Renewable and Sustainable Energy Reviews 145 (2021) 111062

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Renewable and Sustainable Energy Reviews

journal homepage: http://www.elsevier.com/locate/rser

A review on the recent advances in mixed matrix membranes for gas

separation processes
Ashwin R. Kamble, Chetan M. Patel, Z.V.P. Murthy *
Department of Chemical Engineering Sardar Vallabhai National Institute of Technology, Surat, 395007, Gujarat, India

A R T I C L E I N F O A B S T R A C T

Keywords: Gas separation processes are amongst the most important operations in the refineries and gas-related industries.
Gas separation Recently, many efforts are being dedicated towards modifying the gas separation properties of existing polymers
Polymer to further expand their use for extensive industrial gas separation applications. Mixed matrix membranes
2D materials
(MMMs), which are organic–inorganic hybrid membranes, have been proposed as the alternative approach to
Inorganic fillers
Mixed matrix membranes
intensify the comprehensive gas separation performance of the polymeric membranes. In this regard, we analyze
and review the recent scientific and technological advances in the development of MMM’s, including the
emerging class of inorganic fillers like two-dimensional (2D)materials, that have been the focus of much recent
work for gas separation. The review also discusses the current issues associated with the filler materials and
further provides an outline to overcome the emerging challenges for the future development of high performance
MMMs.

1. Introduction
Membrane-based gas separation process is to separate the gases from
a gas mixture by passing them through the membrane (preferentially
made up of polymer). The inlet feed stream which is normally at
elevated pressure comes in contact with the membrane surface (Fig. 1).
Based on the difference in gas permeation rates, more permeable
gaseous components pass across the membrane because of a driving
force, and accumulate on the permeate side, whereas, the components
which transport slower accumulate on the retentate side. The driving
force accountable for the separation of gas components is the partial
pressure gradient between the feed and permeate phase which also can
be stated as the product of mole fraction and total pressure.
In recent years, the use of membranes has been increased in the in­
dustries, specifically which have activities related to gas separation and
gas emissions. They are currently being used in various gas separation
applications viz., O2/N2 separation for oxygen enrichment, CO2/CH4
separation for biogas upgrading, separation of H2 from CO for syngas
ratio adjustment, CO2/N2 separation to stop the direction emission of
CO2 in the atmosphere, etc., as the technology provides significant ad­
vantages such as low capital investment and minimum energy re­
quirements [1,2]. These applications are extended further with the
economic viabilities of membranes to achieve a successful gas
separation process. For instance, as per the International Energy Agency
(IEA) reports, worldwide demand of natural gas is expected to rise by 3%
in the year 2021 after showing a great befall in the year 2020 by 4% [3].
With this rise, membrane market is predicted to raise at considerable
rate in the gas separation industries.
On the other hand, features viz., no phase change, good chemical and
mechanical properties of the membrane, compact size, and economical
operation make the membrane technology an alternative choice to the
conventional methods of gas separation (cryogenic distillation, absorp­
tion, and pressure swing adsorption) [4]. It is also believed that the
technology will help to reduce environmental bourdon by obtaining a
higher concentration of pure gases. On the other hand, use of the
membranes in gas separation is predicted to be five times larger in 2020
that in the year 2000 [5]. In this regard, a number of membrane mate­
rials are being investigated and different successful improvements are
accomplished to date. Plenty of the research work is still going on for
investigation of the new materials and for developing new membrane
structures which would lead to obtaining higher membrane selectivity
and permeability. Separation of gases is obtainable with both porous and
nonporous types of membranes. The porous membranes possess pore
size between 0.5 and 10 μm, which is sufficiently larger than the size of
gases, i.e., the kinetic diameter of the gas molecules [6,7]. Therefore, gas
molecules preferably colloid more with each other than the membrane

* Corresponding author.
E-mail addresses: zvpm2000@yahoo.com, zvpm@ched.svnit.ac.in (Z.V.P. Murthy).

https://doi.org/10.1016/j.rser.2021.111062
Received 31 May 2020; Received in revised form 23 February 2021; Accepted 30 March 2021
Available online 14 April 2021
1364-0321/© 2021 Elsevier Ltd. All rights reserved.
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

Table 2
Permeability and selectivity data for different polymers [1,15].
Polymer O2 Permeability N2 Temp. O2/N2
Type (Barrer) Permeability (0C) Selectivity
(Barrer)

PTMSP 6100 3388 – 1.8

PC 1.5 0.260 35 5.76
CA 1.6 0.330 25 4.8
Polyimide 2.1 0.320 35 6.6
(Matrimid
5218)
PDMS 1000 600 35 1.7
Fig. 1. Schematic of membrane gas separation process. PMP 2700 1350 – 2
PIM-1 370 92.5 – 4
Teflon AF2400 1600 800 25 2
walls, affecting the separation abilities of the porous membranes. As a
PIM-7 190 42.22 – 4.5
consequence, dense membranes are mostly employed in gas separation
in which gas transport is primarily achieved by both solubility and
diffusivity difference of the gases. Solubility difference is associated with air separation.
the molecular interaction of the membrane with the gases which can be
explained by Henry’s law, whereas gas diffusivity is associated with the 2.2. Fractional free volume (FFV) in the polymer
kinetic diameter of penetrant gases [8,9]. Lower the kinetic diameter
higher will be the gas diffusivity through the membrane. Table 1 shows Polymer free-volume contributes significantly in determining the
the kinetic diameters for some of the most cited gases in the literature. transport properties of gases. In gas separation polymers, the void space
Additionally, the polarity of a gas molecule is another important available between the polymer chain segments, i.e., the portion of the
parameter that determines its permeability [10]. Generally, polymers volume unfilled by the electronic clouds of the polymer is known as the
containing polar groups exhibit higher gas permeation for non-polar free volume, which aid in molecular transport through the membrane
gases. [12]. Mostly polymers with medium to high free volume are employed
in the membrane preparation. Fractional free volume (FFV) can further
2. Overview of polymeric membranes be increased by generating molecular motion in the polymer matrix
[12]. The generated motion increases the opening between the polymer
2.1. Various polymer materials used in the gas separation chains and produces free volume in the polymer matrix which further
assists in easy penetration of gas molecules through it. The FFV can be
Gas separation membranes can be applied to different applications, estimated by taking the difference between experimental specific vol­
viz., N2 from the air, O2 from the air, H2 separation from gases like CH4 ume (Vsp ), i.e., nothing but the reciprocal of polymer density and
and N2, H2 recovery from NH3 plants, H2O separation from raw natural theoretical volume (VoC ) occupied by the polymer chains as given in
gases, and helium removal from natural gases. In all of these applica­ equation (1) [16–18]:
tions, polymeric membranes are the heart of commercialization because
of their ease of processability, manufacture, and availability. The use of FFV =
Vsp − VoC
(1)
polymers in the membrane applications has enlarged significantly since Vsp
its beginnings in the 1970s [12]. Even though several polymer materials
have exhibited their potential application in the gas separation only a where can be further estimated by the group contribution method given
few of them have been applied in practice. These include glassy poly­ in equation (2) which represents the sum of the increments of van der
mers, such as polycarbonates (PC), cellulose acetate (CA), polyimides Waals volumes of the groups that form the repeat unit of the polymer:
∑
(PI), polyetherimide (PEI), polysulfone (PS) and poly (phenylene oxide) VoC = 1.3 VW (2)
(PPO); and rubbery polymers, such as poly (dimethylsiloxane) (PDMS)
and ethylene oxide/propylene oxide-amide copolymers. Most often The value 1.3 in equation (2) corresponds to the random packing
glassy polymers are utilized in the gas separation because of their ability coefficient for cylinders. The FFV may differ, depending on the method
to permit the smallest components in a mixture and to derive the highest used to evaluate it. However, only positron annihilation lifetime spec­
selectivities [13]. However, some recently developed glassy polymers troscopy (PALS) measures FFV while the other methods are based on
such as thermally rearranged (TR) polybenzoxazoles and polymers of estimation, as described above [17].
intrinsic microporosity (PIMs) are capable of exceeding the upper bound
trade-off limitations of Robeson plot owning to their excessive free 2.3. Gas transport through polymeric membranes
volume and micro-cavity size distribution [13,14]. Thus, their growth in
the membrane gas separation is awaited in the coming years as the Gas transport activity through polymeric membranes is primarily
technology improves further. Table 2 provides permeability and selec­ described by the solution-diffusion mechanism which is the most widely
tivity data for some important rubbery and glassy polymers employed in accepted and used model for gas permeation in nonporous membranes.
This model assumes no permanent pores in the selective layer of the
Table 1 membrane. Therefore the separation is attained as a result of the dif­
Kinetic diameter for different gases [11]. ference in the diffusion rate of penetrant gases and the number of pen­
etrants which dissolves in the membrane. The model is generally
Gases Kinetic diameter (Ǻ)
expressed in three steps. In the first step, gas penetrants dissolve into the
CO2 3.3
surface side of the polymer film, which is normally exposed to high
CH4 3.8
O2 3.46 pressure. In the second step, gas penetrants diffuse through the polymer
N2 3.64 film and then finally desorb at the bottom side exposed to low pressure
CO 3.75 (Fig. 2).
H2 2.89 In the diffusion step (second step), small molecules are transferred
He 2.60
into the membrane due to the random molecular motion. Also, the

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A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

c=S × p (9)

where, is the solubility coefficient and is the pressure. By substituting

equation (9) into equation (8), one can get the flux equation (10) as,
p1 − p2 Δp
J = DS = DS (10)
l l

where Δp is the difference in pressure across the membrane of thickness

(l). The penetrant permeability can be expressed as the product of and,
which is also called as a permeability coefficient. The widely accepted
unit for permeability coefficient is Barrer, where 1 Barrer = 10− 10 cm3
Fig. 2. Schematic of solution-diffusion process through polymer mem­ (STP) cm/(cm2 s cm Hg) or mol/(m s Pa) in SI units. For the case of a
brane [11]. binary mixture of gases A and B, the flux equation (10) can be written as:
For component A:
diffusion step is very slow relative to step 1 and step 3 and therefore it is pA
the rate-limiting step. Furthermore, in this step, the local scale sectional JA = (xA p1 − yA P2 ) (11)
l
dynamics of the polymer chains induce the opening and closing of
For component B:
transient gaps (i.e., free volume elements) in the polymer which reflects
the mobility of penetrant gases in the polymer matrix [12]. As a result, pA [ ]
JB = (1 − xA ) × p1 − (1 − y)A × P2 (12)
gas molecules exhibit Brownian motion through these free volume ele­ l
ments. The process can be expressed by using Fick’s first law of diffu­ On the other hand, facilitated transport mechanism is also proven to
sion, according to which the flux can be written as given in equation (3): be highly preferred mechanism in the gas separation to improve the gas
( )
∂c transport properties of the membrane [19,20]. The carriers are incor­
J= − D (3) porated in the polymer matrix which can reversibly react with the
∂x
reactive species in the mixture permeant to form its complex. Owing to
where, the proportionality factor D is the coefficient of diffusion. the lower partial pressure on the permeate side, the carrier-gas species
equation (3) accounts for steady-state when the concentration does not complex transport towards the low pressure side, breaks down, releases
vary with the time (t), diffusion flow is constant and the D is indepen­ the gas molecules, and regenerates the carriers.
dent of concentration (C). However, for the non-steady state, the flux
can be derived by using Fick’s second law which is given by equation
2.4. Membrane selectivity
(4):
( 2)
∂c ∂c Another key characteristic of membranes is their selectivity in gas
=D (4)
∂t ∂x2 separation. There are several definitions of this property. If permeation
of different gases proceeds independently, that is, the permeability of
This represents an ideal case in which the membrane is isotropic and one gas is not sensitive to the presence of other permeating gases. In
D is independent of (C) and (t). In the case of polymeric membranes, particular, considering two gas species A and B, membrane selectivity is
there is strong interaction occurs between penetrant molecules and described as given in equation (13):
polymer surface and hence D is depending on the concentration.
Therefore, equation (4) becomes, αAB =
PA
(13)
⎛ ⎞ PB
∂c ∂c
⎜∂D(c) ∂x⎟ Here PA and are the permeability coefficients of gas species A and B
= D⎝ ⎠ (5)
∂t ∂x measured in runs with individual permeation. Generally, A is considered
as the faster gas, that is, αAB > 1. In case of a binary mixture of gases,
It is difficult to solve equation (5) analytically and therefore another components of a mixture exert mutual influence on transport in the
form is used as, membrane and that time ideal separation factors become a rather rough
( ) measure of the selectivity and can be evaluated using equation (14):
∂c ∂c2 ∂D(c) ∂c 2 ( )
= D(c) 2 + (6) yA
∂t ∂x ∂c ∂x yB
d
αAB = ( ) (14)
The term ∂D(c)
∂c in equation (6) is considered to be negligible compared xA
u
to D(c) when experiments are carried out over a small interval of c. As a xB

result, D can be written over concentration range c1 to c2 as,

∫ c2 where, yA and yB are mole fractions of gases in the downstream (d), i.e.,
D= D(c)
dc
(7) permeate and xA and xB are their mole fractions in the upstream (u), i.e.,
c1 c1 − c2 feed side of the membrane.

where and are the penetrant concentrations at the low and high con­
centration sides of the membrane, respectively. As described earlier, in
the steady-state, D is independent of concentration C. In this case
equation (3) can be further solved as,
c1 − c2
J =D
l
The above equation (8) can be easily solved but and are generally
unknown. Therefore, one must address the sorption isotherm like Hen­
ry’s Law. As stated in Henry’s law:
2.5. Permeability-selectivity trade-off in polymeric membranes (robeson
upper bound)
Despite the intrinsic advantages of the polymeric membranes,
(8) described earlier, they suffer from the famous permeability-selectivity
trade-off known as the Robeson upper bound which was first identi­
fied by Robeson in 1991 and later by Freeman, justifying this behavior in
the polymeric membranes [21]. They discovered this typical behavior of
polymeric membranes in which a highly selective polymer exhibits low

3
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

gas permeability and a highly permeable polymer exhibits low selec­
tivity. This trade-off between permeability was quantified in terms of
separation performance of different polymer materials available at that
time and was given on the log-log plot of permeability and selectivity, i.
e., log (PA/PB) versus log PA, for various binary gas systems viz., He/N2,
He/H2, O2/N2, CO2/CH4, CO2/N2, H2/N2, etc. The plots indicated that if
a particular material has a permeability-selectivity combination above
the upper bound; it surpasses all other membranes for the specific gas
separation. For instance, Fig. 3 depicts the case of a trade-off plot for
He/N2 separation.
As seen in Fig. 3 [16], the He/N2 selectivity was plotted against the
He permeability for all polymer materials reported in the open litera­
ture, leading to the formation of diagonal upper bound lines. These two
diagonal lines picture the improvement in polymer materials for He/N2
separation from 1991 to 2008. It also demonstrates that beyond this
upper bound no material is available for He/N2 separation at present.
However, it should be noted that this bound evolves with time as re­
searchers invent new materials. Ever since the Robeson plots are
developed, they are widely being used to perceive the potential of new
polymeric membrane material for gas separation, aiming to exceed the
upper bound line.
2.6. Limitations of the polymeric membranes
While the permeability/selectivity trade-off remains a widely
perceived challenge, there are other major striking material challenges,
viz., plasticization, physical aging, swelling, etc., that limit the perfor­
mance of polymer membranes. Therefore, it is essential to comprehend
the effect of these factors on the performance of gas separation mem­
branes over a long service period. Normally, glassy polymers such as
polyimide (PI), polypropylene oxide (PPO), and polysulfone (PSF) and
polymers with high free volume such as PIMs, Hyflon® and Teflon® AF
are prone to physical aging. The undesirable chain packing and densi­
fication over the time drives the polymer material into non-equilibrium
state, by nature, molecular relaxation takes place which further places
the material closer to equilibrium known as physical aging in the
polymer [22–25]. This reversible change in the polymer properties is
normally accompanied with loss in porosity and free volume which
further leads to decrease in the gas transport through the polymer.
However, addition of non-porous materials can prevent the physical
aging in the polymer. Also, several other techniques such as blending of
polymers, post-modification of the prepared membranes, post-synthetic
modification of polymers, and changes in the polymer backbone design
etc. Are proven to be controlling the aging in the polymer [24].
On the other hand, the sorption of gases on the membrane surface
leads to an enhancement in the local segmental motion of the polymer
chains which further enhances the diffusion rate of the slower compo­
nent in the gas mixture to be separated [26]. For instance, in CO2/CH4
gas pair separation, due to CO2 plasticization, the diffusion rate of
slower component CH4 significantly increases when compared to faster
component CO2. As a result, membrane selectivity decreases, i.e., less
separation is achieved.
Moreover, polymers cannot resist aggressive chemical environments
and high temperatures. This can be a serious problem for industries
dealing with high-temperature applications such as refineries and
petrochemical plants. For these reasons, polymer materials are still
under investigation to get over the existing limitations on the polymeric
membranes to maximize their full potential for gas separation.
3. Mixed matrix membranes for gas separation applications
The performance of majority of the polymer membranes in the gas
separation is constrained by an upper bound trade-off relationship be­
tween permeability and selectivity, as described earlier. This necessi­
tates the development of new membrane fabrication technology which
will produce high-performance membrane material concerning the
membrane selectivity and gas permeability so that industrial applica­
tions of polymeric membranes expand.
On the other hand, some membrane materials, categorically falling
into inorganic membranes shows unprecedented gas separation perfor­
mance, are exceeding the Robeson’s upper bound. They are normally
composed of metals such as palladium, nickel and silver, and oxides such
as alumina, zirconia, silicon nitride, titania, and silicon carbide [27].
Also, these materials offer exceptional chemical, mechanical and ther­
mal stabilities in contrast to polymer materials. Considering their
excellent properties, they are mostly being explored in energy-related
applications, such as removal of H2, H2S, CO2 and N2 present in the
oil reservoir before sending them into the pipeline to avoid gas flaring.
Besides this, they show higher gas fluxes and can sustain a higher
pressure up to 10 MPa when compared to polymeric membranes. Over
the years, different inorganic membranes are commercialized and are
available in three different configurations, i.e., disks, tubes, and
multi-channel/honey-comb configuration. Table 3 provides information
on different inorganic membranes that are available commercially.
However, their higher cost and processability into modules for large
scale applications are the major concerns in using these materials in gas

Table 3
Commercially available inorganic membrane [27].
Manufacturer Trade name Material Pore size Geometry

TECH-SEP CARBOSEP® ZrO2/C 10-300 kD Tube

KERASEP ® TiO2/C 0.14 μm Monolith
TiO2/Al2O3+ 0.1–0.45
TiO2 μm
ZrO2/Al2O3+ 15-300kD
TiO2
Carre – ZrO2/SS – Tube
Fairey STRATA-PORE Ceramics 1–10 μm Tube/Plate
®
USF/SCT MEMBRALOX® ZrO2/Al2O3 20–100 nm Monolith
Whatman ANOPORE® Al2O3 20 nm-0.2 Disk
μm
Osmonics HYTREX® Ag 0.2–5 μm Tube/Plate
Ceramem – Ceramics/ 0.05–0.5 Honeycomb
Cordierite μm
Steenecker – Al2O3 0.4 μm Tube
Fuji Filters – Glass 4–90 nm Tube
Fig. 3. Robeson plot for the He/N2 gas pair [22].

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A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

separation [28–30]. Table 4

To address issues related to inorganic membranes, an effort was Comparison of properties of polymeric, inorganic, and mixed matrix
made to amalgamate the benefits of both polymeric and inorganic ma­ membranes.
terials to develop next-generation membranes, and such an idea was Properties Polymeric Inorganic Mixed Matrix
realized with the origination of the mixed-matrix membranes (MMMs). Membranes Membranes Membranes
The MMMs have the potential to increase permeability and selectivity Fabrication cost Low High Moderate
simultaneously, i.e., without refraining either of it by utilizing inorganic Chemical and Moderate High High
particles as discrete phases and polymer as the continuous phase. They thermal
stability
are derived by dispersing inorganic particles of micro- or nano-size in
Synthesis and Easy Difficult Easy
the continuous organic polymer phase (Fig. 4), combining advantages processability
from each phase. Plasticization Susceptible Insusceptible Insusceptible
Generally, dispersed inorganic phase improve gas permeability and Surface roughness Low High Moderate
exhibit selectivity superior to polymer phase, exceeding the perfor­ Fouling resistance Low Moderate Moderate
Cleaning after Difficult Easy Easy
mance of polymeric membranes without affecting the economic and fouling
processing convenience of the polymers [31,32]. The properties of Swelling Frequently Swelling-free Swelling-free
polymeric, inorganic and mixed matrix membranes are compared and occurs
listed in Table 4. Resistant to Moderate High High
pressure
The advantages of MMMs further promoted many studies to scruti­
Mechanical Good Poor Excellent
nize the gas separation potential of the existing polymeric membranes. strength
Kulprathipanja et al. [33] were the first to report the superior behavior Gas Separation Below the Above the Above the
of MMMs. The authors [33] observed an increment in O2/N2 selectivity performance Robeson’s upper Robeson’s upper Robeson’s upper
with the incorporation of silicalite in the polymer cellulose acetate (CA) bound bound bound

when compared to pure CA membrane. However, to obtain a desired

morphology and gas separation properties, MMMs must overcome some
critical issues related to their fabrication such as particle sedimentation,
agglomeration and defect voids at the polymer-particle interface. The
excessive particle loading in the polymer leads to particle agglomeration
which further deteriorates the membrane performance [28,34]. There­
fore, finding inorganic filler which is compatible with the organic
polymer matrix, i.e., selecting an appropriate polymer/filler pairs for
successful fabrication of MMM is a challenging task. At present, there
available plentiful novel inorganic materials and the same have been
identified to explore the effects on polymeric membranes concerning gas
separation. A comprehensive study on the different inorganic fillers
employed in the preparation of MMMs for various gas separation ap­
plications is given in the latter part of the paper.
As described earlier, MMM is usually synthesized by blending inor­
ganic fillers into the polymer matrix. Most of the time fabrication of
MMM involves difficulties such as particle agglomeration, sedimenta­
tion, and poor dispersion. Apart from that, particle size, amount of
particles being used, polymer chain rigidification, contact (adhesion)
between particle and polymer phase, viscosity of dope containing par­
ticle, stress carried out to particle dispersion in solvent, also affect the
overall preparation of MMMs [35,36]. However, to date, several pro­
tocols have been proposed to finely tune the particles into polymer
matrix to achieve better dispersion and reduce the interfacial gap for­
mation between the two phases during the fabrication of MMMs.
However, these are outlined below:
• Addition of plasticizers viz., polyethylene glycol (PEG), 4-hydroxy
benzophenone, dibutyl phthalate, RDP Fyroflex into the dope solu­
tion to promote the polymer chain mobility and flexibility during the
membrane preparation to form MMM.
• Using the low boiling solvent for the preparation of the dope solution
followed by casting the dope solution at elevated temperature i.e.
casting above or around the Tg of the mixture. This could lead to
maintaining polymer flexibility during the membrane fabrication
and thereby obtaining a better matrix.
• In another protocol, the prepared MMM containing defects is
annealed above Tg to prevent the formation of ‘‘sieve-in-a-cage’’
morphology in the matrix. However, this method considers a serious
limitation of using convenient casting solvents that boil at temper­
atures below the Tg of a typical rigid polymer.
• Deposition of the polymer dope solution onto the surface of dense
liquid with higher surface tension can prevent membrane adhesion
and thereby further preventing the membrane contraction on the
casting surface and mitigating the interfacial defects in the
membrane.
• Blending of polymer additives like PEG with polymer dope solution
can significantly enhance the local segmental motions in the poly­
mer. Consequently, enhancing the adhesion between polymer and
filler phase and therefore skips the formation of voids in the mem­
brane [37,38].
• Modifying the chemical properties of filler materials before incor­
porating into polymer matrix can overall improve the polymer-filler
contact. For instance, during the membrane preparation, specifically
in the phase inversion step, fillers attract the polar solvents like water
on its surface. Therefore modifying the filler properties by attaching
the hydrophobic group on fillers can prevent the nucleation of polar
compounds and thereby preventing the formation of sieve-in-cage
defect around the filler particles [39].
• The use of copolymers reduces the surface tension and prevents the
formation of whiskers on the outer surface of the fillers which
eventually mitigates the formation of voids and leads to the uniform
distribution of fillers in the matrix.

On the other hand, membranes fabricated from ultrathin nano­

structured material have been realized as an alternative to MMMs as
they eliminate the drawbacks of MMMs. Their significant advantages
such as controlled grain size, defect-free structure, requirement of less
membrane area, requirement of less amount of nanomaterials for the
membrane fabrication, atomic thickness which reduces the transport
resistances and maximizes the gas permeance, stable mechanical prop­
erties for large-scale gas separation applications etc. Makes the ultrathin
membranes one of the most desiring morphologies in gas separation
Fig. 4. Schematic representation of ideal MMM morphology.

5
A.R. Kamble et al.
[40].
In addition, recently, inorganic materials together with high free
volume polymers are being explored for obtaining superior performing
MMM material. For instance, Castro-Muñoz et al. [41] in 2020 prepared
a MMM comprising CO2 selective SSZ-16, an aluminosilicate zeolite
along with high free volume 6FDA-based polyimide for CO2/CH4 sepa­
ration. Out of all the prepared membranes, 6FDA-DAM:DABA (3:1)
membrane containing SSZ-16 5 wt% showed the maximum CO2
permeability and CO2/CH4 selectivity of 365 and 34.8, respectively. The
presence of bulky group like –COOH in DABA moiety acted as resistance
to polymer chain packing and enforced creating a bigger gap in the
polymer chain. As a result, higher free volume and gas permeation was
obtained through the membrane.
Furthermore, currently, researchers are focusing on the biopolymers
derived from various natural sources such as vegetables sources (e.g.
starch, alginate, polyisoprene), animal derived (e.g. polybutylene suc­
cinate, polylactic acid), bacterial fermentation products (e.g., collagen,
chitin, chitosan) etc. As they are found as the excellent replacement to
many chemically synthesized polymers and exhibit a great potential for
the preparation of MMMs [42,43]. Their key advantages include
non-toxicity, biocompatibility, low cost, and environment friendly. As a
result, to date several biopolymers have been explored for the MMM
preparation followed by their use in the different applications such as
pervaporation, gas separation, microfiltration and ultrafiltration. For
instance, Casado-Coterillo et al. [44] developed chitosan (CS)-based
MMMs and were subjected to pure CO2 and N2 gas permeation tests. The
maximum CO2 permeation of 4754 ± 1388 Barrer and maximum
CO2/N2 selectivity of 19.3 was obtained with the CS membrane con­
taining 5 wt % of HKUST particles. This was attributed to the good
adhesion and compatibility between CS polymer matrix and HKUST
particles. Qian et al. [45] fabricated CS/graphene oxide (GO) mem­
branes for high-salinity water desalination. The permeate flux was found
to be improved to 30.0 kg/m2⋅h from 12 kg/m2⋅h for 5 wt % NaCl so­
lution at 81 ◦ C and 60 mbar. The lower NaCl diffusion coefficient
compared to H2O contributed in obtaining higher H2O/NaCl selectivity
of the membranes.
In another work of Vinu et al. [46] they incorporated Al-MOF in the
matrix of CS polymer to prepare Al-MOF filled CS MMMs for separation
of water/ethanol mixture through pervaporation process. The flux and
pervaporation separation index (product of flux and separation factor)
was significantly found to be enhanced to 1369 and 852,887 g/m2h,
respectively on addition of 5 wt % filler in the membrane than pure CS
which is 383 and 91,290 g/m2h. However, the reason they attributed to
this increase was the formed microporous defects in the membranes
which provided the transportation path for water molecules to easily
pass through the membrane.
3.1. Key criteria to select fillers for incorporating into polymer phase
Different characteristics of fillers materials such as dispersability,
size, morphology, stability, and hydrophilicity/hydrophobicity etc. Can
affect the overall performance of MMMs and therefore these factors
should be taken into consideration upon the preparation of MMMs [47].
• Dispersability: non-uniform dispersion in the polymer provides non
selective cavities in the polymer matrix which affects the overall
performance of MMMs. Therefore, to block those cavities and to
obtain a strong interfacial network between polymer and fillers good
dispersion should be considered [34].
• Filler size: size of the fillers significantly affects the homogeneity of
the membranes. For instance, larger size particles tend to agglom­
erate and form their clusters in the membranes. The formed clusters
act dominates the polymer area in the membrane and hence acts as
resistance which brings the non-homogeneity in the membrane.
Subsequently, a weak interlock forms between the polymer and
fillers which further reduces the mechanical strength of the
6
Renewable and Sustainable Energy Reviews 145 (2021) 111062
membrane. As a result, membranes succumb to high pressure test
and get torn off easily.
• Hydrophilicity/hydrophobicity: The hydrophilic or hydrophobic
nature of the fillers determines the separation properties of the
MMMs. For instance, thermally driven separation processes like
membrane distillation (MD) are normally implemented for the sep­
aration of water/wastewater treatment when the total (100%)
rejection is required. Mostly, hydrophobic microporous membranes
are used in this process which allows the transport of water vapors
through the membrane and restricts the transport of liquid phase
through the membrane. However, hydrophobic properties of these
MD membranes are further being increased by incorporating hy­
drophobic fillers as they provide more hydrophobic area in the
membrane and improve the membrane-water contact angle to obtain
the high performance through MD MMMs. There is a current trend on
producing superhydrophobic membrane surfaces for MD [230].
4. Different inorganic filler materials based MMMs for gas
separation
4.1. Metal oxide-based MMMs
Metal oxides are one of the most regularly used and widely accepted
inorganic fillers for the development of MMMs. Gas transport properties
of various polymer materials have been successfully improved by
incorporating metal oxides in the polymer matrix. For instance, Hosseini
et al. [48] utilized MgO nanoparticles for the very first time with poly­
imide (Matrimid®5218) to synthesize polyimide/MgO nanocomposite
membranes. The highest gas permeation was achieved at 40 wt% MgO
loading in the membrane. The reason authors attributed to this increase
was higher pore size of MgO particles (30 Å) which contrasts the kinetic
diameter of gases.
In the work of Nematollahi et al. [49] MMMs were fabricated by
blending alumina (Al2O3) nanoparticles with poly (4-methyl-1-­
pentyne), also known as PMP polymer. Their study investigated the ef­
fect of different weight percentage of Al2O3 on the CO2/N2 gas transport
properties of PMP polymer. The resultant membranes exhibited a sig­
nificant enhancement in CO2 permeability with an increment in the
weight percentage of Al2O3. Another observation made was that the
presence of Al2O3enhanced the free volume in the membrane by
breaking off the polymer chain. This increased free volume provided
allowances for gases to pass through the membrane. Consequently,
higher permeation rate and CO2/N2 selectivity were achieved for
PMP/Al2O3 combination at 30 wt% Al2O3 loading in it. Chen et al. [50]
developed Matrimid/silica (SiO2) membranes integrated with tetrame­
thoxysilane, tetraethoxysilane, and tetrapropoxysilane. All the mem­
branes were developed using the sol-gel method. They observed that the
CO2 permeability was raised by factor 2–3 times, whereas for CH4 it was
increased by factor 3–10 times compared to neat Matrimid. Molki et al.
[51] suggested the combination of nickel oxide (NiO) and polyurethane
for CO2 gas separation. The combination resulted in increasing the
CO2/N2, CO2/CH4 and O2/N2 selectivity to 67.72, 21.76 and 2.77 from
25.94, 12.77, and 1.57, respectively, on incorporating NiO loading up to
5 wt% in the membrane. However, the selectivity was further found to
be reduced at elevated loading of 10 wt% of NiO. This decrease was
mainly associated with the excessive amount of NiO particles, which
reduced the available free volume in the membrane and thereby reduced
the gas permeability through the membrane. Farashi et al. [52] suc­
cessfully produced polyether-block-amide (Pebax-1657)/ZnO MMMs by
using solution blending technique and by varying ZnO content from 0 to
10 wt%. The prepared membrane was then evaluated against CO2 and
CH4 gases at a pressure of 3 bar and temperature of 30 ◦ C. The maximum
CO2/CH4 selectivity of ̴24 was obtained with Pebax/ZnO (10 wt%)
membrane.
Recently, Tan et al. [53] modified the polysulfone (PSf) membrane
by embedding Titanium (IV) oxide (TiO2) nanoparticles into the
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

polymer matrix along with octaisobutyl polyhedral oligomeric silses­ Table 6

quioxanes (POSS) as a dispersing agent. Their research was mainly Commonly used MOFs in gas separation, their composition and interpreted
centered on enhancing the gas separation performance of PSf membrane abbreviations [75].
along with reducing TiO2 particle agglomeration inside the PSf matrix. MOF name Formula Interpreted Abbreviation
The results revealed that the 5 wt% of POSS was sufficient to disperse HKUST-1 (MOF- Cu3(BTC)2 Hong Kong University of Science
and stabilize TiO2 nanoparticles in the PSf matrix, which also provided a 199) andTechnology
good inter linkage between polymer and filler and increased the polymer ZIF-8 Zn (MIM)2 Zeolite Imidazolate Framework
chain mobility. Moreover, the gas permeation test conducted on the ZIF-90 Zn(FIM)2
MOF-74 Zn2DOT Metal-Organic Frameworks
PSf/TiO2 membranes showed a great increment in gas permeability as
UiO-66 Zr6O6(BDC)6 Universitetet i Oslo
well as selectivity compared to the membranes prepared without the MIL-53 Al(OH) (BDC) Materials of Institut Lavoisier
addition of POSS and the pure membranes. Table 5 summarizes the MIL-53(Al)– Al(OH) (BDC-NH2)
broad spectrum of metal oxide nanoparticles that have been used in the NH2
open literature, for polymer modification in the gas separation. MIL-101 Cr3O(H2O)2F. (BDC)3.
N H2O

4.2. Metal organic framework (MOF) based MMMs

Another emerging class of inorganic materials that have been

employed in the preparation of MMMs is metal-organic framework
(MOF). The MOFs comprises of secondary building units linked to
organic ligands to form a repeating, cage-like structure [74–78]. Sec­
ondary building units are normally positively charged metal ions and
transition metal oxides. Different techniques such as microwave, elec­
trochemical, sonochemical and mechanochemical have been reported to
synthesize MOFs [75,79,80]. Their key advantages include ultra-high
surface area (up to 1000–10000 m2/g), low density, higher packing
capacity, flexibility in network topology, dimensions and chemical
functionality, tunable porosity, and broad varieties, etc., which provide
accessibility to the membrane researchers to employ them in different
gas separation applications over the other porous materials (silica and
activated carbons, and zeolites) [28,74,81–83]. In the past decade,
several famous MOF structures such as MIL-series, ZIF-series, Cu3
(BTC)2, HKUST-1, and MOF-5, etc., have been successfully employed in
the preparation of MMMs. Table 6 provides the names, composition and
interpreted abbreviations of a few commonly used MOFs in the gas Fig. 5. The 3D structures of different MOFs [83].
separation membranes, whereas Fig. 5 shows the 3D representation of

Table 5
Gas separation performance of different polymer membranes modified with different metal oxides.
Polymer Type Metal Oxide Type Loading (wt.%) Gas Pair Selectivitya Ref.

PMP Al2O3 30 CO2/N2 4.5–5 [49]

Matrimid MgO 40 H2/N2b 90.1 [48]
Polyurethane (PU) NiO 5 CO2/N2b 67.72 [51]
Matrimid 5218 SiO2 13 CO2/CH4 35.6 [50]
PSf TiO2 5 CO2/CH4 5 [53]
Pebax-1657 ZnO 10 CO2/CH4 24 [52]
1,2-Polybutadiene MgO 27c CO2/N2b 7.8 [54]
d
Rubber (ENR) and polyvinyl chloride MgO 5 CO2/N2 6.5 [55]
PSf MgO 10 H2/N2b 42.31 [56]
PIM-1 SiO2 6.7c CO2/N2b 15 [57]
Polybenzimidazole SiO2 20 CO2/N2b 80 [58]
PSf SiO2 8.5 CO2/CH4b 27 [59]
Polyimide Matrimid® Mesoporous silica spheres 8 H2/CH4 79.2 [60]
polydimethylsiloxane SiO2 2 C3H8/H2 35 [61]
PU SiO2 12.5 C3H8/CH4b 7.01 [62]
PVC SiO2 30 CO2/N2b 27.3 [63]
Polystyrene TiO2 7 CO2/N2 2.77 [64]
PSf ZnO 5 CO2/CH4 54.29 [65]
Pebax ZnO 4 CO2/CH4 31.58 [66]
Pebax-1074 ZnO 8 CO2/N2b 62.15 [67]
Poly (Amide-6-b-EthyleneOxide) ZnO 0.1 CO2/N2b 33.16 [68]
PSf TiO2 15 CO2/CH4b 15.13 [69]
Polybenzoxazole SiO2 30 CO2/CH4b 49 [70]
Matrimid 5218 SiO2 15 CO2/CH4b 77.5 [71]
Poly (arylene ether sulfone) TiO2 2 CO2/N2b 64 [72]
PEBAX ZnCO2O4 0.5 CO2/CH4 15.38 [73]
a
Selectivity values are given on the basis of best results obtained.
b
Membrane performance was checked for more than one gas pair and the best results are obtained with the selected gas pair.
c
Nominal volume percent.
d
More than one polymer used to prepare membrane.

7
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

MOFs. Table 7
Liu et al. [84] proposed the use of first continuous MOF based Gas separation performance of various metal oxide frameworks based mixed
membrane in the gas permeation. In their study, the MOF-5 membrane matrix membranes.
was fabricated on the top of porous alumina support using in situ sol­ Polymer Material MOF Type Wt. Gas Selectivitya References
vothermal method. It was revealed that the MOF-5 membrane when % Pair
exposed to H2, N2, CH4, and CO2 gases followed the Knudsen-diffusion 6FDA-DAM ZIF-90 15 CO2/ 37 [85]
mechanism. Bae et al. [85] successfully impregnantedZIF-90 in 6FDA-­ polyimide CH4
DAM polyimide by non-solvent-induced crystallization method to Polyimide Cu3(BTC)2 6 H2/ 240 [94]
CH4b
obtain 6FDA-DAM/ZIF-90 MMMs. Promisingly, incorporation of ZIF-90
Matrimid MOF-5 30 H2/ 120.0 ± 7.7 [95]
in 6FDA-DAM polyimide not only improved gas permeabilities but also CH4b
enhanced membrane selectivity, i.e., permeability of CO2 was found to Matrimid Cu3(BTC)2 30 CO2/ approx. 19 [96]
be boosted dramatically from 390 Barrer to 720 Barrer, whereas N2b
CO2/CH4 selectivity was enhanced from 24 to 37. In Nik et al. [86] work, Poly (vinyl CuTPA (15) 15 CO2/ 40.4 [76]
acetate) CH4
five different MOF UiO-66, UiO-67, NH2-UiO-66, MOF-199 (Cu-BTC), PBI ZIF-7 50 H2/ 7.2 [97]
NH2-MOF-199 were used in the preparation of Matrimid based MMMs. CO2
Out of all the membranes used, the membranes prepared with UiO-66 PSf NH2-MIL-53 25 CO2/ 117 [98]
exhibited higher gas permeation for CO2 gas, whereas the CH4
6FDA-ODA MIL-53 25 CO2/ 44 [99]
amine-functionalized MOF-MMM (NH2-MOF-199) increased both the
CH4
CO2 permeability and CO2/CH4 selectivity. The reason for the selectivity Matrimid MOF-199 25 CO2/ 50.7 ± 2.7 [86]
improvement was related to hydrogen bonding present between –NH2 in CH4
the filler and carboxylic acid groups in the polymer chain which facili­ Matrimid NH2 -MOF- 25 CO2/ 52.4 ± 2.5 [86]
tated the rigidification in the polymer chain at the interface. Conse­ 199 CH4
Matrimid UiO-66 25 CO2/ 42.3 ± 3.2 [86]
quently, permeability was decreased and selectivity was increased.
CH4
In Nafisi and Hägg [87] work, ZIF-8 was impregnated in the matrix of Matrimid NH2 -UiO-66 25 CO2/ 44.7 ± 2.9 [86]
synthesized 6FDA-durene polyimide. The resultant membrane signifi­ CH4
cantly improved the transport pathways all the four gases O2, N2, CO2, 6FDA-ODA NH2-MIL-53 25 CO2/ 66 [99]
CH4
and CH4, whereas, CO2/CH4and CO2/N2gas pair selectivity was found to
Polyimide Al-MIL-53- 32 CO2/ 78 [99]
be decreased. The increase in the gas transport was mainly ascribed to NH2 CH4
the incorporation of ZIF-8 which interrupted the polymer chain and PPO Cu-BTC 10 CO2/ 28 [100]
enlarged the overall fraction free volume in the membrane, while the CH4b
decrease in the selectivity was justified by the relatively higher transport PSf MIL-68 8 H2/ 77 [101]
CH4b
of CH4 and N2 over CO2. Rodenas et al. [88] scrutinized the potential of
Pebax ZIF-7 34 CO2/ 44 [102]
CuBDC MOF for CO2/CH4 separation via synthesizing polyimide/CuBDC CH4
MMMs, comprising different loadings of CuBDC (2–12 wt%). Naseri 6FDA based PI NH2-MIL- 30 CO2/ 41.6 [103]
et al. [89] utilized micron-sized MIL-101 crystals (loading up to 30 wt%) 101 CH4
PMMA CAU-1-NH2 15 H2/ 13 [104]
as the inorganic phase and Matrimid as the continuous polymer phase to
CO2
fabricate MIL-101/Matrimid MMMs. The prepared membranes were 6FDA-Durene ZIF-71 20 CO2/ 14.7 [90]
then evaluated for CO2/CH4 and CO2/N2 separation. The MIL-101 par­ CH4b
ticles showed a higher affinity towards CO2 over CH4 and N2 gases. As a Matrimid MIL-101 10 CO2/ 55.77 [89]
result, the best performance was obtained at 10 wt% loading of MIL-101 CH4b
Matrimid NH2-MIL-53 25 CO2/ 35 [105]
with enhanced CO2 permeability from 4.44 Barrer to 6.95 Barrer and
CH4
CO2/CH4 selectivity from 35 to 56. Matrimid® 5218 MIL-53 38 CO2/ 47 [106]
In Japip et al. [90] study, they investigated the effect of three CH4
different sizes (30 nm, 200 nm, and 600 nm) of ZIF-71 on the gas Matrimid MIL-88 B(Fe) 10 H2/ 80 [107]
CH4
transport properties of 6FDA-Durene. The gas separation performance
PIM-1 TiX-UiO-66 5 CO2/ 24 [108]
obtained with the membranes comprising ZIF-71 of size less than 200 N2
nm were found to be more promising than the membranes prepared with SPEEK PEI-MIL-101 40 CO2/ 57.5 [109]
ZIF-71 of size greater than 200 nm. It was further noticed that the CH4
permeability of O2, N2, and CH4 enhanced with the embedment of 20 wt PI UiO-66 30 CO2/ 35.8 [110]
CH4
% ZIF-71 in the polymer matrix, whereas gas pair selectivity was
Matrimid® 5218 UiO-67 10 CO2/ 75 [111]
observed to be dropped when compared to the pure 6FDA-Durene CH4
membrane. The decrease in the selectivity was mainly ascribed to the Matrimid® 5218 ZIF-8 50 CO2/ 124.9 [112]
larger pore cavity and aperture size of ZIF-71 than the kinetic diameters CH4b
of these light gases. Recently, Bi et al. [91] incorporated Matrimid® 9725 ZIF-8 30 CO2/ 31.5 [113]
CH4b
co-benzenedicarboxylate MOF nanosheets (CBMNs) in the matrix of P84 ZIF-8 17 CO2/ 93.6 [114]
6FDA-durene-DABApolymer. The properties of CBMNs such as higher CH4b
aspect ratio and ultrathin improved the interfacial interactions with the Ultem 1000 ZIF-8 13 CO2/ 36 [115]
polymer matrix which further contributed in obtaining the CO2/CH4 and N2
PEBAX 2533 ZIF-11 10 CO2/ 53 [116]
H2/CH4 selectivities up to 33.6 and 42, respectively. In another study,
N2b
Yang et al. [92] in their review highlighted the modeling studies on gas 6FDA-DAM ZIF-11 10 CO2/ 31.3 [117]
separation using MOFs. Identically, Yu et al. [93] presented a compre­ CH4
hensive review of the various aspects of MOFs, emphasizing CO2 PIM-1 ZIF-71 20 CO2/ 20 [118]
adsorption and separation. They also discussed the development in the N2b
PI NH2-CAU-1 20 H2/ 32.8 [119]
pure as well as MOF mixed matrix membranes from both theoretical and CO2
computational perspectives.
(continued on next page)
Table 7 compiles the number of research studies carried out in the

8
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

Table 7 (continued )
Polymer Material MOF Type Wt. Gas Selectivitya References
% Pair

PI HKUST-1 30 CO2/ 16 [120]

N2b
PSf Bio-MOF-1 30 CO2/ 45.6 [121]
N2b
Polyamide 6 UiO-66- 25 H2O/ 747.7 [122]
NH3+Cl− CH4
PU γ-CD-MOF 0.2 CO2/ 28.56 [123]
CH4
6FDA-DAM Zr-MOF 16 CO2/ 25.4 [124]
CH4
Matrimid® 5218 MOF-76(Y) 30 CO2/ 56.85 [125]
CH4b
6FDA-mDAT SAPO-34 40 CO2/ 60 [126]
CH4
Polymethyl NH2-MIL-53 20 H2/ 53.1 [127]
methacrylate CO2
Polyimide CBMNs 2 H2/ 42 [91]
CH4
a
Selectivity values are given on the basis of best results obtained.
b
membrane performance was checked for more than one gas pair and the best
results are obtained with the selected gas pair.

past decade in the fabrication of MOFs based MMMs and their corre­
sponding use in different gas separation applications.

4.3. Carbon molecular sieve (CMS) based MMMs

A great deal of research has been undertaken on carbon molecular

sieves (CMS) as gas separation membrane materials for their ability to
precisely discriminating certain gas species. Their higher surface area
(200–1200 m2/g), the pore structure of similar dimensions to those of
small molecules, and relative adsorptive strength, etc., characteristics
enables the effective separation of gases and excellent membrane se­
lectivities, simultaneously [128,129]. The CMS are normally obtained
by the carbonization process in which pre-existing polymer is brought to
pyrolysis temperature ranging between 773.15 K and 1273.15 K so that
Fig. 6. Comparison of gas separation performance obtained with pure and
heterogeneous atoms present in the polymer will be completely removed
MMMs for: a) CO2/CH4; b) O2/N2(Reproduced with permission from Elsev­
and a cross-linked and stiff carbon matrix, however, will be left behind
ier [128]).
[129,130]. Normally, thermal decomposition of polymer precursor
produces irregularly arranged carbon atom layers, i.e., turbostratic
maximum CO2/CH4 of 51.7 and 53.7 was obtained with 36 vol% CMS in
carbon structure; whereas, increasing the pyrolysis temperature may
Matrimid® and for 35 vol% CMS in Ultem®, respectively. It was also
result in some graphite structures. On the other hand, they are primarily
observed that Matrimid® MMM consisting of 36 vol% CMS in it could
used for the separation of O2, H2, N2, CO, and inert gases. The most
surpass the upper trade-off curve, indicating the promising potential of
commonly used polymers for the preparation of CMS membranes are
the membrane is O2/N2 separation.
poly (furfuryl alcohol) (PFA), polyimides (PI), and polyacrylonitrile
Although the work carried out by Vu et al. [128] have successfully
(PAN) [131]. Koresh and Soffer [132], for the very first time, prepared
provided insight into the CMS/MMM based gas separation, however,
crack free CMS membrane by carbonizing cellulose and examined
there has been limited research found on the CSM based MMMs in the
against He, CO2, O2, N2, and SF6 gases. Although the CMS membranes
gas separation. For instance, in a subsequent work of Nasir et al. [133],
could potentially surpass the upper bound trade-off curve and overcome
CMS was embedded in the matrix of polyethersulfone (PES) to examine
the limitations of polymeric membranes, researchers noticed that these
the effect of different loading (10, 20 and 30 wt%) of it on the CO2/CH4
materials are associated with drawbacks such as higher fabrication cost;
gas separation performance of PES/CMS MMM. The study revealed that
difficult processability into a high surface area module and brittleness,
the elevated loading of 30 wt% CMS in the membrane resulted in the
etc., which further restricts their application in the gas separation.
formation of CMS clusters in the matrix. However, the formed clusters
Therefore, to overcome these limitations CMS based MMM emerged as a
did not affect the gas permeability, i.e., they obtained CO2/CH4 selec­
new alternative approach to the pure CMS membranes. The typical
tivity as high as 10.94 with CO2 permeability of approximately 67 GPU
CMS/MMM can be synthesized by bringing the polymer to pyrolysis
at 30 wt% CMS loading.
temperature in order to obtain the CMS particles, followed by the
addition of CMS particles in a polymer to frame MMM with desired
properties. For instance, Vu et al. [128] successfully fabricated MMMs 4.4. CNT based MMMs
by dispersing high loading of CMS (up to 36 vol%) into two glassy
polymers, Matrimid®5218 and Ultem®1000. Fig. 6 shows the gas sep­ Carbon nanotubes (CNTs) are considered as one of the most attrac­
aration performance obtained with CMS MMMs concerning the perfor­ tive fillers in the preparation of MMMs due to their superior properties
mance obtained with the pure membranes. As seen in Fig. 6, with the such as high aspect ratio (length to diameter ratio), super flexible, high
increase in the CMS loading, membrane selectivity for both the Matri­ tensile strength, high thermal conductivity, and elastic modulus, etc.,
mid®5218 and Ultem®1000 MMMs was increased. However, the CNTs can further be classified as single-wall CNTs (SWCNTs) and multi-

9
A.R. Kamble et al.
wall CNTs (MWCNTs) (Fig. 7).
The SWCNTs are one-dimensional (1D), cylindrical shaped hollow
tubes, formed by rolling up the graphene sheet, whereas, multiple
single-walled carbon nanotubes are nested inside one another to form
MWCNTs. Furthermore, CNTs offer some excellent properties viz., low
cost, high aspect ratio, nanoscale diameter, high stability and efficiency
[134]. Therefore the addition of CNTs in existing polymers makes it
possible to use these properties in the wide range of gas separation ap­
plications. Skoulidas et al. [135] in their work reported an atomistic
simulation to predict the performance of light gases through CNTs. The
study indicated that the CNTs, if used as filler in the membrane, can
exhibit high flux and selectivity compared to other existing inorganic
fillers such as zeolite. Inspired by the above study, Kim et al. [136], for
the very first time, used SWCNTs to modify the matrix of poly (imide
siloxane) copolymer to verify the hypothesis given by Skoulidas et al.
[135]. They observed [136] that the permeability of O2, N2, and CH4
gases enhanced after the addition of CNTs in the membrane, providing
the practical evidence to Skoulidas et al. work [135]. Subsequently, in
the past decade, many researchers utilized CNTs as an alternative
approach to other inorganic fillers such as zeolites, MOFs, and metal
oxides. For instance, Khan et al. [137] in their work reported the
development of MMM by employing functionalized MWCNTs into the
intrinsic microporosity (PIM-1) matrix. The membranes were developed
by dip-coating method. It was noticed that the MMM comprising pristine
MWCNTs and f-MWCNTs exhibited higher separation performance for
O2, N2, CO2, and CH4 gases than the pure PIM-1 membrane and the
maximum selectivity of 32.9 was achieved for CO2/N2 gas pair in
f-MWCNTs/PIM-1 MMM. Another observation made was that the
MWCNTs when functionalized with PEG de-bundled the highly entan­
gled MWCNTs which improved its dispersion in the membranes than the
direct addition of pristine MWCNTs.
Kusworo and co-workers [138] synthesized the PES/MWCNTs
MMMs for biogas purification. Before the membrane preparation, raw
CNTs were purified by treating them with sulfuric acid and dried in the
oven at 60 ◦ C for 24 h. The method of constant volume-variable pressure
was employed in estimating the gas separation properties of the mem­
branes. The gas permeation results revealed that the addition of 2 wt%
of modified MWCNTs in the membrane increased both the CO2 and CH4
gas permeability by 19.97% and 33.79%, respectively. The reason au­
thors ascribed to this increase was mainly due to the obtained homo­
geneous distribution of CNTs within the polymer matrix which aided the
gas transport through the membrane. Zhang and co-workers [139]
synthesized a composite filler of N-isopropylacrylamide hydrogel-CNTs
(NIPAM-CNTs) by in situ atom transfer radical polymerization. The ob­
tained NIPAM-CNTs filler composite was then incorporated in the poly
Fig. 7. Structure of: a) multi-wall; b) single-wall carbon nanotubes [134].
10
Renewable and Sustainable Energy Reviews 145 (2021) 111062
(ether-block-amide) (Pebax® MH 1657) matrix to investigate the CO2
separation properties. The results obtained from the gas permeation test
indicated that both the CO2 permeability and CO2/CH4 selectivity
increased with an increase in the filler loading, however, the higher
loading of filler, greater than 10 wt% led to the particle agglomeration in
the membrane. Consequently, the CO2 separation performance of the
membrane was decreased.
Sun et al. [140] examined the effect of the addition of acid-treated
functionalized MWCNTs (1–4 wt%) on the gas separation properties of
polyimide (PI) polymer. The membranes were prepared by first
dispersing MWCNTs in poly (amic acid) followed by adding it into the PI
matrix. Gas separation results revealed the significant increment in CO2
gas permeability, and CO2/N2 and CO2/CH4 selectivity. In other words,
the CO2 permeability was improved by 292%, whereas, CO2/N2 and
CO2/CH4 selectivity were improved by 145% and 144%, respectively
after the addition of 3 wt% acid-treated MWCNTs. Overall, their results
indicated that the MWCNTs when subjected under the acid treatment
force the nanotubes to disengage into small fragments and enhances
their distribution in the membrane. This proper distribution further
serves as a channel for gas molecules to easily diffuse and transport more
effectively across the membrane.
Aroon et al. [141] used functionalized MWCNTs to modify the PES
polymer matrix. The raw MWCNTs were functionalized using low mo­
lecular weight chitosan (LMWC). MMMs were then prepared by
embedding different amounts (1, 2 and 3 wt %) of functionalized
MWCNTs in the PES matrix. For the purpose of confirming the attach­
ment of LMWC on the surface of MWCNTs, the prepared membranes
were put through Fourier-transform infrared spectroscopy (FTIR) and
X-ray diffraction (XRD) tests. The best CO2/CH4 separation performance
was obtained by incorporating 1 wt% of f-MWCNT in the PES. Hussain
et al. [142], in their work, employed different amounts of MWCNTs (5,
10 and 15 wt%) in cellulose acetate (CA) matrix for the carbon capture
from natural gas. PEG was used to obtain the polymer chain flexibility.
The permeation results were divided into two parts. In the first part, a
binary mixture of CH4 and CO2 (60:40) was employed, in which
maximum CO2/CH4 selectivity of 38.5 was achieved with 10%
MWCNTs/10%PEG/CA MMM. The pure CH4 and CO2 gases utilized in
the second part increased the CO2/CH4 selectivity up to 48.92.
Recently, Zhang et al. [143] modified the matrix of polyimide
(6FDA-TP) membrane with different loading of SWCNTs. The modified
membranes were then put against pure gas (H2, CH4, N2, O2 and CO2)
permeation test in order to investigate the gas transport properties of the
membranes. The permeability of all the gases was found to be signifi­
cantly increased after the addition of 2 wt % of SWCNTs in the mem­
brane. For instance, CO2 permeability was improved by 300%, i.e., from
20 Barrer to 81 Barrer. This increase in the gas permeability was
ascribed to the enhanced free volume in the membrane along with the
presence of smoother walls inside the CNTs which brought out the rapid
diffusion of gases through it. In another study, Jiang et al. [144] pre­
pared a novel molecular sieve membrane using GO/SWCNTs and
employed in the separation of CO2 and N2 from blast furnace gas. With
this combination of GO and SWCNTs which increased the GO/SWCNT
interlayer spacing and provided the sufficient combined channels for
gases to flow gas permeability was found to be enhanced. For instance,
at the inlet pressure and temperature conditions of 0.20 MPa and 323 K
N2 and CO2 permeabilities were found to be higher i.e. 1897 Barrer and
1976 Barrer than at 0.10 MPa and 323 K which are 1637 Barrer and
1650 Barrer, respectively.
Table 8 summarizes several research studies that indicate the
improvement in the gas transport results of various polymers after the
incorporation of CNTs.
4.5. Zeolite based MMMs
Zeolites, also known as molecular sieves, are an important class of
inorganic microporous crystalline materials with pore size ranging from
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

Table 8 in a gas mixture from going into the pores of zeolite, whereas the other
Gas separation performance of CNTs based MMMs. component enters into the pore and get adsorbed. 2. Thermodynamic
Polymer Type CNT loading (wt. Gas pair Selectivity References selectivity, which gives the quantitative measure of the preferential
%) adsorption of the particular component, when all the components in a
PDMS 2a CO2/ 51.39 [136] gas mixture can enter the pores. 3. Kinematic selectivity, which gives the
CH4 quantitative measure of the ability of the faster component over the
PPO 5 e
CO2/N2 30 [145] slower component to enter the pore and get adsorbed. Hence, to un­
PPO 5c CO2/N2 34 [145] derstand the gas separation performance through zeolites, it requires
PEBA 8 CO2/ 19 [146]
CH4
knowledge of the above three factors. On the other hand, zeolites are
PIM-1 1d CO2/N2f 32.9 [137] expensive. Therefore, to address the issues related to both polymer
PES 2 CO2/ 33.76 [147] membranes and zeolite membranes researchers came up with a new
CH4 strategy of combining them to prepare a novel polymer-zeolite MMM.
PI 3c CO2/N2f 37.74 [140]
Over the years, different zeolites have been found out, however only 20
PDMS 1b CO2/N2f 11.83 [148]
PES (Hollow fiber) 0.5d CO2/N2f 63.8 ± 1.3 [149] out of 245 zeolite structures (natural and man-made) are used as the
PES 1c CO2/ 55.8 ± 2.1 [141] dispersed phase in the membrane preparation followed by the gas sep­
CH4 aration [158,159]. Properties of some most relevant zeolites utilized in
PI 1c CO2/ 16.5 [141] gas separation membranes are presented in Table 10.
CH4f
CA 10 b
CO2/ 48.92 [142]
At higher loading, the difference between polymer and zeolite den­
CH4 sities and physical properties leads to formation of zeolite clusters in the
PEI 1c O2/N2 3.75 [150] polymer matrix, which further increases the unavoidable defects in
6FDPA-TA 2e H2/CH4 88 [143] terms of voids in the membrane that declines the membrane perfor­
cellulose acetate 0.1c CO2/N2 2.887 [151]
mance. However, lower loading of zeolite leads to non-uniform scat­
butyrate
PES 0.02c CO2/N2 1.235 [152] tering of particles in the dope solution. As a result, the viscosity of the
a
casting solution decreases which can bring the non-regularity in the
Pristine SWCNT.
b
membrane. Besides, when membranes are fabricated at elevated tem­
Pristine MWCNT.
c perature the zeolite particles tend to move to surface and agglomerate
functionalized MWCNT.
d (Fig. 8), which is extremely undesirable [75]. Therefore, it is of great
functionalized CNT.
e
Functionalized SWCNT. importance to optimize the zeolite loading to fabricate a defect-free gas
f
membrane performance was checked for more than one gas pair and the best separation membrane. Kulprathipanja et al. [160] in the mid-1980s for
results are obtained with the selected gas pair. the first time performed the study on zeolites/polymer-based MMM.

approximately 3 to 12 Å [153–155]. Their crystalline structure features Table 10

the sharing of corner TO4 tetrahedra atoms, where T is an aluminum or Various zeolites used in the gas separation, their chemical structure and prop­
silicon atom and also the first series of transition metals. There has been erties [155].
numerous application areas found in which zeolites are used, viz., Zeolite Pore Size (A) Structure Structure Si/Al Cation
adsorption, water treatment, catalysis, and gas separation. However, in Type Dimension
recent years, they have been the focus of much attention in gas sepa­
3A 0.29 LTA 3D 1 K+
ration field due to their beneficial properties such as higher surface area 4A 3.8 LTA 3D 1 Na+
due to microporosity, insolubility in water, molecule-sized dimensions, 5A 4.3 LTA 3D 1 Ca2+
ability to accommodate active metal species, high pressure resistant, Silicalite-1 (5.1 × 5.5) and (5.3 MFI 2D >500 –
high thermal and chemical stability, wide ranges of structure and × 5.6)
ZSM-5 (5.1 × 5.5) and (5.3 MFI 2D – –
shapes, etc., than those of previously existing inorganic materials. × 5.6)
Table 9 compares some of the main features of zeolite with other inor­ SAPO-34 3.8 CHA 3D – –
ganic materials. 13X 7.4 Faujasite 3D 1.2 Na+
Separation of any gas mixture in zeolite is affected by the following NaY 7.4 Faujasite 3D – –
ZSM-2 7.4 Faujasite 3D
three factors [157]: 1. Prohibition of one of the gas components present – –

Table 9
Features of some filler materials used for MMM preparation [156].
Zeolites MOFs Silicas Carbon Molecular Sieves

Fixed pore size
High temperature stability
High stability in humidity
Limitations for modification
Pore size crystallographically
controlled
Great potential as supported thin film
Not thermodynamically most stable but
dense
structures
Well-defined molecular sieving
Good sorption and diffusion properties
Cations interconnected by organic
anions
Rather flexible and dynamic
frameworks
Coordinative bonds
Flexible pore size, soft structure
Not well-defined molecular sieving
Low temperature stability
Poor stability in humidity
Thermodynamically unstable
a variety of possibilities
for modification
Directly alter themolecular packing of the High adsorptivity capacity
polymer chains
Increase the free volume of polymers Relatively wide opening with constricted
apertures
Nonpermeability of the nonporous silica particles Better affinity to glassy polymers
Probable weak interaction Good adhesion at interfaces
silica–polymer
High possibility to produce interfacial voids High productivity with excellent
separation
Possibilities for surface modification (e.g., silane Well-defined molecular sieving
coupling)
– Great potential for MMMs
– –
– –

11
A.R. Kamble et al.
Fig. 8. Development of the instability in films cast at elevated temperature (Reproduced with permission from Elsevier [74]).
Since then, various zeolite-based MMMs concerning the gas separation
were studied till date. (Table 11). Some of these membranes found to
exhibit outstanding gas separation performance which could cross the
trade-off curve (Table 11).
5. New emerging inorganic fillers for gas separation
Discovery of monolayer graphene in 2008 by Geim and Novoselov
led to explore various other types of 2D materials, viz., covalent organic
frameworks (COFs), MXenes, molybdenum disulfide (MoS2), layered
double hydroxide (LHD), 2D MOFs, hexagonal boron nitride (h-BN),
[190–194]. Fig. 9 depicts examples of 2D materials.
Recently, these materials have received considerable attention in gas
separation owning to their impressive properties viz., molecular sieving
ability, high surface area, atomic thickness, high dispersion ability (well
dispersed in water and other polar solvents), super-flexible, providing a
possibility to assemble novel types of high efficiency, super-thin gas
separation membranes [190–193]. Many theoretical studies computa­
tionally demonstrated the separation capabilities of 2D materials for
gases by designing sub-nanometer-sized pores within [194–207]. These
computational studies further triggered interest in practical imple­
mentation of the 2D materials in gas separation. Kim et al. [208] were
the first who gave a breakthrough by exploiting the potential of gra­
phene and GO membranes in the gas separation. They fabricated the
membranes by successfully depositing graphene and GO on the poly
(1-methylsilyl-1-propyne) and PES substrate, respectively, and evalu­
ated against CO2/N2and O2/N2 separation. It was observed that the gas
permeability obtained with graphene membrane was decreased with a
gradual increase in the GO layers, whereas O2/N2 selectivity was
improved from 1.5 to 6, transcending the upper bound limitations of the
polymeric membranes. This increase was mainly ascribed to the irreg­
ular alignment of defective graphene sheets which resulted in the
development of gas permeable, slit-like interlayer spacing in the mem­
brane. In contrast to graphene membranes, gas permeability was found
to be increased through thick GO membranes at elevated pressure. Li
et al. [209] deposited a very thin GO coating on anodic aluminum oxide
(AAO) support up to 1.8 nm thickness for highly selective H2 separation.
The first experimental use of MoS2 and Mxenes as membrane material
was performed by Wang et al. [210] and Ding et al. [211] for H2/CO2
separation.
Despite the remarkable molecular transport properties of 2D nano­
porous membranes, their low separation efficiency, production method,
scale-up, larger pore size and performance instability of nano-channel
structure for long-term membrane operations, etc., limits their prac­
tical use in the gas separation. Consequently, 2D based membranes are
currently found to be inappropriate to use in the gas separation appli­
cation [212]. To overcome these drawbacks more recent studies
demonstrated the incorporation of 2D nano-fillers in the polymers to
achieve MMMs as an alternative to pure 2D membranes that might open
the doors for 2D materials for their practical use in the future. As such,
quite a few studies have been found in the open literature which utilizes
12
Renewable and Sustainable Energy Reviews 145 (2021) 111062
2D materials in the preparation of MMMs for gas separation. For
instance, Yang et al. [213] used copper 1,4-benzene dicarboxylate
nanosheets (ns-CuBDC) as 2D inorganic filler for modifying the matrix of
high free volume polymers such as 6FDA-DAM and PIM-1. The gas
separation experiments were conducted at 25 ◦ C and 1 bar using a
CO2/CH4 equimolar binary gas mixture. The results showed a consid­
erable improvement in CO2/CH4 selectivity at low loading (2 wt %)
ns-CuBDC, i.e., the selectivity for 6FDA-DAM/ns-CuBDC and
PIM/ns-CuBDC was increased from 30 to 17 to 43 and 24, respectively.
The possible reason given for this was due to the 2-D topographical
feature of ns-CuBDC and its orientation in the polymer matrix which
obstructs the direct diffusion of the larger CH4 molecules. Consequently,
CH4 molecules diffuse through the more tortuous pathway, resulting in a
considerable loss in CH4 permeability and increase in CO2/CH4 selec­
tivity (Fig. 10).
Shen et al. [214] demonstrated the first time use of MoS2 as an
inorganic nano-filler to prepare Pebax/MoS2 MMMs for CO2/N2 sepa­
ration. Before the membrane preparation, bulk MoS2 was exfoliated in
ethanol/H2O (70/30 by weight) solvent via sonication to obtain the
homogeneous dispersion of MoS2 inside the polymer matrix. The gas
permeation test conducted against pure CO2 and N2 revealed the sig­
nificant improvement in CO2/N2 selectivity at 0.15 wt% of MoS2 in the
Pebax matrix, i.e., selectivity was increased from 44 to 93 for MoS2
(0.15)-Pebax/PDMS/PSf combination. Li et al. [215] successfully
employed the novel ultrathin 2D α-Ni(im)2 nanosheets into a matrix of
Pebax MH 1657. The obtained MMMs exhibited a significant improve­
ment in CO2/CH4 selectivity with no remarkable change in CO2
permeability compared to the pure Pebax membrane. In other words, 2
wt% loading of α-Ni(im)2nanosheets in the membrane improved the
CO2/CH4 selectivity from 19.4 to 33. This improvement was mainly
ascribed to the high aspect ratio of α-Ni(im)2 nanosheets. As a result,
more tortuous diffusion paths were created for larger molecule CH4
which further caused a significant reduction in CH4 permeability and
enhancement in CO2/CH4 selectivity. Shete et al. [216] in their studies
first synthesized 2D Cu(BDC) nanosheets using bottom-up approach and
then the different loading of it (5, 8, and 12 wt%) was successfully
incorporated in the matrix of Matrimid polymer. Both the single gas and
mixed gas permeation tests were carried by employing the prepared
MMMs. The results showed a decreasing trend for selectivities with in­
crease in the pressure which was ascribed to the loss in the gas perme­
abilities through the MMMs. For instance, upon addition of 8 wt% Cu
(BDC) nanosheets CO2 and N2 permeabilities of MMMs were decreased
by 50% and 70%, respectively compared to pristine Matrimid which
resulted in increasing the CO2/N2 selectivity by 70% over the pristine
polymer. Biswal et al. [217] for the very first time used COF based fillers
(TpPa and TpBD) for the preparation of TpPa-1/PBI-BuI and
TpBD/PBI-BuI hybrid membranes, aiming to improving the filler
loading and thereby improving the overall permeability of the mem­
branes. They were able to maintain the highest possible loading of COF i.
e. up to 50 wt %without any defects, owning to the obtained good
adhesion between benzimidazole group of PBI and COFs via hydrogen
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

Table 11
Different zeolites based MMMs for gas separation.
Polymer Type Zeolite Zeolite Gas Selectivity References
Type loading Pair
(Wt.%)

6FDA-6FpDA- ZSM-2 20 CO2/ 24.18 [161]

DABA CH4a
polyimide
PDMS Silicalite-1 50 CO2/ 5.50 [162]
CH4
6FDA-6FpDA- L 20 CO2/ 60 [163]
DABA CH4a
polyimide
PES A 20 O2/ 6 [164]
N2
Udele ® Nu-6 (2) 14.7 H2/ >398 [165]
CH4
PES NaA 50 CO2/ 59.6 [166]
CH4
PDMC SSZ-13 15 CO2/ 41.9 ± 0.7 [167]
CH4
PES SAPO-34 20 CO2/ 24.9 [168]
CH4a
SPEEK MCM-41 30 CO2/ 38.39 [169]
N2a
PDMS zeolite 4A 40 H2/ 3.5 [170]
CO2
PI 4A 30 CO2/ 50.6 [171]
N2
Fig. 9. Examples of the state-of-the-art 2D nanosheet building blocks for the
PI ZSM-5 20 CO2/ 86.2 [171]
N2 preparation of gas separation membranes (Reproduced with permission from
PDMS ZSM-5 38 CO2/ 12.4 [172] The Royal Society of Chemistry [192]).
N2a
Matrimid® SAPO-34 20 CO2/ 67 [173]
bond. Out of all the gases used in the gas permeation experiment, H2 gas
5218 CH4
PES 4A 20 CO2/ 3.20 [174]
showed three-fold increase in the permeability at 40 wt %TpPa-1
CH4 loading i.e. for H2 gas permeability of 18.8 Barrer was achieved
PSf Cloisite 0.5 CO2/ 32.85 [175] compared to pure PBI which is 6.2 Barrer. This rise in H2 permeability
15A® N2a allowed rise in the H2/CH4 selectivity from 155 to 165.5 and H2/N2
PTMSP LiA 15 O2/ 1.55 [176]
selectivity from 69 to 79. Similarly, in the work carried out by Zou et al.
N2
Matrimid 5218 ZSM-5 5 CO2/ 60.1 [177] [218] reported the use of COF nanosheets (TpPa-1 -nc) for improving the
CH4 CO2/N2 separation performance through PEBA polymer. The composite
Matrimid NaY 15 CO2/ 43.3 [178] membranes were prepared by spin coating on the PVDF ultrafiltration
CH4
support. The CO2 and N2 permeabilities measured were found to be
Polyether-b- IWS 8.5 CO2/ 62.8 [179]
amide N2a
higher for MMMs. The maximum selectivity of 64 was obtained PEBA
6FDA-durene zeolite T 1 CO2/ 19.1 [180] matrix containing 1 wt % of TpPa-1-nc. COF-5 nanosheets were chosen
polyimide CH4 by Duan et al. [219] to modify the Pebax-1657 matrix. CO2/N2 selec­
Matrimid® Deca- 20 H2/ 375.27 [181] tivity was found to be promoted to 49.3 from 31.3 after the addition of
dodecasil CH4
0.4 wt % of COF-5 filler. In similar way, Liu et al. [220] in the year 2020
3R
PVDF zeolite 4A 10 CO2/ 4.21 [182] incorporated the Pebax matrix with MXene nanosheets to prepare the
CH4 Pebax-based MMMs for CO2 capture. The addition of MXene enhanced
PU 3A 24 CO2/ 22.08 [183] the CO2 absorption capacity of the membranes. As a result, MXene
N2a loading of 0.15 wt % exhibited the maximum CO2/N2 selectivity of 72.5.
PU 4A 18 CO2/ 24.22 [183]
N2a
A follow up study by Kamble et al. [221–224] also confirmed the
PU ZSM-5 12 CO2/ 22.50 [183] potential of 2D materials in the gas separation via fabricating the flat
N2a dense configuration of polymer/2D MMMs. In their study, experimental
F-PEEK 4A 30 CO2/ 58 [184] verification was carried out by modifying different polymer materials,
N2a
viz., PVDF, PEI and PES with h-BN, MoS2, and GO 2D materials. From
PSf ZCC 1 O2/ 0.914 [185]
N2 their results, it was confirmed that 2D particles when impregnanted in
PU SAPO-34 20 CO2/ 58.59 [186] the polymer, they ruptured the polymer matrix and significantly
N2a enhanced the void fraction in the membrane which further enabled an
Matrimid® Na-ZSM-25 5 CO2/ 169 [187] easy transportation of gas molecules through the membrane. On the
5218 CH4
P84 co- ZCC 1 O2/ 4.92 [188]
other hand, it was found that the higher loading (greater than the
polyimide N2 optimal) of 2D materials formed the particle clusters in the membrane.
Matrimid® 5A 10 CO2/ 34.4 [189] As a result, the performance of the prepared MMMs achieved was
5218 CH4a limited by the selectivity. At present, there are very few studies available
a
Membrane performance was checked for more than one gas pair and the best on 2D material based MMMs for gas separation in the literature
results are obtained with the selected gas pair. (Table 12).
Although the results in the literature validated the concept of poly­
mer/2D and provided a good starting point for the 2D materials, dis­
engaging their layers from each other at higher loading is still the largest

13
A.R. Kamble et al. Renewable and Sustainable Energy Reviews 145 (2021) 111062

Fig. 10. a) 2D structure ns-CuBDC; b) possible orientation of ns-CuBDC in the polymer (Reproduced with permission from The Royal Society of Chemistry [213]).

field of 2D material is one that is growing quickly and there is still much
Table 12
to be explored and learned about it from both an experimental and
Different 2D based MMMs for gas separation.
theoretical perspective. Their use in the gas separation applications is
Polymer 2D material Loading Gas Selectivity References found to be at a premature stage and therefore there remains a great deal
Type type (Wt.%) Pair
of work to be carried out on 2D material based membranes before they
PEBAX MXene 1 CO2/ 63 [225] are to be called as next generation membranes such as methods to
(Ti3C2Tx) N2 incorporate the precise amount of these 2D materials in the polymer
PEBAX COF-5 0.4 CO2/ 49.3 [219]
N2
matrix to avoid the agglomeration, and control over the pore size. From
Matrimid Cu(BDC) 8 CO2/ 48 [216] the market perspective, it is important to fabricate the thinnest possible
N2 membranes to achieve the maximum flux to reduce the separation cost.
PBI COF 40 H2/ 165.5 [217] However, with the available methods for exfoliation 2D materials at
CH4
present such as sonication and ball milling it is difficult to obtain single
6FDA-DAM Cu(BDC) 15 He/ 410 [226]
CH4 layers of 2D materials which hinders the preparation of thin 2D based
Matrimid Cu(BDC) 15 He/ 309 [226] MMMs. However, it is suggested that if the proper shear forces of son­
CH4 ication power or ball milling are employed, one would be able to achieve
PEBAX CuMOF 4 CO2/ 13.54 [227] high performance homogenous membranes. Additionally, other factors
CH4
PBI CuMOF 20 H2/ 26.7 [228]
such as long-term stability and mass production should be considered.
CO2 Furthermore, it is anticipated that selecting an appropriate 2D/
PBI COF 20 H2/ 31.4 [229] polymer pair would lead to formation of very thin membranes with high
CO2 separation performance. There also remains to be seen the potential of
PEBAX MXenes 0.15 CO2/ 72.5 [220]
these polymer/2D MMMs for other gas mixture systems such as
N2
hydrogen/carbon dioxide, and hydrocarbon/methane, etc. However,
the higher price of 2D materials hinders their application in the prepa­
challenge to obtain the better membrane efficiency in terms of gas ration of large spiral wound or hollow fiber membranes. Therefore, it is
permeability and selectivity. Also, further research is needed to unravel still a great challenge to use these materials for large-scale industrial
the best combination of polymer and 2D material for gas separation. It is applications. We hope that the continuous efforts that are being taken
also anticipated that these materials will bring more exciting opportu­ place in achieving the excellent 2D material based MMMs may further
nities and outcomes in the field of membrane gas separation. boost the applications of 2D materials not only in gas separation ap­
plications but also in other membrane-based applications water purifi­
6. Conclusions and future prospects cation, batteries and fuel cells.

Mixed matrix membranes containing different inorganic fillers are

Declaration of competing interest
dominating the research filed in the gas separation as they exhibit a
potential to provide both permeability and selectivity in several order
On behalf of all the authors, the corresponding author states that
higher than the pure polymer membranes. The rapid development in
there is no conflict of interest.
many new families of inorganic materials in recent years is the indica­
tion of MMM becoming future membranes. Therefore, this review ex­
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