higher pressure feed
streams [58].
4.2 Inorganic Membranes
Inorganic membranes are suitable for gas separation under ele-
vated temperatures and pressures. These membranes may be
porous or nonporous. Porous inorganic membranes include
zeolites, which are favorable for natural gas separation. Zeolite
membranes typically consist of polycrystalline layers of alumi-
nosilicates on porous supports [61]. Zeolite favors more
adsorption of CO2 against CH4, increasing the selectivity
[62, 63]. SAPO-34 zeolite membranes on porous alumina sup-
ports provided a CO2/CH4 selectivity of 86 having CO2 perme-
abilities of 20 000–40 000 Barrer [64]. Himeno et al. developed
a supported hydrophobic Deca-dodecasil 3R (DDR) zeolite
membrane that exhibited a CO2 permeability of 2200 Barrer
having a CO2/CH4 selectivity of up to 400 [65]. These mem-
branes separate CO2 gas by molecular sieving principles
[66–68]. Fig. 8 demonstrates the morphology of deca-dodecasil
3-rhombohedral (dd3r) membranes [69].
Only the main drawback of these membranes is their high
cost and issues to scale up without defects.
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Figure 8. FESEM images of deca-dodecasil 3-rhombohedral
(DD3R) membranes [69].
4.3 Mixed-Matrix Membranes
Kulprathipanja et al. [70] stated that a good option for solu-
tion-diffusion transport type polymeric membranes is an
MMM. MMMs are heterogeneous membranes with the combi-
nation of inorganic materials, reinforced in the continuous pol-
ymeric matrix. Researchers reported extensive work on MMMs
[71–76]. Powell et al. reported [77] that the addition of nano-
particles mainly can contribute three effects to the membrane
permeability, i.e., they can act as molecular sieves to change the
permeability, they can alter the membrane matrix structure to
enhance the permeability, and they can also work as a wall to
decrease the permeability.
MMMs are considered a revolutionary method to improve
permeability and selectivity. Previously, many researchers syn-
thesized and characterized different membranes, and the
results were determined and limited. Dense MMMs, carbon
molecular sieve (CMS)+PES, were tested only at 10 bar result-
ing in a selectivity of only 10.94 [78]. In these membranes, the
gas separation performance is enhanced by an inorganic filler
with molecular sieving ability. These fillers may be porous or
nonporous, such as zeolites and carbon molecular sieves
(CMSs). Metal oxides are porous and silica is nonporous.
4.4 SILMs
Several prospects are available to employ ILs in gas separation
membranes. An easy way to use ILs is the application as sepa-
ration agents in SILMs [17]. SILMs [79] can exist as composites
based on MOFs. In SILMs, the pores of porous membranes are
made wetted with RTILs [80]. By capillary forces, ILs keep
stuck inside the pores.
Kreiter et al. [81] reported that the rates of diffusion, uptake,
and release might have affected the performance of SILMs
because the dissolution/desorption processes play a decisive role
in SILMs compared to pure ILs. Barghi et al. [82] fabricated
SILMs by immobilizing [bmim][PF6] IL on an inorganic mem-
brane. Their results demonstrated that CO2 permeance and dif-
fusivity were 30 times higher than that of CH4 in [bmim][PF6]
SILMs. Santos et al. [83] stated that a poly(vinylidene difluoride)
(PVDF) support showed lower permeabilities of 2.7 and
0.4 Barrer for CO2 and N2, respectively. After incorporation of
ILs in that support, permeabilities were increased up to 325 for
CO2 Barrer and 61.5 for N2 Barrer. However, the drawback of
these membranes is that ILs get loose from the polymer
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network because of swelling and leaching in the liquid phase,
e.g., in pervaporation [84].
To overcome this issue, IL polymeric membranes (ILPMs)
were synthesized. The difference in ILPMs and SILMs is that
ILPMs require polymerizable groups along with proper prepa-
ration techniques or physical blending of the IL with a suitable
polymer in the presence of a compatible solvent. Tab. 1 pro-
vides a summary of permeability and selectivity data for gas
separation in SILMs.
from 19 to 30 [89]. Rehman et al. [93] stated an improvement
in selectivity of up to 53 in ethanolamine-based IL membranes.
Details of a few ILPM performances are given in Tab. 2.
Field-emission scanning electron microscopy (FESEM)
images of ILPMs are depicted in Figs. 9 and 10 for surface and
correctional views, respectively. These images demonstrate a
dense and smooth morphology.

4.5 ILPMs

The physical blending of a polymer with attractive solids or liq-

uid compounds provides a desired shift of properties for better
gas separation performance [89]. The blend is classified into
three types, i.e., miscible, immiscible, and partially miscible
blends. In miscible blends, the physical properties of the blend
are in between the properties of its mixed components, and it
develops a homogeneous phase. However, in an immiscible
blend, components do not produce a homogeneous phase. Par-
tially miscible blends are isotropic heterogeneous blends, and
their properties are in between the miscible and immiscible
blends [90]. Figure 9. Surface micrographs of the synthesized membranes
Poly(ethylene) glycol [91] and Matrimid 5218 [92] in dif- PES-IL-50 at 500 [60].
ferent concentrations to PIM-1 have been reported, which
increased the diffusion, solubility, and selectivity of the glassy However, the primary issue that arises in ILPMs is the
polymer PIM-1. The blending of IL [C6mim][Tf2N] with mechanical strength reduction with the addition of ILs. As
PIM-1 also resulted in an increase in selectivity for CO2/N2 indicated in Tab. 3, the decrease in mechanical strength of few

Table 1. Permeability and selectivity data for gas separation in SILMs.

Ionic liquid SILM supports CO2 permeability [Barrer] CO2/CH4 selectivity

[emim][dca] PES with 80 % porosity [85] 1237 24

[emim][CF3SO3] PVDF support [85] 1171 17

[emim][BF4] PES [85] 968 27

[emim][Tf2N] PES [85] 1702 17

[C6mim][Tf2N] PES [85] 1136 9.9

[emim][CF3SO3] PES [85] 1771 22

[EtMepy][(PFBu)SO3] PES [86] 897 6.6

[EMIM][C(CN)3] PTFE [87] 667 19.4

[EMIM][DCA] PAN [21] 41.5 58

[EMIM][DCA] PS-b-P4VP [88] 600 65

[EMIM][C(CN)3] PTFE [87] 667 57

[EMIM][AC] PVDF[83] 878.8 33.7

C2mimTf2N Anodic alumina membranes [41] 1800 12

C6mimTf2N Anodic alumina membranes [41] 2640 20

[EtMepy][(PFBu)SO3] PES [86] 897 12.3

[EMIM][B(CN)4] PTFE [87] 742 49

[EMIM][C(CN)3 PTFE [87] 667 57

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Table 2. Permeability and selectivity data for gas separation in IL polymeric mem- stated an increment in the permeability with
branes. the incorporation of an IL in poly(RTIL)
[100]. Results showed that the presence of
Ionic liquid Polymer CO2 permeability [Barrer] CO2/CH4 selectivity RTIL increases polymer zeolite adhesion in
10 wt % PIM-COP [89] 812 19 MMMs since RTIL also acts as the wetting
[C6mim][Tf2N] agent for the zeolite. Three components,
SAPO-34, RTIL, and zeolite, were mixed to
[EMIM][BF4] CTA [94] 20 42
determine the optimum ratios. Improve-
[EMIM][TFSA] PVDF [95] 985 19 ment in CO2 permeance was observed
increasing with the loading of IL [101].
[EMIM][BF4] CTA [94] 20 28
Oral et al. described the RTIL loadings of
[EMIM][TFSA] PVDF [95] 985 39 emim[Tf2N] and emim[CF3SO3] towards
MMMs composed of polyimide-zeolite
(SAPO-34) and concluded that reinforce-
ment of emim[CF3SO3] had increased the CO2/CH4 selectivity
whereas emim[CF3SO3] was more selective towards CO2/CH4.
Tab. 4 provides permeability and selectivity data for gas separa-
tion in ILMMMs.

Table 4. Permeability and selectivity data for gas separation in

ILMMMs.

Ionic liquid Polymer CO2 CO2/CH4

permeability selectivity

[EMIM][Tf2N] PIL-based [102] 44 27

[EMIM][Tf2N] Styrene [101] 72.1 32.2

[EMIM][Tf2N] PIL-based [102] 44 39

[EMIM][Tf2N] Styrene [101] 72.1 42.4

Figure 10. Cross-sectional micrographs of the synthesized [HMIM][Tf2N] PTFE [103] 600 18
ILPMs PES-IL-50 at low magnification (500) [60].

ILPMs with the addition of ILs into the polymeric membranes
is a crucial challenge. To overcome this issue, the addition of
an inorganic filler is considered to enhance the mechanical
strength of the gas separation membranes without compromis-
ing the gas separation performance. In the upcoming section,
ILMMMs are described. ILs are also suitable to improve the
interphase morphologies of membranes [97] since ILs are
reported to be excellent contributors to improve the polymer
and inorganic filler compatibility [98].
4.6 ILMMMs
ILMMMs reported by Hudiono et al. [99] showed the combi-
nation of RTILs and zeolite in the polymer matrix. Bara et al.
As an IL comprises an anion and a cation, the effect of these
ions towards separation is further highlighted in the next sec-
tion. FESEM images of ILMMMs depicted in Fig. 11 indicate
that ILMMMs were dense and homogeneous, which resulted in
high gas separation performance of ILMMMs with providing
higher mechanical strength of the membrane due to the pres-
ence of the inorganic filler.
Fig. 12 represents the comparison of SILMs, PILMs, and
ILMMMs on a Robeson’s upper bound curves graph and com-
mercial region of membranes. It is obvious that ILPMs and
SILMs both have good permeability values; however, the selec-
tivity values are just touching the commercial region. ILMMMs
exhibit a lower permeability compared to ILPMs and SILMs
with improved selectivity and are present above the commer-
cial region.

Table 3. Mechanical strength data in IL polymeric membranes.

Membrane Young’s modulus [MPa] Tensile strength [MPa] Extension at break [%]

PVDF [96] 1590 22.12 518.36

PVDF/[emim][B(CN)4] (2:1) 62.08 3.53 213.32

PVDF/[emim][B(CN)4] (1:1) 16.76 2.07 81.06

PVDF/[emim][B(CN)4] (1:2) 4.86 0.40 15.03

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4.7 Effect of Cations and Anions

a) b)
on Gas Separation

The anions of ILs have a greater effect on

CO2 solubility than the cations [104]
because CO2 molecules have a stronger
affinity for anions compared to cations
[105]. Bhavsar et al. [106] studied the pol-
y(diallyldimethylammonium) P[DADMA]
d) cation with the variation of different anions
c) such as carboxylates and sulfonates. They
observed that changing the anion affected
the gas sorption. PILs containing an car-
boxylate (especially acetate) anion showed
attractive CO2 sorption measurement as
well as sorption selectivity over H2 and N2,
in contrast to sulfonates and inorganic
anions. The acetate anion possessed a high
selectivity (CO2/N2 = 114.3).
e) Most literature is dominated by bf4, tf2n,
pf6, dca, otf, and sbf6 anions [106]. Solubil-
ity coefficient and solubility selectivity of
these PILs exhibited the highest values for
acetate-based anions. The reason for the
highest selectivity of acetate-based anions
is their higher basicity to other anions.
That means, changing the basicity of an
Figure 11. FESEM images of (a) pure PES [22], (b) PES/SAPO-34 [22], (c) IL3M, (d) IL3M- anion would increase the solubility of CO2
EDA, (e) IL3M-HA [97]. in an IL; however, it is described that the

Figure 12. Robeson’s upper bound curves showing the general tradeoff between permeability and selectivity for CO2/CH4 separation
from this literature review data.

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Review
solubility of non-reactive gases was not affected by the change
in the acid-base interaction within the IL.
Many types of anions are famous and well-studied, such as or-
ganic anions, carboxylates, sulfonates, sulfonamide, and
inorganic anions (BF4, NO3, and Cl) had a distinctive effect on
CO2 sorption properties. Overall, it is concluded that increasing
the basicity of anions is known to enhance CO2 sorption [107].
Another valuable property which affects solubility is the density
of the IL. Higher selectivity values for P[DADMA][Ac] were
reported because of the lower viscosity of P[DADMA][Ac]
compared to other PILs used in this study [106]. So, the varia-
tion of the anion with increasing anion-basicity and decreasing
IL density improves the sorption value of CO2.
Another property affecting the permeability is the viscosity.
Results have shown that ILs having higher viscosity exhibit
lower solubility. For example, emim tfo had a permeability val-
ue of CO2 684 Barrer compared to emim tf2n that exhibited
811 Barrer at 288 K [108]. Also, high CO2 separation perfor-
mances were observed for IL mixtures comprising anions with
cyano groups, namely as dicyanamide and thiocyanate, which
have lower viscosity values. This means that less viscous anions
are essential to achieve improved CO2 separation performances
[109]. An increase in the alkyl chain length of a cation also
causes a higher viscosity of ILs and consequently a weaker per-
meation of CO2 molecules.
5 Experimental and Computational
Studies
Experimental and computational studies provide a way for in-
corporation of ILs in the membranes. A computational study
plays a vital role in finding the correct combination of ILs with
fillers and polymers. Amro et al. [110] examined the tailoring
of zeolitic imidazolate framework-8 (ZIF-8), an important
MOF, by restraining the pairs of bmim[Tf2N] IL within the
cages of ZIF-8 (IL@ZIF-8). Molecular force fields were estab-
lished for both the ZIF-8 framework and the bmim[Tf2N], and
these were used in molecular simulations of the system. Monte
Carlo simulations were applied for sorption of CO2/CH4 and
CO2/N2 computations. The results exhibited an increment of
CO2 sorption because of the existence of the IL, which im-
proved significantly the CO2 selectivity and capacity.
Moreover, the reason for the variation of CO2 selectivity with
the IL composition in the IL@ZIF-8 complex was examined
and the optimum IL composition for the separation efficiency
was determined. The simulations agreed well with reported
experimental points. The simulation data for CO2/N2 and
CO2/CH4 showed an improvement in separation as IL wt %
increased. The overall modeling evaluation proved that incor-
poration of ILs provided a good accuracy compared to the
experimental work. So, in this way, with the help of similar
research studies, it will be helpful to determine different combi-
nations of IL@ZIFs for CO2 capture and to suggest new
IL@ZIFs composites which can achieve better CO2 selectivity
and capacity.
Azar et al. [111] reported the simulation results for binary
mixtures, which also could be well compared with the separa-
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10
tion performance of the reported membranes. It was examined
that the incorporation of MOFs into the polymers almost
doubles the H2 permeabilities, which demonstrates that MOF/
polymer and MMMs are a better option for H2/N2 separation
technologies.
Less experimental studies have been performed using ZIF-8
because of complex synthesis. Molecular simulation can be
helpful to resolve such limitations. Additionally, it contains a
tool that supports understanding about the processes occurring
primarily at a molecular level by providing a path from the
microscopic details of a system to macroscopic properties of
the experimental interest [25]. This approach has been applied
successfully in zeolites, MOFs, and ZIFs [26–30] and with other
inorganic fillers [112].
6 Prospects of ILs in Gas Separation
Membranes
Currently developed membranes for gas separations are defi-
cient in durability and performance. Research indicates that a
filler dispersed in a polymer nonuniformly can produce a noni-
deal filler-polymer interfacial morphology, e.g., interface voids,
a rigid polymer layer around the inorganic fillers, and particle
pore blockage (in case of porous fillers) [9]. Moreover, when
glassy polymers are used as matrix material, poor polymer-
filler contact arises that leads to the development of leaky inter-
facial voids and results in poor selectivity. Another sincere
problem faced during membrane synthesis is filler agglomera-
tion because it creates phase separation between filler and poly-
mer, leading to weakening of the composite and forming non-
selective defects [10].
Therefore, the issues mentioned above lead to challenges for
better gas separation performance. These membranes get dam-
aged and dramatically reduce the selectivity due to weak
mechanical strength at higher pressure streams. According to
literature, such problems arise due to the incompatibility of
inorganic filler with polymer, resulting in poor adhesion of the
filler with the polymer and nonhomogeneous dispersion of fill-
er in polymers. Consequently, exploring efficient technology is
urgently required. To overcome the plasticization issue, thermal
treatment, cross-linking, and polymer blending has to be modi-
fied.
Mohshim et al. stated that the presence of ILs in polymers
increases the plasticization pressure of a membrane [113]. In
the case of CO2/CH4, IL helps to CO2 absorption in a polymer,
resulting in an improvement in both permeance CO2 and selec-
tivity of CO2/CH4 gas [11]. The presence of ILs help to form a
defect-free interfacial morphology. It functionalizes the present
fillers, enhancing the interfacial morphology issue. Moreover, it
is recommended to improve polymer-filler adhesion and to
form defect-free interfacial morphology. ILs, new solvents, new
fillers as well as surface-modified fillers should be explored
[114] and high-quality composite membranes can be synthe-
sized. Moreover, computational studies are also effective to pre-
dict the gas separation performance for complex synthesis sys-
tems.
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Review 11

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Review
Review: Flue gas emissions and its
harmful effects demand the separation
and capture of these gases. This paper
provides a detailed insight into the
recent developments and applications
of ionic liquid membranes for gas
separation including their applications,
issues, challenges, computational study,
and future perspectives for the
separation of various mixed gases
systems.
Chem. Eng. Technol. 2019, 42, No. 00, 1–15
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15
Recent Developments and
Applications of Ionic Liquids in Gas
Separation Membranes
M. Zia ul Mustafa, H. bin Mukhtar*,
N. A. H. Md Nordin, H. A. Mannan,
R. Nasir, N. Fazil
Chem. Eng. Technol. 2019, 42 (XX),
XXX K XXX
DOI: 10.1002/ceat.201800519
ª 2019 WILEY-VCH Verlag GmbH & Co. KGaA www.cet-journal.com