Separation and Purification Technology 188 (2017) 431–450

Contents lists available at ScienceDirect

Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Review

Recent progress of fillers in mixed matrix membranes for CO2

separation: A review
Mari Vinoba a,⇑, Margandan Bhagiyalakshmi b, Yousef Alqaheem a, Abdulaziz A. Alomair a, Andrés Pérez a,
Mohan S. Rana a
a
Petroleum Research Center, Kuwait Institute for Scientific Research, Ahmadi, Kuwait
b
Department of Chemistry, Central University of Kerala, Kasaragod, India

a r t i c l e i n f o a b s t r a c t

Article history: Among various CO2-mitigation technologies, membrane-based technology has offered a more energy effi-
Received 19 May 2017 cient and eco-friendly process for CO2 separation from large emission sources, in order to reduce CO2
Received in revised form 17 July 2017 emission level into atmosphere. In general, polymeric and inorganic membranes have been used in gas
Accepted 17 July 2017
separation processes, but each has its own pros and cons. Currently, membrane research has addressed
Available online 22 July 2017
the trade-off limitations of membranes in different ways through fabrication of new type of mixed matrix
membranes (MMMs) by incorporation of inorganic particles as fillers into polymer matrices. The perfor-
Keywords:
mance of MMMs depends on textural properties of fillers, molecular sieving effect and membrane–pen-
Mixed matrix membranes
CO2 separation
etrant interactions. The main challenges in the fabrication of MMMs is selection of fillers, which controls
Zeolites the gas separation characteristics of membranes. In this review, the influences of fillers like zeolite, car-
Carbon fillers bon, and metal organic framework in MMMs fabrication and their CO2 permeability and CO2/CH4 and
Metal organic frameworks CO2/N2 selectivity were compiled from recent reports. Further, a new protocol is introduced for screening
of fillers, which will helps to development of new fillers as well as for fabrication of new MMMs with high
CO2 separation capacity.
Ó 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
2. Membrane principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
2.1. Definition, formula and units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
2.2. Classification of membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
3. Mixed matrix membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
3.1. Classification of fillers based on permeability and selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
4. Zeolites and related fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
4.1. Zeolites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
4.2. Mesoporous silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438

Abbreviations: CA, cellulose acetate; b-CD, beta-cyclodextrins; CCS, carbon capture and sequestration; COK, Centrum voor Oppervlaktechemie en Katalyse; CMS, carbon
molecular sieves; CNFs, carbon nanofibers; CNTs, carbon nanotubes; ETS, engelhardt titanosilicate; 6FDA-DAM, 2,2-bis(3,4-carboxyphenyl) hexafluoropropane dianhydride-
diaminomesitylene; GO, graphene oxide; GPU, gas permeation unit; GTA, glycerol triacetate; IL, ionic liquids; IPCC, Intergovernmental Panel on Climate Change; MCM, mobil
composition of matter; MFI, mordenite framework inverted; MWCNTs, multi-walled carbon nanotubes; MIL, materials institute lavoisier; MMMs, mixed matrix membranes;
MOFs, metal organic frameworks; PDMS, polydimethylsiloxane; PEBA or PEBAX, poly(ether-block-amide); PEI, polyethylenimine; PEG, poly(ethylene glycol); PEO, poly
ethylene oxide; PES, polyethersulfone; PF, permeability factor; PI, polyimide; PIM, polymers of intrinsic microporosity; PMP, poly(4-methyl-1-pentyne); PMPS,
polymethylphenylsiloxane; POZ, poly(2-ethyl-2-oxazoline); PSf, polysulfone; PVC-g-POEM, poly(vinyl chloride)-g-poly(oxyethylene methacrylate); PVDF, poly(vinylidene
fluoride); PU, polyurethane; SAPO, sodium-alumino-phosphate; SF, separation factor; SBA, santa barbara amorphous; SWCNTs, single walled carbon nanotubes; SEBS,
polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene; SPEEK, sulfonated poly(ether ether ketone); TS, titanium silicalite; UiO, University of Oslo; UNFCCC,
United Nations Framework Convention on Climate Change; ZIF, zeolitic imidazolate framework; ZSM, zeolite socony mobil.
⇑ Corresponding author at: Petroleum Research Center, Kuwait Institute for Scientific Research, P.O. Box 24885, Safat 13109, Kuwait.
E-mail addresses: vinoba76@gmail.com, vmari@kisr.edu.kw (M. Vinoba).

http://dx.doi.org/10.1016/j.seppur.2017.07.051
1383-5866/Ó 2017 Elsevier B.V. All rights reserved.
432 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450

4.3. Silica nanospheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438

4.4. Overview of zeolite-based fillers in MMMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
5. Carbon fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
5.1. Carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438
5.2. Carbon molecular sieves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
5.3. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
5.4. Overview of carbon-based fillers in MMMs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
6. Metal organic framework fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
6.1. UiO-66 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
6.2. Zeolitic imidazolate frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
6.2.1. ZIF-7 and ZIF-8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
6.2.2. ZIF-11 to ZIF-302 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
6.3. MIL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
6.3.1. MIL-53 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
6.3.2. MIL-68 to MIL-125 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
6.4. Cu-based MOFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
6.5. Overview of MOF-based fillers in MMMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
7. Profile of zeolite, carbon, and MOF fillers in MMMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
8. Conclusion and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447

1. Introduction been evolved as a competitive technique in energy production

The current world energy demand and industrialization
requires a large amount of fossil fuel, which results in enormous
CO2 emission into the atmosphere from power plants, ends up in
major changes in the biological world, and affects all levels due
to trapping the earth’s surface temperature resulting in global
warming. Intergovernmental Panel on Climate Change (IPCC)
report has projected that by the year 2035, CO2 level will increase
to 450 ppm, which will lead to a chance of increase in 2 °C global
temperature [1]. It also reveals that the global increase rate of
CO2 is about 11.7 ppm from 2005 to 2011, and based on the predic-
tions of the simulation model, globally averaged CO2 from the
preindustrial era to the present increases by 794–1149 ppm by
the year 2100 [2]. According to the Keeling curve, each 188 million
tons of CO2 emission contributes to raise in 1 ppm of atmospheric
CO2 concentration and the level reached 408.84 ppm in June 2017
[3]. The United Nations Framework Convention on Climate Change
(UNFCCC) COP 21 (Conference of Parties) at Paris, December 2015,
has set a task for all countries to control the increasing atmo-
spheric warming well below 2 °C and move to a low carbon path-
way for energy production [4]. The major CO2 emitters are energy
sectors, steel and cement industries, and the existing mitigation
policies in these sectors are mainly focused on increasing energy
efficiency processes, switching to low carbon-intensive sources of
energy, and carbon capture and sequestration (CCS). Further, the
refineries have also been marked as huge CO2 emitting sectors
due to the unregulated pumping of CO2 in refineries. Compared
to other sources, about 4% of the global CO2 emissions, close to
1 bmt CO2/year, has been contributed by the refineries, which
ranked 3rd among stationary CO2 producers [5]. Thus, there is an
urgent need to develop CO2 mitigation processes, and it becomes
mandatory at all levels of CO2 emission sources. A number of tech-
nologies have been employed for CO2 removal, such as pre-
combustion, post-combustion, and oxy-fuel combustion. Among
these, the post-combustion CO2 capture is generally compatible
with CCS activity which includes, commercial absorption tech-
nique by alkanolamines [6–8], adsorption [9–11], chemisorption
[12,13], membrane separation [14,15], cryogenics separation
[16,17], and enzymatic [18–20] processes; still they have their
own demerits like corrosive nature, low CO2 separation yield, high
cost regeneration process, etc.
In fact, the interest for commercial CO2 separation and capture
can be efficiently achieved by membrane technology, which has
and natural gas industries [21–23]. It is fairly reported that mem-
brane process has inherent attributes like low energy consumption
with continuous operation, cost-effectiveness, and process flexibil-
ity compared to the traditional methods [24,25]. Membrane per-
formances can be categorized based on various aspects such as
separation mechanism, nature and structure of materials. Further,
diffusion phenomena are also governed by the morphological and
physical properties such as total pore volume, pore size distribu-
tion, average pore diameter, and pore length of membrane. These
textural properties are innate characteristics, which depend on
the type of membrane materials, and can be subjected to surface
enrichment or modifications. In general, molecular diffusion
depends on the diameter and the length of molecules [26,27].
Fig. 1 shows the kinetic diameter of various gas molecules and pore
diameter required for their separation.
Many new membranes are still being developed for rapid CO2
separation from emission streams. Generally, polymeric mem-
branes are used for CO2 separation due to cost-effective process,
durable in industrial processing, energy efficient, and flexible com-
pared to the other available CO2 separation processes. Upon fabri-
cation with either glassy or rubbery materials, polymer
membranes can achieve better CO2 separation based on molecular
sieving by difference in size and diffusion principle [28,29]. Fur-
ther, rubbery material separates components based on condens-
ability whereas the glassy material stringently separate gases
based on difference in size or kinetic diameter [28,30]. Thus, the
glassy polymers perform better in gas selectivity with high perme-
ability than rubbery polymers. However, the polymeric mem-
branes have restrictions due to their ‘‘trade-off” between
permeability and selectivity of gases, these limitations have been
resolved and the productivity of polymeric membrane might be
improved by the modification of polymeric membranes, which
could diminish the selectivity or vice versa [31,32].
Inorganic membranes possess molecular sieve-like properties
show significantly higher diffusivity and selectivity of gas mole-
cules compared to polymeric membranes due to their discriminat-
ing ability based on pore size and shape. Further, these inorganic
membranes are advantageous in terms of thermal and chemical
stability, mechanical strength, and longer lifespan [33]. Specifi-
cally, inorganic membranes efficiently favor CO2 separation
because of their narrow pore size distribution, and high operating
temperature and pressure. Yet, the other parameters of these
membranes, such as fabrication of defect-free membrane for
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
Fig. 1. Cutoffs of pore diameter required for different separation techniques.
large-scale operation, brittleness, and operation cost, also matter,
when putting them into operational streams [34–37]. Thus, the
development of a new membrane technology for gas separation
is still fascinating the researchers to overcome the boundaries of
the polymeric and inorganic membranes and provide an alterna-
tive membrane with better separation properties. Recently,
inorganic-polymer composite materials are being involved in
membrane science to overcome the trade-off effect of membranes
[31]. The heterogeneous membrane, also called as mixed matrix
membranes (MMMs), which are obtained through synergistic
interaction between inorganic filler and polymer matrix. The
polymer-inorganic filler interaction avoids the particle agglomera-
tion, pore blockage, void formation, and polymer rigidification in
MMMs fabrication, and enhances the gas separation performance
[38]. Sometimes, based on the nature of the fillers, these interac-
tions also caused reverse effects and revealed poor performances
[39,40].
The choice of proper inorganic filler materials is quite challeng-
ing in MMMs’ fabrication due to the textural characteristics and
interaction of fillers with polymers [35,41,42]. Generally, porous
filler materials like zeolites, carbon, MOFs and mesoporous silicas
give better compatibility with polymer than nonporous filler, due
to pore size distribution and surface chemistry, which resulted in
a higher gas separation performance. The fillers influence the
enhancement of gas permeability in different ways through molec-
ular sieving effect, membrane–penetrant interaction, free volume,
and chain rigidity of polymer [43–46]. In other words, the incorpo-
ration of appropriate fillers, by a small fraction, into the polymer
matrix can significantly increase the overall separation efficiency
and could result in superior gas selectivity performance by MMMs
[47,48]. A few types of fillers when used for MMMs’ fabrication
could simultaneously enhance both the permeability and the selec-
433
tivity than pristine polymer membrane. In this regard, zeolite
[49,50] fillers such as ZSM-5, 3A, 4A, 5A, and Na-X; silica-type filler
materials such as MCM-41, SBA-15, and SiO2; carbon fillers like
CMS, CNTs, and graphene [51], and metal organic frameworks
(MOFs) [52,53] such as UiO-66 [54], ZIF [55,56], MIL [57], and
Cu-based MOFs are investigated for MMMs’ fabrication. Nowadays,
the fabrication of MMMs is facilitated by the dispersion of a single
or a combination of nano-sized fillers into polymer matrices, which
could increase better interfacial contact with polymer matrices for
better CO2 separation [58]. This review provides a better under-
standing of the incorporation of inorganic fillers in MMMs’ and
the outlook of fillers for CO2/CH4 and CO2/N2 separation. This arti-
cle discusses the effect of three kinds of fillers, which are catego-
rized under zeolites, carbon materials, and MOFs. In addition, it
also discusses the current scenario on the development of MMMs
by several research groups for CO2 separation. Finally, the reported
results of MMMs have been analyzed based on fillers, and the
enhancement of permeability and selectivity of CO2, and the out-
comes are discussed.
2. Membrane principles
2.1. Definition, formula and units
The separation efficiency of membranes can be evaluated by
quantifying the permeability and selectivity of gases. The perme-
ability is the mass transfer through a membrane of defined area
per unit time per cross-membrane pressure, and selectivity is the
ratio of single-gas permeability from a mixture of species permeat-
ing through the membrane. The gas transport separations in mem-
brane is executed through absorption, diffusion, and desorption of
molecules on membranes, and depends on driving forces such as
434 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
pressure (DP), temperature (DT), gradient concentration (DC), and
electric potential (DV). The non-SI and SI-units given for perme-
ability are Barrer and gas permeation unit (GPU), respectively. Per-
meability (P) can be calculated using the P = (gas flow
rate
membrane thickness)/(exposed membrane area x pressure
difference across the membrane), and GPU is defined as the ratio
of the molar flux of penetrate gas and pressure difference between
the feed and penetrate gas [52]. The following equations were used
for the calculation of permeability and selectivity in all reports and
are as follows:
Pð1 BarrerÞ ¼ 1010 ½cm3 ðSTPÞcm=½cm2 s cmHg
1 GPU ¼ 106 ½cm3 ðSTPÞcm=½cm2 s cmHg
Selectiv ityðai;j Þ ¼ Pi =P j
From the gas separation performance results reported in various
research articles, the enhanced gas transport properties (permeabil-
ity and selectivity) by fillers were calculated from the ratio between
the gas separation by MMMs (polymer + fillers) and individual
polymer membranes, using the following equations:
Permeability factor ðPFÞ ¼ PðMMMsÞ=PðpolymerÞ
Selectiv ity factor ðSFÞ for ai;j ¼ ai;j ðMMMsÞ=ai;j ðpolymerÞ
The obtained enhanced gas transport properties (permeability and
selectivity) were plotted for a better understanding of the fillers’
impact.
2.2. Classification of membranes
Generally, membranes can be classified into two types based on
their nature and geometry. The membranes are further subdivided
in terms of nature, into biological and synthetic. The applications of
synthetic membrane have spread out in many fields and have been
categorized based on various aspects, such as material type, config-
uration, structure, composition, support material, driven process,
and industrial reactions as shown in Fig. 2. There are many other
changeable parameters that may significantly influence the separa-
tion process, which are further classified in Fig. 3. Feed type and
Fig. 2. Classification of membranes.
process conditions are independently responsible for molecular
separation or the mass transfer from higher to lower pressure via
gas sorption and diffusion processes. In general, the permeance
of gas molecules through sorption phenomena is strongly influ-
enced by the thermodynamic equilibrium on either side of the
membrane transport process. Further, the three major subdivisions
are categorized based on the other parameters as shown in Fig. 3.
3. Mixed matrix membranes
ð1Þ Recently, membrane science involves the development of
nanocomposite-based membrane for gas separation, which over-
ð2Þ comes the ‘‘trade-off” challenge of individual polymeric and inor-
ganic membranes and increases the separation performance.
ð3Þ Each membrane has its own merits and demerits as shown in
Table 1. The low surface area, inadequate thermal stability, and
chemical properties are the main challenges faced in the develop-
ment of efficient commercial membranes. In addition to the above-
mentioned membrane characteristics, mechanical properties such
as crushing, abrasion, and attrition is also important in order to
commercialize membrane technology. Thus to meet some of these
ð4Þ objectives and to overcome the disadvantages of individual poly-
meric and inorganic membranes, MMMs or composite membranes
ð5Þ are obtained by mixing the inorganic and polymeric phases, which
may be linked via van der Waals forces and covalent or hydrogen
bonds [59]. Therefore, selective literature has been compiled as a
review on the composite membrane, especially focusing on the
CO2 separation by MMMs.
The review is to address the role of filler with an aim to over-
come the disadvantages of individual (inorganic or polymer) mem-
brane used as a composite material to take advantage of the
favorable characteristics of both the systems. Many inorganic
materials such as SiO2 [60,61], TiO2 [62], MgO [63], ZIF-8 [64],
and carbon [65] have been tried as a filler with polymeric matrix
and their influence of loading fraction on carbon dioxide perme-
ability and selectivity is shown in Fig. 4. The permeability of these
materials varies with the individual filler and as a function of the
filler content. The role of polymeric contribution has been removed
physically but practically, the synergistic effect provided by the
composite material cannot be separated. It is expected that the
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450 435

Polymeric Textural

Material Type Inorganic Morphology

Composite Composition
Permeability
Influence Feed Type
Liquid
Aqueous

Process condition Gas

Organic

Flow
Low
Pressure
High
Temperature

Fig. 3. Factors influencing membrane permeability.

Table 1
Characteristics of different membranes.

Membranes Advantages Disadvantages

Polymeric  Easy synthesis and fabrication  Low chemical and thermal stability
membranes  Low production cost  Plasticization
 Good mechanical stability  Pore size not controllable
 Easy for upscaling and making variations in module form  Follows the trade-off between permeabil-
 Separation mechanism: Solution diffusion ity and selectivity
Inorganic  Superior chemical, mechanical, and thermal stability  Brittle
membranes  Tunable pore size  Expensive
 Moderate the trade-off between permeability and selectivity  Difficulty in scale up
 Operate at harsh conditions
 Separation mechanism: Molecular sieving (<6 Å), surface diffusion (<10–20 Å), capillary con-
densation (<30 Å), and Knudsen diffusion (<0.1 lm)
Mixed matrix  Enhanced mechanical and thermal stability  Brittle at high fraction of fillers in poly-
membranes  Reduced plasticization meric matrix
 Lower energy requirement  Chemical and thermal stability depends
 compacting at high pressure on the polymeric matrix
 Surpasses the trade-off between permeability and selectivity
 Enhanced separation performance over native polymer membranes
 Separation followed by the combined polymeric and inorganic membrane principle

permeability increases with an increase in inorganic filler fraction,
but in some cases, negative effects are also shown indicating that
either the role of filler or the synergetic effect could not be devel-
oped in the composite membrane. Particularly, SiO2-polysulfone
(PSf) MMMs showed an increasing trend for CO2 gas permeability
with increasing the silica content. On the other hand, other com-
posite SiO2-polyuretane (PU) reveals a decreasing trend in the
selectivity of CO2/CH4 or vice versa, and other composites are also
restricted by the trade-off trend between gas permeability and
selectivity, as reported in Fig. 4. Thus, the selection of inorganic fil-
ler along with a suitable polymer matrix is a key element for
enhancing the performance of membranes, and the surface mor-
phology of fillers are shown in Fig. 5. This review comprise the
influence of inorganic fillers in MMMs for CO2 separation.
and fillers for enhancement of gas separation properties. The per-
meability and selectivity factors are calculated based on the perfor-
mance of membranes. The reports are discussed in the review, and
if the factor is one, the value is due to pure polymer membrane,
and the value above or below one factor is due to filler influence.
In this review, gas separation results have been compiled using
the recent published works, and the enhanced activities of MMMs
by fillers are classified based on permeability and selectivity fac-
tors. From literature, most of the MMMs show improved perme-
ability than selectivity of about 2:1 ratio compare to neat
polymer membrane. In addition, from reported data, enhanced
separation factors by fillers are categorized into four regions (A,
B, C, and D) as per their permeability and selectivity properties,
as shown in Table 2.

3.1. Classification of fillers based on permeability and selectivity 4. Zeolites and related fillers

The major challenges in the fabrication of MMMs are the selec- Zeolites are well-established candidates for gas separation,
tion of fillers in order to increase the interaction between polymer which possess uniform molecule-sized pores, tetrahedral, arranged
436 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450

Fig. 4. Effect of inorganic filler loading fraction in the mixed matrix membrane for the permeability of CO2 (A) and selectivity of CO2/CH4 (B) [60–65].

Fig. 5. SEM image of few fillers. (A) Zeolite-A, (B) Mesoporous silica (SBA-16,) (C) Mesoporous silica (SBA-15), (D) Silica nanospheres, (E) TiO2, (F) MWCNT, (G) CNF, (H)
Graphene, and (I) MOF-74.

Table 2
Classification of fillers for mixed matrix membranes.

Region Permeability factor (PF) Selectivity factor (SF) Fillers suitability for MMMs
PCO2 aCO2 =CH4 ðN2 Þ
Trade-off <1.00 <1.00 Poor Poor
A >1.00 to <3.00 >1.00 to <2.00 Fair Fair
B >1.00 to <3.00 >2.00 Fair Good
C >3.00 >1.00 to <2.00 Good Fair
D >3.00 >2.00 Good Good

by shared oxygen at the corners of aluminosilicate geometric pat- of polymer membranes, such as thermal decomposition or defor-
terns with high thermal and chemical stability. Considering the mation at high temperature, high pressure, and oxidative atmo-
above-mentioned properties, zeolites overcomes the limitations spheres. Generally, zeolite membranes can be divided into two
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
types: zeolitic films on support by film precursors growth on the
support surfaces, and self-supporting membranes by continuous
process. Further, zeolitic films can be classified as zeolite-filled
mixed matrix membrane, self-supported and supported zeolite
layers. Gas separation over zeolite-based membranes is performed
through three plausible mechanisms such as molecular sieving
with the pore sizes that are smaller or similar to gas molecules;
diffusion-controlled separation that depends on the relative size
of the diffusing gas molecule through the pore size of membrane;
and adsorption-controlled separation by adsorptive interaction
between the zeolite framework and the permeation gas molecules
[66,67].
4.1. Zeolites
Recently, zeolite-based MMMs fabricated by the interaction
between polymer segments and surface modified zeolite by chem-
ical coupling linkers have been extensively studied, which shows
high performance [68,69]. The other conventional Grignard or
solvothermal treatment for surface altering by the formation of
Mg(OH)2 nanowhiskers, which enhances the surface roughness of
zeolite crystals and enhances the zeolite – polymer interface,
shows appreciable results [70–72]. The defect-free membrane with
polymer matrix is fabricated by growing inorganic nanostructure
on the surface of zeolite by ion-exchange or dealumination from
the extra framework cation of aluminosilicate zeolite [73]. The dif-
ferent forms of zeolites were involved in gas separation such as
NaA, NaX, NaY, ZSM-5, MFI, and silicates [74]; other zeotype and
silica materials, such as TS-1[75], ETS-10 [75], SAPO-34 [76], AlPO
[77], MCM-41[78], COK-12 [79], and SiO2 particles [80], were used
as fillers in MMMs.
Beiragh et al. fabricated MMMs by incorporating ZSM-5 in poly
(ether-block-amide) (PEBAX) matrix. PEBAX provides a good inter-
action with ZSM-5 because of the high chain mobility of poly ethy-
lene oxide (PEO) soft segments and upon varying the polymer/
zeolite interface with respect to ZSM-5 loading from 5 to 15 wt%,
which leads to void reduction and also hinders gases’ permeability
due to ZSM-5 particles, which occupy soft ether segments in poly-
mer. Thus, the superior permeability of CO2 is achieved, about 78%
at 5 wt% ZSM-5 loading, due to the availability of more free volume
by amide chain distribution and PEO segments’ interaction, which
leads to the higher permeability of CO2 than CH4. The nano-porous
ZSM-5 restricts the mobility of polymer chain and leads to the for-
mation of tortuous pathways in polymer, which reduces the diffu-
sivity of CH4 when compared to CO2 [81]. Whereas, ZSM-5 particles
were dispersed into Matrimid matrix, up to 30 wt% loading, via the
phase inversion approach. The higher loading of ZSM-5 particles
leads to the void formation at polymer-filler interfaces due to
incompatibility with Matrimid chains. Thus, the higher permeabil-
ity with good selectivity was obtained at 6 wt% ZSM-5 loading [82].
Other group reported that ZSM-5/Matrimid MMMs can provide
better size and shape selectivity, due to the penetration of polymer
segments into the ZSM-5, which reduces the nonselective voids
between them. The enhanced selectivity of ZSM-5/Matrimid for
CO2/CH4 and CO2/N2 were 34.7 and 17.8, respectively [83]. How-
ever, ZSM-5/polydimethylsiloxane (PDMS) composite was success-
fully coated on a-alumina support for MMMs. PDMS-coated ZSM-5
membranes surpassed the selectivity of CO2/CH4 and CO2/N2, about
47.9% and 118.8%, respectively, than bare ZSM-5 membrane, due to
the presence of PDMS layer on the membrane surface, which
retained the non-zeolitic pores of ZSM-5 [84].
Bryan et al. investigated CO2 separation using synthesized zeo-
lite 13X/PEBAX membranes. The gas permeation properties were
studied on 13X filler loading up to 15 wt% in PEBAX, and improved
permeability and selectivity of about 40% and 14.6%, respectively,
were achieved than neat PEBAX membrane [85]. Whereas, 10 wt
437
% 4A/PEBAX membrane showed that the enhanced permeability
and selectivity of CO2/CH4 and CO2/N2 were 73.8%, 47.2%, and
34.3%, respectively compare to the neat PEBAX membrane, due
to the combination of solution diffusion and molecular sieving
properties [86]. In addition, PEBAX possesses polyamide and poly-
ether segments that provide hard and flexible properties in MMMs
[87,88]. Pakizeh et al. fabricated MMMs using PSf and surface mod-
ified zeolite 4A by the Grignard method with Mg(OH)2. The whis-
ker structure on the zeolite 4A surface greatly improved the
interfacial adhesion between the two phases, and the selectivity
of CO2/CH4 was 68.9% higher than pure PSf membrane [89]. Gong
et al. studied the systematically modified zeolite 5A by ion-
exchange surface treatment used as filler on Matrimid for MMMs
fabrication. A series of MMMs were obtained by varying the load-
ing of nanostructured Mg(OH)2 surface modified 5A fillers. 5A/
Matrimid exhibited significant CO2 permeability and selectivity
of CO2/CH4, of 119.6% and 8.3%, respectively, compared to the neat
polymer membrane. The presence of Mg(OH)2 nanostructures in
MMMs provided better zeolite-polymer interfacial morphology
by the adsorption and entanglement of polymer domains within
the nanostructures, and greater mechanical resistance was gained
[90]. Zarshenas et al. investigated the influence of zeolite NaX filler
on two-layered MMMs for CO2 separation, which was fabricated
via the phase inversion technique by solvent evaporation. NaX fil-
lers were embedded into PEBAX, without any aggregation and
void-free interface due to the presence of the soft polyether seg-
ments in the PEBAX and the support layer coated on the top of
MMMs with polyethersulfone (PES), which showed higher CO2/
N2 selectivity about 145%, than PEBAX/PES membrane. Further-
more, a study on the influence of filler size, pressure, and temper-
ature for good gas separation performance reveals the presence of
nano-sized zeolite NaX, which increases the feed pressure with
optimal temperature [91]. Sanaeepur et al. reported the fabrication
of NH2-NaY/cellulose acetate (CA) MMMs, and the permeability of
CO2 increased about 122%, by the increase of NaY loadings up to
20 wt% into the CA membrane, without decrease in the selectivity
of CO2/N2. In addition, CA-based membranes can play a vital role in
the permeance and flux due to the existence of hydroxyl, carbonyl,
and oxycarbonyl groups in CA [92].
Yu et al. studied the gas transport properties of MFI-type zeolite
and PES-based MMMs. The impregnation of MFI particles can mod-
ify the molecular arrangement in the membrane interface, and
10 wt% MFI/PES membranes have shown the enhanced values of
CO2 permeability of 80%, and CO2/N2 selectivity of 71%, than pure
PES membrane [93]. Martin-Gil et al. synthesized three types of
titanosilicate zeolite and used them as fillers for fabricating MMMs
with Matrimid. A series of flat dense MMMs were fabricated by
varying filler loadings up to 30 wt% and studied for gas separations.
TS-1-100 (Si/Ti = 100) and TS-1-25 (Si/Ti = 25) possess tetrahedral
and ETS-10 (Engelhard Corporation Titanosilicate) has octahedral
structured titanium silicate zeolites. TS-1-100 MMMs revealed
the improved CO2 permeability about 90%, than neat polymer
membrane, because TS-1particles promoted a better adhesion
between fillers and polymeric matrix, which increased CO2 adsorp-
tion. However, TS-1-25 showed a better CO2/CH4 selectivity than
TS-1-100 due to some ‘‘sieve in a cage” morphology defects. The
improved permeability and selectivity of ETS-10 MMMs were
24% and 33%, respectively, than unfilled polyimide membrane
[75]. Zhao et al. reported sodium-alumino-phosphate (SAPO)-
based MMMs fabricated by dispersing SAPO-34 homogeneously
in the PEBAX. Their results exhibited the increased CO2 permeabil-
ity of about 250% at 50 wt% SAPO-34, than the neat PEBAX mem-
brane, without altering the selectivity of CO2/CH4 and CO2/N2
[76]. Jeong et al. reported nanocomposite membranes fabricated
with a polyimide and a porous layered aluminophosphate, these
MMMs shows better selectivity about 3-fold than neat PI mem-
438 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
brane whereas its permeability (<1-fold) falls on trade-off region
[77].
4.2. Mesoporous silica
The silica-based fillers were used for MMMs’ fabrication and
applied in gas separation. Laghaei et al. investigated the effect of
mesoporous MCM-41 fillers and PES matrix in MMMs. The amine
or chlorine groups were grafted on the surface of MCM-41 and
incorporated into the PES matrix; these MMMs showed enhanced
CO2 permeability compared to the neat PES membrane. Among
three fillers, MCM-41 and NH2-MCM-41 showed enhanced CO2
permeability of about 150%, and Cl-MCM-41 revealed about 94%
permeability due to poor interaction with PES. Regardless of these
types of fillers, NH2-MCM-41 contributed an improved selectivity
of CO2/CH4 and CO2/N2 than other fillers, due to polar NAH groups
that provided a strong interfacial adhesion with polymer segments,
which facilitated the fabrication of interfacial void free membranes
with better thermal stability and Young’s modulus [94]. Wu et al.
facilitated the gas transport on MMMs by abundant amine groups
that contain MCM-41 penetrating into the PEBAX polymer. The
polyethylenimine (PEI) grafted in the pore channels and on the sur-
face of MCM-41 produced strong interfacial interactions between
filler and polymer matrix, and unique CO2 permeability was
increased by 210% and 145% in PEI-MCM-41 and MCM-41 than
the neat PEBAX. PEI-MCM-41 embedded membranes showed
enhanced selectivity for CO2/CH4 and CO2/N2 about 115% and
96%, respectively, at 20 wt% filler loading, and surpassed the Robe-
son 2008 upper bound line [78]. Mesoporous COK-12 filler with
Matrimid-based MMMs also showed better CO2 permeability of
about 108.6% at 30 wt% COK-12 than neat polymer, while the
selectivity of CO2/CH4(N2) was almost unchanged [79].
4.3. Silica nanospheres
Hassanajili et al. investigated the effect of hydrophobic nature
on SiO2/Polyesterurethane MMMs for gas separation. The commer-
cial silica nanoparticles were modified with octylsilane and PDMS
to implant hydrophobic properties on the surface. The hydrophobic
chains contain fillers that reduced the aggregation of nanoparticles,
and increased better dispersion than unmodified particles in
MMMs. The unmodified silica nanoparticles reveal better CO2 per-
meability and CO2/CH4 selectivity than other fillers, due to the
presence of hydrophobic branches that increased impenetrable
barriers for CO2 diffusion in MMMs. Based on dynamic free volume
mechanism, the hydroxyl functional groups in the interfacial
region may furnish relatively lower-resistance pathways in the
polyesterurethane/unmodified SiO2 nanocomposite membranes,
which facilitate CO2 diffusion compared to CH4 [80]. Ghadimi
et al. fabricated SiO2/poly (ether block amide) (PEBA) MMMs using
different approaches, including sol-gel, and surface modification by
physical and chemical methods. Poly(ethylene glycol) (PEG) and
cis-9-octadecenoic acid (OA) were used as surface modification
precursors on silica spheres by chemical modification. The surface
modified SiO2 nanoparticles thereby improved their dispersion in
the PEBA matrix and the highest gas separation was achieved with
OA-SiO2 due to the elimination of the agglomeration of filler in
matrix, and the enhanced CO2 permeability and selectivity of
CO2/CH4(N2) were 36% and 125% (128%), respectively, than PEBA
membrane alone. The other sol-gel and physically modified SiO2
nanoparticles showed a lower gas separation and could not pre-
vent the agglomeration of the SiO2 nanoparticles due to the forma-
tion of hydrogen bond [95].
Xin et al. investigated the silica microsperes synthesized by
Stöber method and functionalized with carboxyl (SiO2AC), sulfonic
acid (SiO2AS), and pyridine (SiO2AN) groups using methacrylic
acid, p-styrenesulfonate, and 4-vinylpyridine, respectively. The
functionalized silica microsperes were incorported into sulfonated
poly(ether ether ketone) (SPEEK) matrix and studied for the gas
separation. Fabricated MMMs revealed CO2 permeability, about
1.6 to 3.1-fold higher than pure SPEEK membrane, and surpassed
the trade-off limit in Robeson 2008 [31]. However, the SiO2AN fil-
ler doped MMMs showed higher CO2 permeability (2043 Barrer)
than SiO2AC, SiO2AS, and pristine SiO2-doped MMMs due to the
penetration into SPEEK matrix chains and the creation of CO2 path-
ways with the aid of the amine groups on SiO2 microspheres. Over-
all, the functionalized SiO2 fillers enhanced their respective MMMs’
selectivity for CO2/CH4(N2) than pristine SiO2-doped MMMs. In
addition, the SiO2AN-doped MMMs surpassed the selectivity of
CO2/CH4 and CO2/N2 about 142% and 95%, respectively, due to
affinity between CO2 and acid-base sites at polymer-filler interface
[96].
4.4. Overview of zeolite-based fillers in MMMs
Fig. 6a shows actual permeability and selectivity of zeolite-
based fillers in mixed matrix membrane and their corresponding
polymer matrix for CO2 gas separation. Fig. 6b shows profile of
enhanced permeability and selectivity factors of zeolite-based fil-
lers in mixed matrix membrane for CO2 gas separation. Fig. 6b
was constructed based on the results reported in recent literatures
as shown in Table 3, which reveals that the zeolite-based fillers
have enhanced the permeability and selectivity of CO2 about 95%,
and 85%, respectively. However, Fig. 6b reflect that the enhanced
permeability and selectivity of zeolite fillers correspond to 85%
and 80% and all fall in the A region. The other regions (B, C and
D) were covered the separation factors of about less than 10% fil-
lers. Further, Fig. 6 reveals that the enhanced permeability and
selectivity of MMMs of SiO2-N/SPEEK, SiO2/PU and MCM-41-NH2/
PEBAX falls in the D region. From all the three combination of fil-
ler/polymer matrix, it is understood that filler with ANH2 or
AOH group on the surface shows better gas separation. In spite
of low surface area around 100 m2/g, the silica nanoparticles with
particle size from 14 to 180 nm along with surface functionaliza-
tion with ANH2, AOH and ACOOH group shows better gas separa-
tion. While considering, fillers with large surface area such as
MCM-41, surface modification with ANH2 illustrates better gas
separation. Therefore, it is observed that the surface modified fil-
lers along with suitable polymer matrix show better permeability
and selectivity.
5. Carbon fillers
Carbon-based MMMs were recognized as one of the best candi-
dates for CO2 separation, which efficiently overcome Robeson’s
upper bound trade-off limit [31,101]. In MMMs approach, carbon
fillers, such as multi-walled carbon nanotubes (MCNTs), single
walled carbon nanotubes (SCNTs), carbon molecular sieves
(CMS), carbon nanofibers (CNFs), and graphene oxide (GO) materi-
als, were embedded along with polymer matrices and used for the
separation of CO2. These fillers play a vital role in gas separation
application due to their gas transport and mechanical properties.
5.1. Carbon nanotubes
Carbon nanotubes (CNTs) consist of sp2 hexagonal carbon
atoms and are constructed through seamless tube made by rolling
up graphene. CNTs are classified as single and multi-walled CNTs
and recognized as filler in MMMs. CNTs are uniformly dispersed
in polymer matrices, and they have strongest carbon-carbon bond
in the graphite layer, which leads to the enhancement of the
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450 439

104
a - Zeolite b

Selectivity Factor (SF) of CO 2 /CH4 and CO2 /N2

CO2/CH4
(MMMs) Trade-off
- Mesoporous silica
2008 Upper Bound for CO 2/CH4 (Polymer) region - Silica nanoparticles
Selectivity (CO2 /CH4 and CO2 /N2 )

CO2/CH4
- Other fillers
(MMMs)
103 CO2/N2
101
CO2/N2
(Polymer)

B D
102 Enhanced
region

A C
101
100
100 101 Trade-off
region
100
10
-4
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4 Permeability Factor (PF) of CO2
Permeability of CO2

Fig. 6. Profile of zeolite-based fillers in mixed matrix membrane for CO2 gas separation; (a) Actual permeability and selectivity of MMMs and their corresponding polymer
matrix [75–100] and 2008 upper bound for CO2/CH4 [31]. (b) Permeability and Selectivity factors, filled and unfilled symbols represent the selectivity factor of CO2/CH4 and
CO2/N2 respectively (Data obtained from Table 3).

Table 3
CO2 separation performance of zeolite-based fillers in mixed matrix membranes.

Filler Type Fillers Polymer matrix Filler (wt.%) P (bar) T (°C) PF (PCO2) SF (aCO2/CH4) SF (aCO2/N2) Ref
Zeolite ZSM-5 PEBAX 5 1 35 1.78 1.16 – [81]
ZSM-5 Matrimid 6 2 35 1.29 1.04 – [82]
ZSM-5 Matrimid 20 10 35 1.19 1.90 1.54 [83]
ZSM-5 PDMS 15 1.5 27 0.20 1.48 2.19 [84]
13X PEBAX 15 – – 1.40 – 1.15 [85]
4A PEBAX 10 25 RT 1.74 1.47 1.34 [86]
4A PSf 35 5 RT 1.00 1.69 – [89]
5A Matrimid 20 1 40 2.20 1.08 – [90]
Na-X PEBAX 20 7 25 0.78 – 2.45 [91]
Na-Y CA 20 4 25 2.23 – 1.19 [97]
Na-Y-NH2 CA 20 2 25 1.85 – 1.04 [92]
MFI PES 10 – 35 1.80 – 1.71 [93]
SAPO-34 PEBAX 50 7 35 3.50 1.00 1.00 [76]
AlPO PI 10 4 35 0.44 3.05 2.85 [77]
Mesoporous Silica MCM-41 PES 20 8 25 2.54 1.04 0.93 [94]
MCM-41-NH2 PES 20 8 25 2.46 1.39 1.26 [94]
MCM-41-Cl PES 20 8 25 1.94 1.01 0.90 [94]
MCM-41 PEBAX 20 1 25 1.53 1.00 1.00 [78]
MCM-41-PEI PEBAX 20 1 25 3.10 2.16 1.96 [78]
COK-12 Matrimid 30 10 25 2.09 0.97 0.97 [79]
Silica nanoparticles SiO2 PEBA 8 2 25 1.36 2.25 2.28 [95]
SiO2 PU 15 10 26 5.17 2.16 – [80]
SiO2-OS PU 15 10 26 3.00 1.62 – [80]
SiO2-PDMS PU 15 10 26 3.53 1.22 – [80]
SiO2 SPEEK 20 10 65 2.80 0.75 0.74 [96]
SiO2-C SPEEK 20 10 65 2.90 2.06 1.60 [96]
SiO2-S SPEEK 20 10 65 2.60 1.87 1.51 [96]
SiO2-N SPEEK 20 10 65 4.09 2.42 1.95 [96]
SiO2 PEBAX 8 3 25 1.37 1.20 – [98]
Others TS-100 Matrimid 30 8 35 1.92 0.85 – [75]
TS-1 Matrimid 30 8 35 1.90 1.23 – [75]
ETS-10 Matrimid 20 8 35 1.24 1.33 – [75]
TiO2 PEBAX 3 20 25 1.56 – 1.18 [99]
TiO2 PEBAX-PEG 8 2 25 1.36 1.14 – [100]
TiO2 PEBAX 8 3 25 1.36 1.19 – [98]
Al2O3 PEBAX 8 3 25 1.48 1.28 1.40 [98]

mechanical strength of MMMs even at a low concentration in ther, it is reported that surface functionalized CNTs strongly inter-
matrix [102]. CNTs possess several possible adsorption sites, such act with polymer matrices in MMMs than pristine polymer [103].
as interstitial channel sites, with high binding energy and pore Aroon et al. reported that the b-CD (beta-cyclodextrins) func-
sites with large surface area, which assist the rapid gas transport tionalized MWCNTs were embedded on poly CA matrix by wet
rates, as a result, CNTs exhibit extremely high permeability. Fur- phase inversion method. The effect of filler loading was varied,
440 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
up to 0.20 wt%, and the highest enhanced permeability of CO2 and
selectivity of CO2/N2, about 85% and 22%, respectively, were
achieved because of uniform dispersion and better interfacial
interaction between filler and matrix. It is reported that increasing
the filler load above 0.20 wt% results in decreasing the gas trans-
port of permeance and the selectivity of CO2/N2 about 65% and
74.5%, respectively, due to excessive agglomeration. Whereas the
b-CD-functionalized MWCNTs in polyimide matrix are reported
to have an enhanced selectivity of about 160% [104]. Further,
Aroon et al. extended that the chitosan functionalized MWCNTs
embedded in polyimide and produced as asymmetric flat sheet
membranes. These MMMs possessed a lower permeability of about
38% than pure matrix, when pristine MWCNTs were used as a filler,
and their poor interaction with matrix was also discussed. How-
ever, surface modified filler had good interaction with polyimide
and had enhanced permeability and selectivity about 121% and
51%, respectively, than the neat polymer [105].
Zhang et al. reported that the N-isopropylacrylamide hydrogel
coated MWCNTs were embedded into PEBAX matrix. The enhanced
CO2 permeability about 267 Barrer, and enhanced selectivity of
CO2/CH4 and CO2/N2 was 1 and 14, respectively. In these composite
coating of hydrogel layer on the outer walls of CNTs help to
increase the water content of MMMs that influences both CO2 per-
meability and CO2 selectivity [106]. Further, Khan et al. studied the
MMMs fabricated by acyl chloride modified MWCNTs with PIM-1
(polymers of intrinsic microporosity) matrix by the solution cast-
ing method by varying the filler loading in a polymer matrix from
0.5 to 3.0 wt%. The results showed that gas transport properties at
2 wt% filler loading shows better permeability without altering
selectivity. The results were also compared with PEG functional-
ized MWCNTs/PIM-1 membrane, which revealed that the perme-
ability was 97.6% more than PIM-1 alone, due to the fact that the
good dispersion of PIM-1 matrix increases the solubility of the
polar CO2 gas and reduces the nonpolar N2 gas [107]. Ismail et al.
reported on amine siloxane functionalized MWCNTs dispersed into
PSf matrix at different concentration, and revealed that the
increased gas selectivities of CO2/CH4 and CO2/N2 were 388% and
316% at 0.5 wt%, respectively, than matrix alone. However, the per-
meance of CO2 was achieved by 23.5% at 3.0 wt% filler loading and
selectivity reduced due to the trade-off membrane mechanism
[65]. Zhao et al. fabricated MMMs by dispersing NH2-MWCNTs into
glycerol triacetate (GTA) modified PEBAX. The gas transport prop-
erties increased CO2 permeability up to 1208 Barrer and improved
selectivity up to 10% in GTA containing MMMs, due to CO2-philic
acetate groups, than in PEBAX matrix. Whereas NH2-MWCNTs/
PEBAX shows permeability about 226 Barrer without altering
selectivity. The result indicates that GTA containing MMMs accel-
erates the gas transport about 5.3-fold, than unmodified PEBAX
in MMMs [108,109]. Similarly, MWCNTs and hydrophilic PEG mod-
ified PEBAX matrix show that accelerated CO2 permeability and
CO2/N2 selectivity in MMMs were 68% and 38%, respectively, than
PEG/PEBAX composite alone [110].
Cong et al. reported MMMs were fabricated by reinforcing the
fillers, SWCNTs (5–17 wt%) and MWCNTs (2–9 wt%) into bromi-
nated poly (2,6 diphenyl-1,4-phenylene oxide) matrix. SWCNTs
shows higher enhanced CO2 permeability and CO2/N2 selectivity
than MWCNTs, due to the uniform dispersion of SWCNTs in matrix.
It is also reported that when mechanical tensile strength increased
by 44% and 67%, CO2 permeability increased by 93% and 102%,
respectively, than pure polymer [111]. Kim et al. prepared MMMs
by carboxylate zwitter ions containing octadecylammonium mod-
ified SWCNTs embedded into PSf matrix, which disclose the greater
permeability of about 33% than pristine matrix. The selectivity of
CO2/N2 was increased about 21% and the CO2/CH4 selectivity was
found to decrease in proportion to the amount of SWNTs in the
polymer matrix [112]. Kiadehi et al. reported the effect of amine
groups on the surface of carbon nanofiber in PSf matrix for improv-
ing the selectivity of CO2/CH4 and CO2/N2, as resultant the surface
modified CNF by 2.5 factor higher selectivity than unmodified fil-
ler. The unmodified CNF shows maximum permeability achieved
at 1.0 wt% loading, whereas the surface modified CNF reveals at
0.5 wt% filler loading onwards, which might be due to the inter-
stice between CNF and polymer chain [113].
5.2. Carbon molecular sieves
Carbon molecular sieves (CMSs) have been identified as one of
the promising filler in MMMs because of their pore diameter win-
dow about 3–5 Å, which is close to the kinetic diameter of gases.
Membrane technologies have developed defect-free CMS mem-
branes, which could overcome the major demerit, inherent brittle-
ness, and are cost-effective due to the less cost for fabrication and
replacement. Mass transport of gas on porous membrane can exhi-
bit the following mechanism such as Knudsen diffusion, capillary
diffusion, Poiseuille flow, and molecular sieving [114]. CMSs are
porous in nature and contain constrictions of apertures that help
diffuse the gas molecules, due to the dispersive and repulsive inter-
actions between the gas molecules and carbon atoms. The perme-
ation properties of CMS membrane depend on operating
temperature and pressure. CMS was dispersed in two glassy poly-
mers, Matrimid and Ultem, and MMMs were fabricated by varying
the filler loading from 16 to 36 vol% by Vu et al. The enhanced gas
transport permeability was about 3 Barrer, and selectivity of CO2/
CH4 was about 15 by CMSs in both polymer matrices, which was
achieved at 35–36 vol% loading [115,116]. Thus, CMSs’ filler acts
as a good filler in both polymer matrices and gives the same gas
transport capacity. Recently, Nasir et al. studied the properties of
the CMS in PES matrix. PES/CMS reveal that CO2 permeance and
CO2/CH4 selectivity were higher, 2.40-fold and 3.35-fold, respec-
tively, than pure PES membrane, due to the formation of interface
voids in CMS particle – polymer interface and solvent evaporation
during membrane formation. The performance was near to Robe-
son 2008 upper bound curve, up to 30 wt% CMS loading in PES
[117].
5.3. Graphene
Graphene is a two-dimensional (2D) allotropic form of pure car-
bon, with atoms arranged in a single planar sheet of sp2-hybrid
carbon atoms connected by r- and p-bonds in the honey comb like
2D hexagonal crystal lattice. Graphene exhibits unusual structure
characteristics, such as lightness, CAC bond length; and interplanar
spacing of stack sheets being 0.77 mg/m2, 0.142 nm, and 0.335 nm,
and has remarkably large specific surface area, high internal mobil-
ity, a high Young’s modulus, and thermal and electronic conductiv-
ity [118]. Graphene can be synthesized by top-down [119] and
bottom-up [120] approaches. The oxide form of graphene is used
widely in many applications, due to its hydrophilic nature and neg-
ative charge at an entire pH range. Further, graphene can be pro-
duced in the form of size-selective membranes, which allow
smaller molecules to pass through pores effectively than larger
molecules due to its atomic thickness and relative inertness of
gases [121].
A theoretical report on molecular dynamics shows that porous
graphene of a certain pore size can efficiently separate carbon
dioxide from nitrogen with high permeance, which reflects the
high CO2/N2 selectivity of about 300 with a free energy barrier
for the permeation of 24.7 and 9.6 kJ/mol for CO2 and N2, respec-
tively [122]. The separation factor was improved by introducing
water into CO2 from CO2/O2, CO2/N2, and CO2/CH4 gas mixtures
using a porous graphene membrane. Another investigation on
the separation of gas-mixtures using a graphene membrane by
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450 441

introducing a water slab between the gas-mixture and graphene port through nanopores. In the near future, graphene will play a
membrane, which results in the high selectivity of CO2 separation vital role in membrane science for gas separation.
[123]. Based on the above properties, it can be concluded that gra-
phene material shows uniform dispersion in the polymer matrix. 5.4. Overview of carbon-based fillers in MMMs
Hence, the graphene based MMMs shows better gas separation.
Li et al. reported the fabrication of multi-permselective MMMs The actual data and enhanced permeability and selectivity fac-
by the incorporation of functionalized GO with PEG and PEI carrier tors calculated for carbon fillers in MMMs obtained from the
in PEBAX matrix. The CO2 permeability and selectivity of PEG and results of the recent reports are plotted in Fig. 7a and b respec-
PEI modified GO fillers were enhanced by 166% and 130%, respec- tively. The data for Fig. 7b are obtained from Table 4. The data
tively, than pure PEBAX matrix. The improved gas permeability of interpret that 10–15% of carbon fillers are lined up in the trade-
membranes due to the interaction between GO and polymer lead off region, and 85–90% of fillers fall in enhanced regions. About
to the enhanced d-spacing of the membrane, avoiding the void for- 70% of fillers possess 3-fold enhanced premeability of CO2 and fit
mation in MMMs, and the presence of ethylene oxide groups in the A region, and around 15% of fillers are in B region. It is also
increased the solubility of polar CO2 than other nonpolar gases observed that 55% of fillers have >100% enhanced CO2/CH4 and
(N2 or CH4) [124]. Peng et al. prepared MMMs using zinc ion – CO2/N2 selectivity with respect to neat polymer membrane, and
dopamine modified graphene oxide (GO-DA-Zn2+) as filler and dis- less than 5% of fillers are in D region. From the Table 4, it can be
persed in PEBAX matrix. Zinc ions could form a p-complexation seen that the MMMs fabricated by surface modified carbon fillers
with CO2, which led to a gas transport, and high aspect ratio disperse uniformly into polymer matrices and hence increases
reduced tortuous gas transport channels by the dispersion of gra- the permeability and selectivity of CO2. Further, MMMs fabricated
phene sheet in matrix. This property was favorable for reducing with CMS and GO filler fit in B regions that imparts good CO2/CH4
the penetration of larger CH4 molecule and thus resulted in CO2 and CO2/N2 selectivity. The submicron particle size (2 lm) of the
permeability and CO2/CH4 selectivity of about 49% and 78%, respec- CMS filler and high aspect ratio GO nanosheets in polymer matrix
tively, than pristine polymer membrane [125]. Shen et al. reported that generate a rigid interface between polymer and GO enhances
that MMMs fabricated with GO sheets were dispersed in PEBA CO2 selectivity. Especially, graphene-based fillers can produce
matrix, which showed the strong interaction of polymer chains ultrathin membrane with a better performance than other carbon
with GO sheets, which led to the barrier effect for nonpolar gas. fillers. In addition, the surface functionalized CNF shows higher
This favors gas transport parameters and results in enhanced CO2 CO2 permeability and CO2/CH4 selectivity due to strong interaction
permeability and CO2/N2 selectivity by GO, of 42% and 90%, respec- between CO2 and functional groups on the CNF surface and hence
tively, than pristine PEBA membrane [126]. Zahri et al. fabricated fit in D region.
GO/PSf MMMs, that shows a good interaction facilitated by the sur-
face functional groups of GO with PSf domain and consequently 6. Metal organic framework fillers
improved the dispersion of GO in PSf. Thus, the nanofiller of GO
enhanced the permeance of CO2, about 14%, and the selectivity of The combination of nanomaterials with polymer matrix in fab-
both CO2/N2 and CO2/CH4 was 158% and 74%, respectively, com- rication of MMMs provoked researchers to develop MOF-based
pared to that of neat PSf matrix [127]. From the above reports, it MMMs for improving membrane properties. MOFs act as a good fil-
can be concluded that graphene materials are recognized as a good ler due to their superior characteristics such as tailoring pore size,
candidate for developing MMMs with suitable polymer matrices high surface area, high adsorption capacity, and greater chemical
due to their atomistic thickness, remarkable mechanical strength, and thermal properties. The organic moiety of MOFs enhances
high dispersion in polymer, and potential for size selective trans- the wetting properties between the two phases and also increases

10 4
Selectivity Factor (SF) of CO2 /CH4 and CO2 /N2

a CO2/CH4
(MMMs) Trade-off - CNTs b
2008 Upper Bound for CO2 /CH - CNF
(Polymer) region
CO2/CH4 - CMS
Selectivity (CO2 /CH4 and CO2 /N2)

3 (MMMs) - GO
10 CO2/N2
101
CO2/N2
(Polymer)

B D
10 2 Enhanced
region

A C
10 1

100
100 101 Trade-off
region
10 0
-4 -3 -2 -1 0 1 2 3 4 Permeability Factor (PF) of CO2
10 10 10 10 10 10 10 10 10
Permeability of CO2

Fig. 7. Profile of carbon-based fillers in mixed matrix membrane for CO2 gas separation (a) Actual permeability and selectivity of MMMs and their corresponding polymer
matrix [65,103–133]. (b) Permeability and Selectivity factors, filled and unfilled symbols represent the selectivity factor of CO2/CH4 and CO2/N2 respectively (Data used from
the reference given in Table 4).
442 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450

Table 4
CO2 separation performance of carbon-based fillers in mixed matrix membranes.

Fillers Polymer matrix Filler (Wt.%) P (bar) T (°C) PF (PCO2) SF (aCO2/CH4) SF (aCO2/N2) Ref
CNTs CA 0.1 1.5 RT 1.85 – 1.22 [103]
PI 6 25 15 0.23 2.60 – [104]
PI 1 25 15 2.21 1.51 – [105]
PEBAX 5 2 RT 1.89 1.03 1.25 [106]
PIM 3 – 30 1.98 1.05 1.00 [107]
PES 0.5 3 27 0.62 4.88 4.16 [65]
PEBAX 33 7 35 2.67 0.88 1.04 [108]
PEBAX 0.5 3 30 1.40 – 2.28 [128]
PEBAX-GTA 33 7 35 7.04 1.11 1.10 [109]
PEBAX-PEG 5 10 25 1.69 – 1.38 [110]
BPPO 5 0.68 25 1.93 – 0.99 [111]
BPPO 9 0.68 25 2.02 – 1.07 [111]
PSf 10 4 35 1.33 0.78 1.21 [112]
CNF PSf 0.5 2 RT 7.14 3.9 – [113]
PSf 1 4 RT 6.86 3.26 2.27 [129]
CMS Matrimid 36 3.5 35 1.26 1.46 1.06 [115]
Ultem 35 3.5 35 3.09 1.38 1.18 [116]
PES 30 2 25 2.40 3.35 – [117]
GO PEBAX 10 2 30 2.66 2.25 2.35 [124]
PEBAX 1 2 30 1.96 4.57 – [125]
PEBA 0.1 3 25 1.62 – 1.40 [126]
PSf 0.25 5 25 1.14 1.74 2.58 [127]
PEO–PBT 0.065 0.5 25 0.95 1.23 1.40 [130]
PEO-ED 1 3.5 35 2.25 – 0.99 [131]
PSf 30 1 7 1.43 – 1.65 [132,133]

the strong interaction with polymer matrix. Further, MOFs surpass
the zeolites in most of the applications due to their synthesis by
click chemistry with less energy, which do not require structure-
directing agents, calcination step, etc. Thus, nanocomposite-based
membranes were fabricated by the incorporation of MOF fillers
into the polymer matrix, and these MMMs explored remarkable
gas separation properties. This report compiles zirconium, zinc,
aluminum, and copper-based MOFs as a filler in MMMs for CO2
separation from gas mixture and discusses the influence of MOF fil-
lers in gas transport.
6.1. UiO-66
Zirconium-based MOFs (UiO-66; UiO = University of Oslo) is a
subfamily of MOFs, which possess exceptional stabilities due to
the fact that each Zr-metal center is connected with benzene-
1,4-dicarboxylate (BDC) linkers to form the face centered cubic
(FCC) crystal structure framework, with the formula Zr6O4(OH)4(-
BDC)6 and aperture size 6 Å [134]. The surface modified UiO-66
has polar and basic functionalities such as hydroxylated (AOH),
amino (ANH2), nitro(ANO2), and methoxy(AOMe) groups. Particu-
larly, polar groups-modified UiO-66 are reported to enhance the
CO2 adsorption and are favorable to increase CO2/CH4 and CO2/N2
selectivity [135–137].
Shen et al. reported that UiO-66/PEBA MMMs possessed good
affinity with CO2 molecules, and the enhanced CO2 permeability
and CO2/N2 selectivity were about 80–90% and 40–65%, respec-
tively, than PEBA membrane [138]. Whereas, Ti- exchanged UiO-
66 in PIM-1, and showed improved permeability of CO2 about
8200 Barrer, without a loss of selectivity than pure PIM-1. The
enhanced permeability of these materials was reported due to a
strong interaction between filler and matrix, which led to the for-
mation of interfacial free volume and strong affinity for CO2 [54].
Khdhayyer et al. studied the effect of amino and carboxylic group
containing Zr-based UiO-66 filler with PIM-1 matrix. UiO-66 and
NH2-UiO-66 fillers showed that the higher permeability was
1100 and 1600 Barrer, respectively, without disturbing the selec-
tivity of CO2/CH4. Whereas (COOH)2-UiO-66 revealed a lower per-
meability of about 300 Barrer and a decreasing selectivity of about
25% than PIM-1, due to the presence of free carboxylic groups in
(COOH)2-UiO-66/PIM-1, which reduced the intrinsic microporosity
and the free volume with interconnected voids of PIM-1 [139].
Venna et al. fabricated MMMs by phenyl acetyl (PA), decanoyl
acetyl (DA), and succinic acid (S) modified UiO-66 and combined
with Matrimid matrix. The surface functionalization of UiO-66 fil-
lers shows a good interaction with polymer. The PA modified NH2-
UiO-66/Matrimid illustrated that increased permeability of CO2
and CO2/N2 selectivity were 200% and 32%, respectively, than con-
trol experiment due to the strong interaction of ANH2 of UiO-66
and amide group of polymer through hydrogen bond, and aromatic
ring of PA group and imide group of polymer interacted through p-
p bonds. However, DA and S functionalized UiO-66 showed low
transport performance of CO2 compared to PA and ANH2 contain-
ing UiO-66, due to poor interaction between the polymer and the
fillers (polar of SA, nonpolar alkyl group of DA), and formed defec-
tive interface, which altered the diffusion path for non-selective
gases [140]. Anjum et al. fabricated MMMs through covalent inter-
action between the polyimide matrix and amine functionalized Zr-
terephthalate UiO-66 fillers. The gas transportation increased by
attaching benzoic acid (BA) and aminobenzoic acid (ABA) on
NH2-UiO-66, and high permeability (450 Barrer) and selectivity
(54%) were achieved with NH2-UiO-66-ABA filled MMMs than neat
matrix, and other MMMs showed lower performance about 2.5
folds, than NH2-UiO-66-ABA [141].
6.2. Zeolitic imidazolate frameworks
Zeolitic imidazolate frameworks (ZIFs), a subfamily of MOFs,
possessed zeolite topology with tunable pore structures. Zeolites
are replaced by these ZIFs due to their high thermal/chemical sta-
bilities [142]. ZIFs consisted of metal nodes connected to imidazole
linkers by replacing the bridging oxygen in the Si/AlAOAAl/Si (zeo-
lite) repeating unit with imidazolates and Si/Al atoms with transi-
tion metals, also ZIFs bond angle of metal-linker-metal (145°)
resembles the Si/AlAOAAl/Si repeating unit in zeolites [143]. A ser-
ies of ZIF materials can be produced by varying the organic linkers
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
of imidazolate ligands and metal ions (zinc or cobalt) such as ZIF-7,
ZIF-8, ZIF-11, ZIF-71, ZIF-78, ZIF-108, and ZIF-302. Generally, ZIFs
have large cavities with narrow pore apertures, which is close to
the kinetic diameter of CO2 (3.3 Å) and allows a suitable filler
material in MMMs for CO2 separation.
6.2.1. ZIF-7 and ZIF-8
Li et al. fabricated defect-free ZIF-7/PEBAX and achieved high
permeability at 22 wt% filler loading, and upon increasing the filler
composition up to 34% resulted in higher selectivity. But perme-
ability decreased from 145 to 41 Barrer due to the rigidification
of the PEBAX chain on higher filler loading [14]. Whereas, ZIF-8 fil-
lers are strongly formed with a soft domain of PEBAX, and the CO2
permeability enhanced about 4.32 parts than PEBAX. The perme-
ability up to 994 Barrer by 35 wt% ZIF-8/PEBAX at 6 bar was
achieved, and selectivity of CO2 by N2 or CH4 was 32 and 9, respec-
tively [144]. Dong et al. derived MMMs by in-situ growth of ZIF-8
on the surface of GO and used as filler in PEBAX, and studied the
influence of GO and ZIF-8 for CO2 separation. The ultra-
microporosity of ZIF-8 increases the CO2 permeability by 1.38-
fold in ZIF-8/PEBAX. Further, ZIF-8@GO/PEBAX showed enhanced
permeability and selectivity ratio of 1.92 and 1.78, respectively,
than pure PEBAX due to the influence of GO [145]. GO nanosheets
acted as a selective barrier and allowed gas molecules to diffuse
with less resistance than larger molecules, which reflect enhanced
gas diffusivity and diffusivity selectivity [146,147]. However, the
combined silicalite-1-ZIF -8 fillers in preparation of MMM shows
poor gas separation due the difficulty in confinement of large
silicalite-1 particles between small ZIF-8 particles (ca. 100 nm)
that lower affinity towards CO2 [148].
Nordin et al. developed MMMs by uniformly dispersing ZIF-8
(0.5% loading) in PSf matrix with excess free volume, which
resulted in CO2 permeation and selectivity up to 1.37 and 1.19-
fold. However, upon increasing the filler concentration up to
10 wt% ZIF-8 in PSf, the gas pair selectivity drastically diminished
due to the formation of a large number of clusters, which resulted
in unselective channels between the layers [149]. Tanh Jeazet et al.
examined the CO2 separation by ZIF-8/PSf, and the gas separation
properties of permeability and selectivity increased by 2.0 and
1.52-fold at 8 wt% ZIF-8 loading than lean PSf membrane. Addition-
ally, the maximum permeability, about 4.8-fold was achieved at
24 wt% ZIF-8 loading and selectivity decreased to 1.04 due to
trade-off membrane properties [150]. Sorribas et al. developed
MMMs by ZIF-8 crystal growth on the outer layer of mesoporous
silica by in-situ process in PSf matrix and achieved improved per-
meability of CO2 about 300%, on 32 wt% filler loading at 35 °C than
control, and selectivity of CO2/CH4 remained the same. It can con-
cluded that the operating temperature plays an important role in
permeability as high temperature could enhance the diffusivity
of the gas and flexibility of the polymer domains. Further studies
reveal that the enhanced CO2 permeability of 24.4–73.1 Barrer
was obtained at 35 °C and 150 °C. The maximum CO2/CH4 selectiv-
ity was achieved, about 6.25% on 32 wt% ZIF-8 loading at 35 °C,
because the mechanical strength indicated that beyond 32 wt% fil-
ler concentration in polymer, MMMs become brittle in nature due
to the agglomeration phenomenon [151].
Thompson et al. fabricated MMMs by surface modified ZIF-8
using 2-benziimidazole, and 2-aminobenziimidazole organic
ligands with Matrimid. The results illustrated that 2-
benziimidazole modified ZIF-8 showed the highest CO2 permeabil-
ity value of 10 Barrer, and selectivity of CO2/CH4 decreased by 4%
when compared to the lean polymer [152]. Basu et al. explored
the effect of ZIF-8, MIL-53, and Cu3(BTC)2 fillers in polyimide
matrix for gas transport and achieved enhanced CO2 permeability
of 130%, 90%, and 65%, respectively, than neat polyimide mem-
brane. However, Cu3(BTC)2 and MIL-53(Al) reveal higher CO2/CH4
443
selectivity than ZIF-8, due to the strong CO2 interaction with poly-
mer than ZIF-8. These interactions favor high quadrupole moment;
hence CO2 is selectively attracted towards the specific electron-
rich sites in Cu3(BTC)2, and through breathing mechanism between
the hydroxyl groups of the MIL-53[153].
Chi et al. fabricated new MMMs using soft organic matrix of
poly(vinyl chloride)-g-poly(oxyethylene methacrylate) (PVC-g-
POEM), which offered uniform distribution and reported Tg value
of matrix that increased from 62.0 to 58.88° due to better inter-
facial interaction of ZIF-8 and POEM phases. ZIF-8/PVC-g-POEM
exhibited about 9.80-fold of enhanced CO2 permeability and
14.4% selectivity of CO2/N2 than bare PVC-g-POEM [154]. Chi
et al. investigated styrene-based MMMs by dispersing different
sized ZIF-8 particles uniformly within a polystyrene-block-poly(e
thylene-ran-butylene)-block-polystyrene (SEBS) copolymer
matrix, without disturbing the microphase-separated structure of
the polymer matrix. The results illustrated that CO2 permeability
was 2.66 factors by medium size ZIF-8 (280 nm), and correspond-
ing selectivity of CO2/CH4 and CO2/N2 were 5.4 and 12, respectively
[155]. However, IL@ZIF-8 showed superior gas separation perfor-
mances than Robesons 2008 upper bound of polymeric membrane.
IL@ZIF-8 exhibited excellent long-term stability, and enhanced CO2
permeability and selectivity of CO2/CH4 and CO2/N2 were 292 Bar-
rer, and 15.1 and 64.9, respectively than plain ZIF-8 [156]. In addi-
tion, ZIF-8 in polymethylphenylsiloxane (PMPS), and resultant CO2
permeability increased by 2.71-fold, with low selectivity values
than pure PMPS due to trade-off phenomena [157]. Whereas, ZIF-
8 gave good adhesion with polyetherimide matrix, which showed
the enhanced CO2 permeability, over 20% than pure polymer mem-
brane [158].
6.2.2. ZIF-11 to ZIF-302
Safax et al. developed MMMs by dispersing ZIF-11 into 6FDA-
DAM (2,2-bis(3,4-carboxyphenyl) hexafluoropropane
dianhydride-diaminomesitylene) matrix for increasing the d-
space between the centers of the polymer domains. The d-space
increment plays an important role in gas separation process. The
d-spacing values of 5.27–5.80 Å were achieved by 20 wt% ZIF-11
loading in 6FDA-DAM, which shows the enhanced CO2 permeabil-
ity about 236 Barrer, and reached the 2008 Robeson upper bound.
The selectivity of CO2/N2 was significantly lower than pure 6FDA-
DAM [159]. Hao et al. fabricated ZIF-71/PIM, PIM having ‘sites of
contortion’ properties, which helped enhance the fractional free
volume of MMMs. This, resulted in the superior CO2 permeability
of 5042 Barrer by 30 wt% ZIF-71/PIM than pure PIM membrane.
The selectivity of CO2/CH4 remained the same in pure PIM and
MMMs [160]. Bae et al. studied the CO2 separation using different
polymer matrices with ZIF-90. The polymer matrices were in-
house prepared 6FDA-DAM, and two commercially available poly
(imide)s, Ultem and Matrimid, were used for developing MMMs
with ZIF-90. It was clear that the effect of polymer matrix in selec-
tive gas permeability with ZIF-90, and the order of enhanced CO2
permeability of 6FDA-DAM, Matrimid, and Ultem-based MMMs
with 15 wt% ZIF-90 were 330, 4, and 2.4 Barrer, respectively. The
selectivity of CO2 in 6FDA-DAM/ZIF-90 was 54% higher than other
MMMs [161]. Ban et al. synthesized cobalt metal substituted ZIF-
108 and PSf matrix. ZIF-108 has numerous active sites for the
accommodation of other metal substitutions. The secondary metal
Co-doped ZIF-108/PSf showed CO2 permeability about 7-fold and
17-fold higher than ZIF-108/Psf and pure PSf, respectively. The
incorporation of Co metal in ZIF-108 framework resulted in the
enlargement of pore size, which led to a high compatibility of fil-
lers with PSf membrane and showed superior separation factors
and permeability of CO2 [162]. Sarfraz et al. fabricated MMMs by
dispersing the hybrid GO/ZIF-302 into the PSf matrix, and noticed
that d-spacing value shifted from 5.21 Å to 5.17 Å due to the strong
444 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450

interaction between GO/ZIF-302 and PSf, and the PSf inter-chain Ahmadi Feijani et al. fabricated MMMs by embedding MIL-53
distance also reduced. These properties enhanced CO2 permeability (Al) and NH2-MIL-53(Al) fillers with poly(vinylidene fluoride)
and CO2/N2 selectivity by 2-fold than neat PSf membrane (PVDF) matrix through hydrogen bond, which showed the highest
[132,163]. enhanced CO2 permeability up to 104% and 85% by MIL-53(Al) and
NH2-MIL-53(Al), respectively. The aforementioned MMMs possess
much larger pore size than the kinetic diameter of CO2 and CH4 in
6.3. MIL
unfilled MIL [169], and there exist an interaction between CO2 and
AOH group of MIL-53(Al) during adsorption as a result of enhanced
Materials Institute Lavoisier (MIL) is a series of MOFs, which is
permeability. However, -NH2 functionalized MIL reveals higher
constructed through the organic linker connected with metal ions
CO2/CH4 selectivity than unfilled MIL due to a good compatibility
(Al, Cr, Ti) by corner sharing forming three-dimensional structures.
with PVDF, which could lead to a strong affinity between the
MILs exhibit their attractive characteristics such as large pore vol-
surface-NH2 of MIL and CO2 [170]. In addition, the incorporation
ume, high surface area, superior gas adsorption capacity, and pos-
of NH2-MIL-53(Al) into glassy PSf matrix, which possessed hydro-
sess some unique structure-breathing properties due to the
gen bonding interactions and hence exhibited improved CO2/CH4
framework consisting of unidirectional diamond-shaped pore
selectivity by 7-fold than pure polymer [171]. Rodenas et al. stud-
channels. Based on recent literature, MILs act as a good filler in
ied the effect of polymer and filler in MMMs. The two filers of NH2-
the development of membranes because of their uniform disper-
MIL-53(Al) and MIL-101(Al) were dispersed separately in polysul-
sion and good compatibility with polymers, as resultant surpass
fone and polyimide (PI) matrices. The gas transport performance of
gas separation. MILs are reported in different forms and used as fil-
MIL-101(Al)/PSf and MIL-53(Al)/PI reveals the enhanced perme-
ler in MMMs, such as MIL-53(Al), MIL-68(Al), MIL-101(Cr), and
ability about 60% than pure matrix without disturbing selectivity
MIL-125(Al).
[172].

6.3.1. MIL-53 6.3.2. MIL-68 to MIL-125

Zhu et al. reported that the surface modified NH2-MIL-53(Al)/ Dong et al. investigated the influence of MIL-68(Al)/polyimide
Ultem showed higher CO2 permeability than unmodified MIL-53 MMMs for CO2 separation. The results illustrated higher perme-
(Al) containing MMMs, and selectivity also increased by 10% than ability and selectivity of CO2 about 2.25-fold than pure polymer,
pure Ultem. The gas transport performance was higher due to because of the strong interaction of the surface hydroxyl groups
the interaction of bridging hydroxyl group of MIL-53(Al) with car- of MIL-68(Al) with polymer and the increased adsorption affinity
bonyl groups of polymers. Moreover, the organic terephthalate of CO2 [173]. Xin et al. reported about the fabrication of MMMs
ligands and surface ANH2 groups also improved the compatibility using the bare and polyethylenimine (PEI) modified MIL-101(Cr)
with matrix [164,165]. Abedini et al. fabricated MMMs by dispers- fillers incorporated into SPEEK. The PEI modified filler interacts
ing NH2-MIL-53 in Poly(4-methyl-1-pentyne) (PMP) matrix and through the surface NH2 groups of PEI with sulfonic acid group
found that CO2 permeability was 259 Barrer and selectivity of of SPEEK through electrostatic interaction and hydrogen bond,
CO2/CH4 was 15 at 30 wt% filler loaded MMMs than pure PMP which results in an enhanced permeability of 1945 Barrer, and
membrane. The separation performance of NH2-MIL-53/PMP over- the selectivity of CO2/CH4 and CO2/N2 were 47 and 36, respectively,
come the Robeson upper bound at 30 °C [166]. Sabetghadam et al. than pure polymer. The bare MIL-101(Cr)/SPEEK membrane also
explored the effect of 6FDA-DAM matrix in MMMs. NH2-MIL-53 gives better permeability of CO2 (1010 Barrer) and increased selec-
(Al)/6FDA-DAM reveals the enhanced permeability of CO2, up to tivity (about 25%) than neat SPEEK membrane [174]. Tanh Jeazet
300 Barrer than pure matrix [167]. Further, the surface modified et al. reported the fabrication of MMMs with ZIF-8, MIL-101(Cr)
6FDA-DAM-HAB matrix with NH2-MIL-53(Al) MMMs exhibited and combined 1:1 ratio fillers with PSf matrix. The combined
higher CO2 separation and approached the 2008 Robeson’s upper MIL-101(Cr)-ZIF-8/PSf harvests higher CO2 permeation about
bound [168]. 500%, than pure PSf due to the synergistic effects of membrane

10 4
a (MMMs) - UiO-66 b
Selectivity Factor (SF) of CO2 /CH4 and CO2 /N2

CO2/CH4 Trade-off
2008 Upper Bound for CO2/CH4
- ZIFs
(Polymer) region - MILs
Selectivity (CO 2 /CH 4 and CO 2 /N 2 )

CO2/CH4

(MMMs) - Cu, Mg, others

10 3 CO2/N2
101
CO2/N2
(Polymer)

B D
10 2 Enhanced
region

A C
10 1

100
100 101 Trade-off
0
region
10
-4 -3 -2 -1 0 1 2 3 4 Permeability Factor (PF) of CO2
10 10 10 10 10 10 10 10 10
Permeability of CO2

Fig. 8. Profile of metal organic framework fillers in mixed matrix membrane for CO2 gas separation. (a) Actual permeability and selectivity of MMMs and their corresponding
polymer matrix [14,54,138–186]. (b) Permeability and Selectivity factors, filled and unfilled symbols represent the selectivity factor of CO2/CH4 and CO2/N2 respectively (Data
used from Table 5).
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450 445

with combined fillers, and CO2/CH4 selectivity remains the same.
The other ZIF-8/PSf, MIL-101(Cr)/PSf MMMs also shows better per-
meability about 300% and 260%, respectively, than control [150].
Waqas Anjum et al. investigated the effect of NH2 group for gas
transportation; MIL-125(Al) and NH2-MIL-125(Al) fillers embed-
ded in polyimide matrix showed enhanced permeability of 21
and 44 Barrer, respectively, than control. The selectivity of CO2/
CH4 increased up to 23%. However, NH2-MIL-125(Al)/PSf reveals
that the improved permeability and selectivity were 13.3 barrer
and 10%, respectively than pure PSf membrane [175].

Table 5
CO2 separation performance of MOF-based fillers in mixed matrix membranes.

Fillers Polymer Matrix Filler (wt.%) P (bar) T (°C) PF (PCO2) SF (aCO2/CH4) SF (aCO2/N2) Ref
UiO-66 PEBA 2–20 3 25 1.95 – 1.41 [138]
NH2-UiO-66 PEBA 2–20 3 25 1.82 – 1.67 [138]
Ti-UiO-66 PIM-1 5.0 2 25 2.54 – 1.05 [54]
UiO-66 PIM-1 9.1 1 25 1.22 1.06 – [139]
(COOH)2-UiO-66 PIM-1 9.1 1 25 1.06 0.74 – [139]
NH2-UiO-66 PIM-1 9.1 1 25 1.33 1.29 1.20 [139]
NH2-UiO-66 Matrimid 23 1 RT 3.00 – 1.32 [140]
NH2-UiO-66-PA Matrimid 23 1 RT 3.50 – 1.32 [140]
NH2-UiO-66-C10 Matrimid 23 1 RT 2.88 – 1.00 [140]
NH2-UiO-66-SA Matrimid 23 1 RT 2.50 – 1.11 [140]
NH2-UiO-66 Matrimid 30 9 35 2.63 1.20 – [141]
NH2-UiO-66-BA Matrimid 30 9 35 2.54 1.26 – [141]
NH2-UiO-66-ABA Matrimid 30 9 35 5.54 1.53 – [141]
UiO-66-GO PI – 1 30 2.0 1.37 – [180]
ZIF-7 PEBAX 34 3.75 25 1.54 2.14 2.85 [14]
ZIF-8 PSf 0.5 4 27 1.37 1.19 – [149]
ZIF-8 PSf 24 – – 4.80 1.04 – [150]
ZIF-8 PSf 32 3.3 35 4.00 1.03 – [151]
ZIF-8 PVC-g-POEM 30 – 35 9.80 0.89 1.14 [154]
ZIF-8 SEBS 30 1 35 2.66 1.26 0.97 [155]
ZIF-8 [bmim][Tf2N] 6 20 25 2.51 1.69 3.43 [156]
ZIF-8 Matrimid 15 3.45 35 2.25 1.00 – [152]
ZIF-8 Matrimid 30 10 35 2.30 1.10 1.04 [153]
ZIF-8 PMPS 8.3 1.2 RT 2.71 0.88 0.80 [157]
ZIF-8 Ultem 17 6.89 35 1.86 – 1.20 [158]
ZIF-8 PEBAX 35 6 RT 4.32 0.90 1.08 [144]
ZIF-8 6FDA-Durene 10 3.5 30 3.05 4.03 – [181]
ZIF-8@GO PEBAX 6 1 25 1.92 – 1.78 [145]
ZIF-11 6FDA-DAM 20 4 30 12.48 0.95 – [159]
ZIF-71 PIM-1 30 3.5 35 2.53 1.10 0.91 [160]
ZIF-90 6FDA-DAM 15 2 25 1.85 1.54 – [161]
ZIF-90 Ultem 15 2 25 5.80 1.03 – [161]
ZIF-90 Matrimid 15 2 25 1.50 1.01 – [161]
Co-ZIF-108 PSf 0.037 1 25 17.00 1.63 1.57 [162]
ZIF-302@GO PSf 30 1 25 2.17 – 1.96 [132]
ZIF-8/SC PSf 16 2.75 35 2.00 0.75 0.58 [148]
MIL-53 Ultem 5 5 35 2.29 0.98 – [164]
NH2-MIL-53(Al) Ultem 10 5 25 2.65 – 1.33 [164]
NH2-MIL-53 (Al) PMP 30 8 30 4.24 2.81 [166]
NH2-MIL-53 (Al) 6FDA-DAM 20 9 25 1.86 1.14 – [167]
NH2-MIL-53 (Al) 6FDA-DAM)x-(HAB)y 10 10 35 2.33 2.05 – [168]
NH2-MIL-53 (Al) PVDF 10 5 25 1.85 2.06 – [170]
MIL-53 (Al) PVDF 10 5 25 2.02 1.86 – [170]
NH2-MIL-53(Al) PVDF 10 5 25 1.23 1.04 – [182]
NH2-MIL-53 (Al) PSf 25 – 35 1.06 6.71 – [171]
NH2-MIL-53 (Al) PSf 25 3 35 1.06 1.62 – [172]
NH2-MIL-53 (Al) Matrimid 25 3 35 1.56 1.53 – [172]
MIL-53(Al) Matrimid 30 10 35 1.90 1.18 1.04 [153]
NH2-MIL-101(Al) PI 8 3 35 1.11 1.11 – [183]
NH2-MIL-101(Al) PSf 25 3 35 1.70 1.71 – [183]
MIL-101(Cr) PSf 24 – – 3.60 1.22 – [150]
MIL-101(Cr)/ZIF-8 PSf 35 – – 6.00 1.04 – [150]
MIL-101(Cr) SPEEK 40 1 25 2.84 1.28 4.00 [174]
MIL-101(Cr)-PEI SPEEK 40 1 25 4.57 2.91 0.69 [174]
MIL-68(Al) Matrimid 10 1 100 2.24 2.26 – [173]
MIL-68(Al) PSf 8 3 35 0.87 1.17 – [184]
NH2-MIL-125(Ti) PSf 20 3 35 2.40 1.09 – [185]
NH2-MIL-125(Ti) Matrimid 30 9 35 8.33 1.23 – [175]
MIL-125(Ti) Matrimid 30 9 35 4.50 1.23 – [175]
Cu-MOF PEBAX 5 2 RT 13.00 – 0.33 [176]
Cu-MOF POZ 9 2 RT 1.02 – 0.06 [176]
Mg-MOF-74 PIM-1 20 – – 3.23 1.55 – [177]
Cu3(BTC)2 Ultem 10 3.5 35 5.25 1.11 1.07 [178]
Cu3(BTC)2 Matrimid 30 10 35 1.65 1.23 1.27 [153]
SIFSIX-3-Zn XLPEO 10 1 25 1.32 2.00 1.90 [179]
HKUST-1 6FDA-Durene 10 2 25 1.41 1.32 1.17 [186]
HKUST-1/S1C PSf 16 2.75 35 2.00 0.93 1.45 [148]
446 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
6.4. Cu-based MOFs
Kim et al. explored the influence of matrix, such as amorphous
poly(2-ethyl-2-oxazoline) (POZ) and semi crystalline PEBAX, with
Cu-based MOF as filler for MMMs. Cu-MOF/PEBAX-based MMMs
reveal higher permeability and selectivity due to decreased crys-
tallinity of matrix in the presence of Cu-MOFs. Cu-MOF/POZ
showed low separation due to the decreased d-spacing of POZ
value upon Cu-MOF addition, which reflected changes in the POZ
chain structure, while PABAX maintained the d-spacing values
upon the addition of filler [176]. Ten-Binh et al. has developed
Mg-based MOF with narrow pore channels, and it has exception-
ally high CO2 capture capacity. Mg-MOF-74 dispersed in PIM-1
matrix formed strong interaction between the intrinsic micropores
of PIM-1 and inner pores of filler associated throughout the net-
work of the MMMs. On behalf of Mg-MOF-74 in MMMs, the
enhanced uppermost permeability of CO2 was 14,500 barrer, and
55% CO2/CH4 selectivity was achieved at 20 wt% loading of MOF-
74 [177]. Duan et al. reported Cu3(BTC)2/Ultem MMM for gas sep-
aration, which was based on the trade-off mechanism. On increas-
ing Cu3(BTC)2 loading in polymer, the permeability enhanced up to
8.5 Barrer at 40 wt% filler loading and selectivity inversely reduced
about 35% compare to pure matrix [178]. Gong et al. fabricated
MMMs using Zn and pyrazine pillared by hexafluorosilicate
(SIFSIX-3-Zn) filler with crosslinked polyethylene oxide matrix.
The filler strongly interacted with matrix, and resulted in the
enhanced permeability of 150 Barrer, and the selectivity of CO2/
CH4, and CO2/N2 were 15 and 10, respectively, than control [179].
6.5. Overview of MOF-based fillers in MMMs
Fig. 8a and b shows the real data and enhanced gas separation
performance of MOF based MMMs for CO2 separation
[14,54,138–186]. Fig. 8b was constructed using the data are given
in Table 5. In general, MMMs with MOF fillers shows increased per-
meability of about 98% than pure polymer membranes. However,
about 10–15% MOF filler fall in trade-off region due to low selectiv-
ity. From the results, it can be inferred that about 70% MOF fillers in
MMMs shows 100% enhancement in CO2 permeability and selec-
tivity than pure polymer membrane. From Fig. 8, it can be seen that
A Permeability (PCO )
Fig. 9. Overall contribution of zeolites, carbon, and MOF fillers in MMMs for CO2 separation. A. Suitable fillers for enhancing permeability and selectivity factors, B. Fillers’
contribution with respect to permeability and selectivity (Data obtained from Tables 3–5).
about 10% and 25% of reported fillers fit in B and C regions, while
less than 5% of fillers are in D region. It is observed that ZIFs and
MILs fillers fit in C region, these fillers possess large porosity and
increased free volume in polymer matrix due to breaking of poly-
mer chain packing and linking which contributes to improved per-
meability. These data illustrate that the free amine moiety
containing MOF fillers in MMMs reveals better CO2 separation per-
formance than unmodified MOFs, and most of MOF fillers shows
enhanced permeability with limited selectivity.
7. Profile of zeolite, carbon, and MOF fillers in MMMs
With respect to the reported results, it is clear that the selection
of fillers in MMMs is one of the most challenging task because each
filler has its own advantages and disadvantages. An overview of
this is shown in Fig. 9, constructed based on recent literature
reports (Tables 3–5). The ordinance of y-axis is denoted as relative
permeability and selectivity of zeolite, carbon, and MOF fillers in
MMMs, and x-axis denotes the suitability of fillers for MMMs,
which is represented as fair, good, and trade-off regions as per
Table 2. It can be noticed that all of the three fillers enhanced
the permeability and selectivity about 90%, due to well-defined
dispersion and strong interaction with the polymer matrix fillers,
and formed defect-free MMMs. However, a few fillers in MMMs
have been restricted into their ‘‘trade-off” between the gas trans-
port properties.
About 10% of MMMs within all three fillers lie in the ‘‘trade-off”
regions. In recent days, most of the literature reported that 70%
MMMs developed with all the fillers are covered in ‘‘fair” regions.
From Table. 2 it can be understood that fair fillers have improved
CO2 separation performance of permeability (>1 to <3-fold) and
selectivity (>1 to <2-fold) than pure polymer membranes. Further,
about 10% fillers are under ‘‘good” regions, which possess
enhanced permeability, >3-fold, and selectivity, >2-fold, than the
neat polymer. As per reports, only MOF fillers (about 30% fillers)
shows enhanced permeability, i.e., >3-fold, than other fillers but
were covered under C regions due to the diminishing of selectivity
<2-fold, and few fillers lie in the D region (<5%). Thus, based on the
analysis, the order of fillers in MMMs for the enhanced selectivity
of CO2/CH4 and CO2/N2 is carbon>MOFs>zeolites, which might be
100
B 2
Selectivity ( CO2/CH4
)
80 Selectivity ( )
CO /N
2 2
Fillers contribution (%)
60
40
20
0
Trade-off Fair Good
Fillers suitability
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
due to the interstitial channel and large surface area of fillers. Thus,
in order to make a milestone in membrane technology for CO2 sep-
aration, the researchers should focus on the development of new
fillers for achieving next generation of MMMs, whose enhanced
permeability and selectivity could lie in the D region.
8. Conclusion and future prospects
The state-of-the-art membrane systems for CO2 separation from
emission streams were outlined in this review. Among the three
types of membrane system, namely, polymeric, inorganic, and
hybrid (mixed matrix) membranes, this review provides an over-
view on the importance of various types of inorganic fillers in
MMMs. Even though many review reports are available for MMMs,
the studies on MMMs will be continued until the new inorganic
materials are developed, because it is understood that inorganic fil-
lers play a vital role in MMMs for achieving high permeability with
better selectivity in gas separation.
This comprehensive review reveals that MMMs possess remark-
able performance and overcomes the drawbacks like low perme-
ability and/or selectivity of polymeric and inorganic membranes.
The properties of fillers such as size, shape, porous nature, and sur-
face moieties, improve the interfacial interaction between polymer
and fillers and effectively reduce the formation of void defects in
the MMMs. It is also acknowledged that porous fillers in MMMs
allow gas molecules through molecular sieves, and nonporous fil-
lers enhance gas separation by changing the polymer chain orien-
tation. The intense studies reveal that remarkable gas transport by
MMMs is achieved by a low filler loading, enhanced dispersion of
fillers into the polymer matrix, and fabrication of ultrathin-
layered MMMs, as a result of the inverse relationship of gas sepa-
ration and thickness of membrane. From the reported investiga-
tions, it can be observed that surface modified fillers revealed
better gas transport than unmodified fillers. Still, a lot of attention
has been devoted to study the effect of surface modification of fil-
lers in MMMs’ fabrication. From the available reports, it is under-
stood that among various fillers employed in MMMs, MOFs are
recognized as potential fillers to overcome the trade-off limitation
of membranes, which increases the CO2 permeability than zeolite
and carbon fillers, due to their superior textural properties. Fur-
ther, the result illustrates that the order of fillers in MMMs for
the enhanced selectivity of CO2/CH4 and CO2/N2 is car-
bon > MOFs > zeolites, which might be due to the interstitial chan-
nel and large surface area that selects CO2 compared to the light
gases.
This critical review deals with the influence and screening of
the fillers for the fabrication of MMMs for CO2 separation. It is
important to consider suitable properties of filler during their
selection based on the CO2 emission spot. For instance, CO2 perme-
ability is more preferred than CO2 selectivity during CO2 separation
from flue gas in post combustion process, whereas both properties
are important in CO2 separation from syngas (precombustion).
Thus, based on emission spot, filler grouped under C or D region,
may be selected for fabrication of MMMs. Accordingly, new type
of fillers can be developed based on CO2 separation process. In
addition, the challenges of MMMs against reliability, lifetime, and
removal efficiency should also be given attention.
References
[1] L. Bernstein, P. Bosch, O. Canziani, Z. Chen, R. Christ, K. Riahi, IPCC, 2007:
climate change 2007: synthesis report, IPCC, 2008.
[2] IPCC, The physical science basis. Contribution of working group I to the fifth
assessment report of the intergovernmental panel on climate change, in: T.F.
Stocker, D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung, A. Nauels, Y.
Xia, V. Bex and P.M. Midgley (Eds.), Cambridge University Press, Cambridge,
United Kingdom and New York, NY, pp. 1-1535, 2013.
447
[3] The Keeling Curve, https://www.co2.earth/, June, 2017.
[4] UN Climate Change Paris Agreement, 2016. http://newsroom.unfccc.int/paris-
agreement/175-states-sign-paris-agreement/.
[5] J. van Straelen, F. Geuzebroek, N. Goodchild, G. Protopapas, L. Mahony, CO2
capture for refineries, a practical approach, Int. J. Greenhouse Gas Control 4
(2010) 316–320.
[6] M. Vinoba, M. Bhagiyalakshmi, A.N. Grace, D.H. Kim, Y. Yoon, S.C. Nam, I.H.
Baek, S.K. Jeong, Carbonic anhydrase promotes the absorption rate of CO2 in
postcombustion processes, J. Phys. Chem. B 117 (2013) 5683–5690.
[7] M. Vinoba, M. Bhagiyalakshmi, A.N. Grace, D.H. Chu, S.C. Nam, Y. Yoon, S.H.
Yoon, S.K. Jeong, CO2 absorption and sequestration as various polymorphs of
CaCo3 using sterically hindered amine, Langmuir 29 (2013) 15655–15663.
[8] M. Vinoba, M. Bhagiyalakshmi, S.Y. Choi, K.T. Park, H.J. Kim, S.K. Jeong,
Harvesting CaCO3 polymorphs from in situ CO2 capture process, J. Phys.
Chem. C 118 (2014) 17556–17566.
[9] M. Bhagiyalakshmi, L.J. Yun, R. Anuradha, H.T. Jang, Utilization of rice husk
ash as silica source for the synthesis of mesoporous silicas and their
application to CO2 adsorption through TREN/TEPA grafting, J. Hazard. Mater.
175 (2010) 928–938.
[10] M. Bhagiyalakshmi, P. Hemalatha, M. Ganesh, M.M. Peng, H.T. Jang, Synthesis
of copper exchanged heteropolyacids supported on MCM-48 and its
application for CO2 adsorption, J. Ind. Eng. Chem. 17 (2011) 628–632.
[11] M. Bhagiyalakshmi, R. Anuradha, S. Do Park, H.T. Jang, Octa(aminophenyl)
silsesquioxane fabrication on chlorofunctionalized mesoporous SBA-15 for
CO2 adsorption, Microporous Mesoporous Mater. 131 (2010) 265–273.
[12] M. Bhagiyalakshmi, J.Y. Lee, H.T. Jang, Synthesis of mesoporous magnesium
oxide: its application to CO2 chemisorption, Int. J. Greenhouse Gas Control 4
(2010) 51–56.
[13] M. Bhagiyalakshmi, P. Hemalatha, M. Ganesh, P.M. Mei, H.T. Jang, A direct
synthesis of mesoporous carbon supported MgO sorbent for CO2 capture, Fuel
90 (2011) 1662–1667.
[14] T. Li, Y. Pan, K.V. Peinemann, Z. Lai, Carbon dioxide selective mixed matrix
composite membrane containing ZIF-7 nano-fillers, J. Membr. Sci. 425–426
(2013) 235–242.
[15] C. Zhang, Y. Wu, Y. Zhang, Y. Bai, J. Gu, Y. Sun, Poly(ether-b-amide)/ethylene
glycol monophenyl ether gel membrane with superior CO2/N2 separation
performance fabricated by thermally induced phase separation method, J.
Membr. Sci. 508 (2016) 136–145.
[16] G. Xu, F. Liang, Y. Yang, Y. Hu, K. Zhang, W. Liu, An improved CO2 separation
and purification system based on cryogenic separation and distillation
theory, Energies 7 (2014) 3484.
[17] G. Xu, L. Li, Y. Yang, L. Tian, T. Liu, K. Zhang, A novel CO2 cryogenic liquefaction
and separation system, Energy 42 (2012) 522–529.
[18] M. Vinoba, D.H. Kim, K.S. Lim, S.K. Jeong, S.W. Lee, M. Alagar, Biomimetic
sequestration of CO2 and reformation to CaCO3 using bovine carbonic
anhydrase immobilized on SBA-15, Energy Fuels 25 (2011) 438–445.
[19] M. Vinoba, M. Bhagiyalakshmi, S.K. Jeong, S.C. Nam, Y. Yoon, Carbonic
anhydrase immobilized on encapsulated magnetic nanoparticles for CO2
sequestration, Chem. Eur. J. 18 (2012) 12028–12034.
[20] M. Vinoba, M. Bhagiyalakshmi, S.K. Jeong, Y.I. Yoon, S.C. Nam, Capture and
sequestration of CO2 by human carbonic anhydrase covalently immobilized
onto amine-functionalized SBA-15, J. Phys. Chem. C 115 (2011) 20209–
20216.
[21] M. Rezakazemi, A.E. Amooghin, M.M. Montazer-Rahmati, A.F. Ismail, T.
Matsuura, State-of-the-art membrane based CO2 separation using mixed
matrix membranes (MMMs): an overview on current status and future
directions, Prog. Polym. Sci. 39 (2014) 817–861.
[22] N. MacDowell, N. Florin, A. Buchard, J. Hallett, A. Galindo, G. Jackson, C.S.
Adjiman, C.K. Williams, N. Shah, P. Fennell, An overview of CO2 capture
technologies, Energy Environ. Sci. 3 (2010) 1645–1669.
[23] Y. Alqaheem, A. Alomair, M. Vinoba, A. Perez, Polymeric gas-separation
membranes for petroleum refining, Int. J. Polym. Sci. 2017 (2017) 4250927.
[24] S. Sridhar, B. Smitha, T.M. Aminabhavi, Separation of carbon dioxide from
natural gas mixtures through polymeric membranes – a review, Sep. Purif.
Rev. 36 (2007) 113–174.
[25] N. Du, H.B. Park, M.M. Dal-Cin, M.D. Guiver, Advances in high permeability
polymeric membrane materials for CO2 separations, Energy Environ. Sci. 5
(2012) 7306–7322.
[26] Z. Mao, S.B. Sinnott, Separation of organic molecular mixtures in carbon
nanotubes and bundles: molecular dynamics simulations, J. Phys. Chem. B
105 (2001) 6916–6924.
[27] Z. Mao, K.-H. Lee, S.B. Sinnott, Nanotubes as membranes: Predictions of
atomistic simulations, Energeia 14 (2003) 1–4.
[28] G.C. Kapantaidakis, S.P. Kaldis, G.P. Sakellaropoulos, E. Chira, B. Loppinet, G.
Floudas, Interrelation between phase state and gas permeation in
polysulfone/polyimide blend membranes, J. Polym. Sci., Part B: Polym. Phys.
37 (1999) 2788–2798.
[29] S. Wang, X. Li, H. Wu, Z. Tian, Q. Xin, G. He, D. Peng, S. Chen, Y. Yin, Z. Jiang, M.
D. Guiver, Advances in high permeability polymer-based membrane
materials for CO2 separations, Energy Environ. Sci. 9 (2016) 1863–1890.
[30] N. Jusoh, Y.F. Yeong, T.L. Chew, K.K. Lau, A.M. Shariff, Current development
and challenges of mixed matrix membranes for CO2/CH4 separation, Sep.
Purif. Rev. 45 (2016) 321–344.
[31] L.M. Robeson, The upper bound revisited, J. Membr. Sci. 320 (2008) 390–400.
[32] G. Maier, Gas separation with polymer membranes, Angew. Chem. Int. Ed. 37
(1998) 2960–2974.
448 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
[33] A. Jamil, O.P. Ching, A.B.M. Shariff, Current status and future prospect of
polymer-layered silicate mixed-matrix membranes for CO2/CH4 Separation,
Chem. Eng. Technol. 39 (2016) 1393–1405.
[34] R. Nasir, H. Mukhtar, Z. Man, D.F. Mohshim, Material advancements in
fabrication of mixed-matrix membranes, Chem. Eng. Technol. 36 (2013) 717–
727.
[35] Y. Zhang, J. Sunarso, S. Liu, R. Wang, Current status and development of
membranes for CO2/CH4 separation: a review, Int. J. Greenhouse Gas Control
12 (2013) 84–107.
[36] S. Zhao, P.H.M. Feron, L. Deng, E. Favre, E. Chabanon, S. Yan, J. Hou, V. Chen, H.
Qi, Status and progress of membrane contactors in post-combustion carbon
capture: a state-of-the-art review of new developments, J. Membr. Sci. 511
(2016) 180–206.
[37] A.A. Alomair, S.M. Al-Jubouri, S.M. Holmes, A novel approach to fabricate
zeolite membranes for pervaporation processes, J. Mater. Chem. A 3 (2015)
9799–9806.
[38] H. Vinh-Thang, S. Kaliaguine, Predictive models for mixed-matrix membrane
performance: a review, Chem. Rev. 113 (2013) 4980–5028.
[39] R. Mahajan, W.J. Koros, Factors controlling successful formation of mixed-
matrix gas separation materials, Ind. Eng. Chem. Res. 39 (2000) 2692–2696.
[40] R. Mahajan, R. Burns, M. Schaeffer, W.J. Koros, Challenges in forming
successful mixed matrix membranes with rigid polymeric materials, J. Appl.
Polym. Sci. 86 (2002) 881–890.
[41] G. Dong, H. Li, V. Chen, Challenges and opportunities for mixed-matrix
membranes for gas separation, J. Mater. Chem. A 1 (2013) 4610–4630.
[42] Y. Zhang, X. Feng, S. Yuan, J. Zhou, B. Wang, Challenges and recent advances in
MOF-polymer composite membranes for gas separation, Inorg. Chem. Front. 3
(2016) 896–909.
[43] B. Zornoza, C. Téllez, J. Coronas, Mixed matrix membranes comprising glassy
polymers and dispersed mesoporous silica spheres for gas separation, J.
Membr. Sci. 368 (2011) 100–109.
[44] M.J.C. Ordoñez, K.J. Balkus Jr, J.P. Ferraris, I.H. Musselman, Molecular sieving
realized with ZIF-8/MatrimidÒ mixed-matrix membranes, J. Membr. Sci. 361
(2010) 28–37.
[45] S. Rafiq, Z. Man, A. Maulud, N. Muhammad, S. Maitra, Separation of CO2 from
CH4 using polysulfone/polyimide silica nanocomposite membranes, Sep.
Purif. Technol. 90 (2012) 162–172.
[46] C.A. Scholes, G.W. Stevens, S.E. Kentish, Membrane gas separation
applications in natural gas processing, Fuel 96 (2012) 15–28.
[47] T.S. Chung, L.Y. Jiang, Y. Li, S. Kulprathipanja, Mixed matrix membranes
(MMMs) comprising organic polymers with dispersed inorganic fillers for gas
separation, Prog. Polym. Sci. 32 (2007) 483–507.
[48] R.H.B. Bouma, A. Checchetti, G. Chidichimo, E. Drioli, Permeation through a
heterogeneous membrane: the effect of the dispersed phase, J. Membr. Sci.
128 (1997) 141–149.
[49] N. Rangnekar, N. Mittal, B. Elyassi, J. Caro, M. Tsapatsis, Zeolite membranes – a
review and comparison with MOFs, Chem. Soc. Rev. 44 (2015) 7128–7154.
[50] J. Sublet, M. Pera-Titus, N. Guilhaume, D. Farrusseng, L. Schrive, P. Chanaud, B.
Siret, S. Durécu, Technico-economical assessment of MFI-type zeolite
membranes for CO2 capture from postcombustion flue gases, AIChE J. 58
(2012) 3183–3194.
[51] G. Liu, W. Jin, N. Xu, Graphene-based membranes, Chem. Soc. Rev. 44 (2015)
5016–5030.
[52] H.B. Tanh Jeazet, C. Staudt, C. Janiak, Metal-organic frameworks in mixed-
matrix membranes for gas separation, Dalton Trans. 41 (2012) 14003–14027.
[53] T. Rodenas, I. Luz, G. Prieto, B. Seoane, H. Miro, A. Corma, F. Kapteijn, F.X.
Llabrés i Xamena, J. Gascon, Metal–organic framework nanosheets in polymer
composite materials for gas separation, Nat. Mater. 14 (2015) 48–55.
[54] S.J.D. Smith, B.P. Ladewig, A.J. Hill, C.H. Lau, M.R. Hill, Post-synthetic Ti
exchanged UiO-66 metal-organic frameworks that deliver exceptional gas
permeability in mixed matrix membranes, Sci. Rep. 5 (2015) 7823.
[55] J. Yao, H. Wang, Zeolitic imidazolate framework composite membranes and
thin films: synthesis and applications, Chem. Soc. Rev. 43 (2014) 4470–4493.
[56] C. Zhang, W.J. Koros, Zeolitic imidazolate framework-enabled membranes:
challenges and opportunities, J. Phys. Chem. Lett. 6 (2015) 3841–3849.
[57] B. Li, H. Wang, B. Chen, Microporous metal–organic frameworks for gas
separation, Chem. Asian J. 9 (2014) 1474–1498.
[58] H. Sun, T. Wang, Y. Xu, W. Gao, P. Li, Q.J. Niu, Fabrication of polyimide and
functionalized multi-walled carbon nanotubes mixed matrix membranes by
in-situ polymerization for CO2 separation, Sep. Purif. Technol. 177 (2017)
327–336.
[59] H. Siddique, E. Rundquist, Y. Bhole, L.G. Peeva, A.G. Livingston, Mixed matrix
membranes for organic solvent nanofiltration, J. Membr. Sci. 452 (2014) 354–
366.
[60] J. Ahn, W.-J. Chung, I. Pinnau, M.D. Guiver, Polysulfone/silica nanoparticle mixed-
matrix membranes for gas separation, J. Membr. Sci. 314 (2008) 123–133.
[61] M. Sadeghi, M.A. Semsarzadeh, M. Barikani, M.P. Chenar, Gas separation
properties of polyether-based polyurethane–silica nanocomposite
membranes, J. Membr. Sci. 376 (2011) 188–195.
[62] F. Moghadam, M.R. Omidkhah, E. Vasheghani-Farahani, M.Z. Pedram, F.
Dorosti, The effect of TiO2 nanoparticles on gas transport properties of
Matrimid5218-based mixed matrix membranes, Sep. Purif. Technol. 77
(2011) 128–136.
[63] S.M. Momeni, M. Pakizeh, Preparation, characterization and gas permeation
study of PSf/MgO nanocomposite membrane, Braz. J. Chem. Eng. 30 (2013)
589–597.
[64] A.F. Bushell, M.P. Attfield, C.R. Mason, P.M. Budd, Y. Yampolskii, L.
Starannikova, A. Rebrov, F. Bazzarelli, P. Bernardo, J.C. Jansen, M. Lanč, K.
Friess, V. Shantarovich, V. Gustov, V. Isaeva, Gas permeation parameters of
mixed matrix membranes based on the polymer of intrinsic microporosity
PIM-1 and the zeolitic imidazolate framework ZIF-8, J. Membr. Sci. 427
(2013) 48–62.
[65] A.F. Ismail, N.H. Rahim, A. Mustafa, T. Matsuura, B.C. Ng, S. Abdullah, S.A.
Hashemifard, Gas separation performance of polyethersulfone/multi-walled
carbon nanotubes mixed matrix membranes, Sep. Purif. Technol. 80 (2011)
20–31.
[66] Y.S. Lin, I. Kumakiri, B.N. Nair, H. Alsyouri, Microporous inorganic
membranes, Sep. Purif. Methods 31 (2002) 229–379.
[67] J. Caro, M. Noack, P. Kölsch, Zeolite membranes: from the laboratory scale to
technical applications, Adsorption 11 (2005) 215–227.
[68] A. Ebadi Amooghin, M. Omidkhah, A. Kargari, The effects of aminosilane
grafting on NaY zeolite–MatrimidÒ5218 mixed matrix membranes for CO2/
CH4 separation, J. Membr. Sci. 490 (2015) 364–379.
[69] O.G. Nik, X.Y. Chen, S. Kaliaguine, Amine-functionalized zeolite FAU/EMT-
polyimide mixed matrix membranes for CO2/CH4 separation, J. Membr. Sci.
379 (2011) 468–478.
[70] J. Liu, T.-H. Bae, W. Qiu, S. Husain, S. Nair, C.W. Jones, R.R. Chance, W.J. Koros,
Butane isomer transport properties of 6FDA–DAM and MFI–6FDA–DAM
mixed matrix membranes, J. Membr. Sci. 343 (2009) 157–163.
[71] M.E. Lydon, K.A. Unocic, T.-H. Bae, C.W. Jones, S. Nair, Structure–property
relationships of inorganically surface-modified zeolite molecular sieves for
nanocomposite membrane fabrication, J. Phys. Chem. C 116 (2012) 9636–
9645.
[72] T.-H. Bae, J. Liu, J.S. Lee, W.J. Koros, C.W. Jones, S. Nair, Facile high-yield
solvothermal deposition of inorganic nanostructures on zeolite crystals for
mixed matrix membrane fabrication, J. Am. Chem. Soc. 131 (2009) 14662–
14663.
[73] O. Bakhtiari, S. Mosleh, T. Khosravi, T. Mohammadi, Synthesis and
characterization of polyimide mixed matrix membranes, Sep. Sci. Technol.
46 (2011) 2138–2147.
[74] A.L. Ahmad, M.G. Mohd Nawawi, L.K. So, Characterization and performance
evaluations of sodium zeolite-Y filled chitosan polymeric membrane: Effect
of sodium zeolite-Y concentration, J. Appl. Polym. Sci. 99 (2006) 1740–1751.
[75] V. Martin-Gil, A. López, P. Hrabanek, R. Mallada, I.F.J. Vankelecom, V. Fila,
Study of different titanosilicate (TS-1 and ETS-10) as fillers for mixed matrix
membranes for CO2/CH4 gas separation applications, J. Membr. Sci. 523
(2017) 24–35.
[76] D. Zhao, J. Ren, H. Li, K. Hua, M. Deng, Poly(amide-6-b-ethylene oxide)/SAPO-
34 mixed matrix membrane for CO2 separation, J. Energy Chem. 23 (2014)
227–234.
[77] H.K. Jeong, W. Krych, H. Ramanan, S. Nair, E. Marand, M. Tsapatsis, Fabrication
of polymer/selective-flake nanocomposite membranes and their use in gas
separation, Chem. Mater. 16 (2004) 3838–3845.
[78] H. Wu, X. Li, Y. Li, S. Wang, R. Guo, Z. Jiang, C. Wu, Q. Xin, X. Lu, Facilitated
transport mixed matrix membranes incorporated with amine functionalized
MCM-41 for enhanced gas separation properties, J. Membr. Sci. 465 (2014)
78–90.
[79] A.L. Khan, S.P. Sree, J.A. Martens, M.T. Raza, I.F.J. Vankelecom, Mixed matrix
membranes comprising of matrimid and mesoporous COK-12: preparation
and gas separation properties, J. Membr. Sci. 495 (2015) 471–478.
[80] S. Hassanajili, M. Khademi, P. Keshavarz, Influence of various types of silica
nanoparticles on permeation properties of polyurethane/silica mixed matrix
membranes, J. Membr. Sci. 453 (2014) 369–383.
[81] H. Hosseinzadeh Beiragh, M. Omidkhah, R. Abedini, T. Khosravi, S. Pakseresht,
Synthesis and characterization of poly (ether-block-amide) mixed matrix
membranes incorporated by nanoporous ZSM-5 particles for CO2/CH4
separation, Asia-Pac. J. Chem. Eng. 11 (2016) 522–532.
[82] F. Dorosti, M. Omidkhah, R. Abedini, Enhanced CO2/CH4 separation properties
of asymmetric mixed matrix membrane by incorporating nano-porous ZSM-5
and MIL-53 particles into MatrimidÒ5218, J. Nat. Gas Sci. Eng. 25 (2015) 88–
102.
[83] Y. Zhang, K.J. Balkus Jr, I.H. Musselman, J.P. Ferraris, Mixed-matrix
membranes composed of MatrimidÒ and mesoporous ZSM-5 nanoparticles,
J. Membr. Sci. 325 (2008) 28–39.
[84] F. Banihashemi, M. Pakizeh, A. Ahmadpour, CO2 separation using PDMS/ZSM-
5 zeolite composite membrane, Sep. Purif. Technol. 79 (2011) 293–302.
[85] N. Bryan, E. Lasseuguette, M. Van Dalen, N. Permogorov, A. Amieiro, S.
Brandani, M.C. Ferrari, Development of mixed matrix membranes containing
zeolites for post-combustion carbon capture, Energy Procedia 63 (2014) 160–
166.
[86] R.S. Murali, A.F. Ismail, M.A. Rahman, S. Sridhar, Mixed matrix membranes of
Pebax-1657 loaded with 4A zeolite for gaseous separations, Sep. Purif.
Technol. 129 (2014) 1–8.
[87] E. Tocci, A. Gugliuzza, L. De Lorenzo, M. Macchione, G. De Luca, E. Drioli,
Transport properties of a co-poly(amide-12-b-ethylene oxide) membrane: a
comparative study between experimental and molecular modelling results, J.
Membr. Sci. 323 (2008) 316–327.
[88] J. Potreck, K. Nijmeijer, T. Kosinski, M. Wessling, Mixed water vapor/gas
transport through the rubbery polymer PEBAXÒ 1074, J. Membr. Sci. 338
(2009) 11–16.
[89] M. Pakizeh, S. Hokmabadi, Experimental study of the effect of zeolite 4A
treated with magnesium hydroxide on the characteristics and gas-
 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
permeation properties of polysulfone-based mixed-matrix membranes, J.
Appl. Polym. Sci. 134 (2016) 44329.
[90] H. Gong, S.S. Lee, T.H. Bae, Mixed-matrix membranes containing inorganically
surface-modified 5A zeolite for enhanced CO2/CH4 separation, Microporous
Mesoporous Mater. 237 (2017) 82–89.
[91] K. Zarshenas, A. Raisi, A. Aroujalian, Mixed matrix membrane of nano-zeolite
NaX/poly (ether-block-amide) for gas separation applications, J. Membr. Sci.
510 (2016) 270–283.
[92] H. Sanaeepur, A. Kargari, B. Nasernejad, Aminosilane-functionalization of a
nanoporous Y-type zeolite for application in a cellulose acetate based mixed
matrix membrane for CO2 separation, RSC Adv. 4 (2014) 63966–63976.
[93] J. Yu, L. Li, N. Liu, R. Lee, An approach to prepare defect-free PES/MFI-type
zeolite mixed matrix membranes for CO2/N2 separation, J. Membr. Sci. 48
(2013) 3782–3788.
[94] M. Laghaei, M. Sadeghi, B. Ghalei, M. Shahrooz, The role of compatibility
between polymeric matrix and silane coupling agents on the performance of
mixed matrix membranes: polyethersulfone/MCM-41, J. Membr. Sci. 513
(2016) 20–32.
[95] A. Ghadimi, T. Mohammadi, N. Kasiri, A novel chemical surface modifi cation
for the fabrication of PEBA/SiO2 nanocomposite membranes to separate CO2
from syngas and natural gas streams, Ind. Eng. Chem. Res. 53 (2014) 17476–
17486.
[96] Q. Xin, Y. Zhang, Y. Shi, H. Ye, L. Lin, X. Ding, Y. Zhang, H. Wu, Z. Jiang, Tuning
the performance of CO2 separation membranes by incorporating
multifunctional modified silica microspheres into polymer matrix, J.
Membr. Sci. 514 (2016) 73–85.
[97] H. Sanaeepur, B. Nasernejad, A. Kargari, Cellulose acetate/nano-porous zeolite
mixed matrix membrane for CO2 separation, Greenhouse Gases Sci. Technol.
5 (2015) 291–304.
[98] N. Azizi, T. Mohammadi, R.M. Behbahani, Comparison of permeability
performance of PEBAX-1074/TiO2, PEBAX-1074/SiO2 and PEBAX-1074/Al2O3
nanocomposite membranes for CO2/CH4 separation, Chem. Eng. Res. Des. 117
(2017) 177–189.
[99] A.A. Shamsabadi, F. Seidi, E. Salehi, M. Nozari, A. Rahimpour, M. Soroush,
Efficient CO2-removal using novel mixed-matrix membranes with modified
TiO2 nanoparticles, J. Mater. Chem. A 5 (2017) 4011–4025.
[100] N. Azizi, T. Mohammadi, R.M. Behbahani, Synthesis of a new nanocomposite
membrane (PEBAX-1074/PEG-400/TiO2) in order to separate CO2 from CH4, J.
Nat. Gas Sci. Eng. 37 (2017) 39–51.
[101] L.M. Robeson, Correlation of separation factor versus permeability for
polymeric membranes, J. Membr. Sci. 62 (1991) 165–185.
[102] S.L. Ruan, P. Gao, X.G. Yang, T.X. Yu, Toughening high performance ultrahigh
molecular weight polyethylene using multiwalled carbon nanotubes,
Polymer 44 (2003) 5643–5654.
[103] A.L. Ahmad, Z.A. Jawad, S.C. Low, S.H.S. Zein, A cellulose acetate/multi-walled
carbon nanotube mixed matrix membrane for CO2/N2 separation, J. Membr.
Sci. 451 (2014) 55–66.
[104] M.A. Aroon, A.F. Ismail, T. Matsuura, Beta-cyclodextrin functionalized
MWCNT: a potential nano-membrane material for mixed matrix gas
separation membranes development, Sep. Purif. Technol. 115 (2013)
39–50.
[105] M.A. Aroon, A.F. Ismail, M.M. Montazer-Rahmati, T. Matsuura, Effect of
chitosan as a functionalization agent on the performance and separation
properties of polyimide/multi-walled carbon nanotubes mixed matrix flat
sheet membranes, J. Membr. Sci. 364 (2010) 309–317.
[106] H. Zhang, R. Guo, J. Hou, Z. Wei, X. Li, Mixed-matrix membranes containing
carbon nanotubes composite with hydrogel for efficient CO2 separation, ACS
Appl. Mater. Interfaces 8 (2016) 29044–29051.
[107] M.M. Khan, V. Filiz, G. Bengtson, S. Shishatskiy, M.M. Rahman, J. Lillepaerg, V.
Abetz, Enhanced gas permeability by fabricating mixed matrix membranes of
functionalized multiwalled carbon nanotubes and polymers of intrinsic
microporosity (PIM), J. Membr. Sci. 436 (2013) 109–120.
[108] D. Zhao, J. Ren, H. Li, X. Li, M. Deng, Gas separation properties of poly(amide-
6-b-ethylene oxide)/amino modified multi-walled carbon nanotubes mixed
matrix membranes, J. Membr. Sci. 467 (2014) 41–47.
[109] D. Zhao, J. Ren, Y. Wang, Y. Qiu, H. Li, K. Hua, X. Li, J. Ji, M. Deng, High CO2
separation performance of PebaxÒ/CNTs/GTA mixed matrix membranes, J.
Membr. Sci. 521 (2017) 104–113.
[110] S. Wang, Y. Liu, S. Huang, H. Wu, Y. Li, Z. Tian, Z. Jiang, Pebax-PEG-MWCNT
hybrid membranes with enhanced CO2 capture properties, J. Membr. Sci. 460
(2014) 62–70.
[111] H. Cong, J. Zhang, M. Radosz, Y. Shen, Carbon nanotube composite
membranes of brominated poly(2,6-diphenyl-1,4-phenylene oxide) for gas
separation, J. Membr. Sci. 294 (2007) 178–185.
[112] S. Kim, L. Chen, J.K. Johnson, E. Marand, Polysulfone and functionalized
carbon nanotube mixed matrix membranes for gas separation: theory and
experiment, J. Membr. Sci. 294 (2007) 147–158.
[113] A.D. Kiadehi, M. Jahanshahi, A. Rahimpour, S.A.A. Ghoreyshi, The effect of
functionalized carbon nano-fiber (CNF) on gas separation performance of
polysulfone (PSf) membranes, Chem. Eng. Process. Process Intensif. 90 (2015)
41–48.
[114] M.B. Rao, S. Sircar, Nanoporous carbon membranes for separation of gas
mixtures by selective surface flow, J. Membr. Sci. 85 (1993) 253–264.
[115] D.Q. Vu, W.J. Koros, S.J. Miller, Mixed matrix membranes using carbon
molecular sieves: I. Preparation and experimental results, J. Membr. Sci. 211
(2003) 311–334.
449
[116] D.Q. Vu, W.J. Koros, S.J. Miller, Mixed matrix membranes using carbon
molecular sieves: II. Modeling permeation behavior, J. Membr. Sci. 211 (2003)
335–348.
[117] R. Nasir, H. Mukhtar, Z. Man, M.S. Shaharun, M.Z.A. Bakar, Development and
performance prediction of polyethersulfone-carbon molecular sieve mixed
matrix membrane for CO2/CH4 separation, Chem. Eng. Trans. (2015) 1417–
1422.
[118] H. Shinohara, A. Tiwari, M. Sharon, M. Sharon, Graphene: An Introduction to
the Fundamentals and Industrial Applications, John Wiley & Sons, 2015.
[119] Z. Chen, W. Ren, L. Gao, B. Liu, S. Pei, H.-M. Cheng, Three-dimensional flexible
and conductive interconnected graphene networks grown by chemical
vapour deposition, Nat Mater 10 (2011) 424–428.
[120] H. Huang, W. Chen, S. Chen, A.T.S. Wee, Bottom-up growth of epitaxial
graphene on 6H-SiC(0001), ACS Nano 2 (2008) 2513–2518.
[121] S.P. Koenig, L. Wang, J. Pellegrino, J.S. Bunch, Selective molecular sieving
through porous graphene, Nat. Nanotechnol. 7 (2012) 728–732.
[122] H. Liu, S. Dai, D.E. Jiang, Insights into CO2/N2 separation through nanoporous
graphene from molecular dynamics, Nanoscale 5 (2013) 9984–9987.
[123] J. Lee, N.R. Aluru, Water-solubility-driven separation of gases using graphene
membrane, J. Membr. Sci. 428 (2013) 546–553.
[124] X. Li, Y. Cheng, H. Zhang, S. Wang, Z. Jiang, R. Guo, H. Wu, Efficient CO2
capture by functionalized graphene oxide nanosheets as fillers to fabricate
multi-permselective mixed matrix membranes, ACS Appl. Mater. Interfaces 7
(2015) 5528–5537.
[125] D. Peng, S. Wang, Z. Tian, X. Wu, Y. Wu, H. Wu, Q. Xin, J. Chen, X. Cao, Z. Jiang,
Facilitated transport membranes by incorporating graphene nanosheets with
high zinc ion loading for enhanced CO2 separation, J. Membr. Sci. 522 (2017)
351–362.
[126] J. Shen, M. Zhang, G. Liu, K. Guan, W. Jin, Size effects of graphene oxide on
mixed matrix membranes for CO2 separation, AIChE J. 62 (2016) 2843–2852.
[127] K. Zahri, K.C. Wong, P.S. Goh, A.F. Ismail, Graphene oxide/polysulfone hollow
fiber mixed matrix membranes for gas separation, RSC Adv. 6 (2016) 89130–
89139.
[128] S.A. Habibiannejad, A. Aroujalian, A. Raisi, Pebax-1657 mixed matrix
membrane containing surface modified multi-walled carbon nanotubes for
gas separation, RSC Adv. 6 (2016) 79563–79577.
[129] A.D. Kiadehi, A. Rahimpour, M. Jahanshahi, A.A. Ghoreyshi, Novel carbon
nano-fibers (CNF)/polysulfone (PSf) mixed matrix membranes for gas
separation, J. Ind. Eng. Chem. 22 (2015) 199–207.
[130] M. Karunakaran, R. Shevate, M. Kumar, K.V. Peinemann, CO2-selective PEO-
PBT (PolyActive[trade mark sign])/graphene oxide composite membranes,
Chem. Commun. 51 (2015) 14187–14190.
[131] S. Quan, S.W. Li, Y.C. Xiao, L. Shao, CO2-selective mixed matrix membranes
(MMMs) containing graphene oxide (GO) for enhancing sustainable CO2
capture, Int. J. Greenhouse Gas Control 56 (2017) 22–29.
[132] M. Sarfraz, M. Ba-Shammakh, Synergistic effect of incorporating ZIF-302 and
graphene oxide to polysulfone to develop highly selective mixed-matrix
membranes for carbon dioxide separation from wet post-combustion flue
gases, J. Ind. Eng. Chem. 36 (2016) 154–162.
[133] M. Sarfraz, M. Ba-Shammakh, Synergistic effect of adding graphene oxide and
ZIF-301 to polysulfone to develop high performance mixed matrix
membranes for selective carbon dioxide separation from post combustion
flue gas, J. Membr. Sci. 514 (2016) 35–43.
[134] J.H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, K.P.
Lillerud, A new zirconium inorganic building brick forming metal organic
frameworks with exceptional stability, J. Am. Chem. Soc. 130 (2008) 13850–
13851.
[135] G.E. Cmarik, M. Kim, S.M. Cohen, K.S. Walton, Tuning the adsorption
properties of UiO-66 via ligand functionalization, Langmuir 28 (2012)
15606–15613.
[136] H. Wu, Y.S. Chua, V. Krungleviciute, M. Tyagi, P. Chen, T. Yildirim, W. Zhou,
Unusual and highly tunable missing-linker defects in zirconium metal–
organic framework UiO-66 and their important effects on gas adsorption, J.
Am. Chem. Soc. 135 (2013) 10525–10532.
[137] S. Biswas, P. Van Der Voort, A general strategy for the synthesis of
functionalised UiO-66 frameworks: characterisation, stability and CO2
adsorption properties, Eur. J. Inorg. Chem. 2013 (2013) 2154–2160.
[138] J. Shen, G. Liu, K. Huang, Q. Li, K. Guan, Y. Li, W. Jin, UiO-66-polyether block
amide mixed matrix membranes for CO2 separation, J. Membr. Sci. 513
(2016) 155–165.
[139] M.R. Khdhayyer, E. Esposito, A. Fuoco, M. Monteleone, L. Giorno, J.C. Jansen,
M.P. Attfield, P.M. Budd, Mixed matrix membranes based on UiO-66 MOFs in
the polymer of intrinsic microporosity PIM-1, Sep. Purif. Technol. 173 (2017)
304–313.
[140] S.R. Venna, M. Lartey, T. Li, A. Spore, S. Kumar, H.B. Nulwala, D.R. Luebke, N.L.
Rosi, E. Albenze, Fabrication of MMMs with improved gas separation
properties using externally-functionalized MOF particles, J. Mater. Chem. A
3 (2015) 5014–5022.
[141] M.W. Anjum, F. Vermoortele, A.L. Khan, B. Bueken, D.E. De Vos, I.F.J.
Vankelecom, Modulated UiO-66-based mixed-matrix membranes for CO2
separation, ACS Appl. Mater. Interfaces 7 (2015) 25193–25201.
[142] A. Phan, C.J. Doonan, F.J. Uribe-Romo, C.B. Knobler, M. O’Keeffe, O.M. Yaghi,
Synthesis, structure, and carbon dioxide capture properties of zeolitic
imidazolate frameworks, Acc. Chem. Res. 43 (2010) 58–67.
[143] K.S. Park, Z. Ni, A.P. Côté, J.Y. Choi, R. Huang, F.J. Uribe-Romo, H.K. Chae, M.
O’Keeffe, O.M. Yaghi, Exceptional chemical and thermal stability of zeolitic
450 M. Vinoba et al. / Separation and Purification Technology 188 (2017) 431–450
imidazolate frameworks, Proc. Natl. Acad. Sci. U.S.A. 103 (2006) 10186–
10191.
[144] V. Nafisi, M.B. Hägg, Development of dual layer of ZIF-8/PEBAX-2533 mixed
matrix membrane for CO2 capture, J. Membr. Sci. 459 (2014) 244–255.
[145] L. Dong, M. Chen, J. Li, D. Shi, W. Dong, X. Li, Y. Bai, Metal-organic framework-
graphene oxide composites: A facile method to highly improve the CO2
separation performance of mixed matrix membranes, J. Membr. Sci. 520
(2016) 801–811.
[146] R.K. Joshi, P. Carbone, F.C. Wang, V.G. Kravets, Y. Su, I.V. Grigorieva, H.A. Wu,
A.K. Geim, R.R. Nair, Precise and ultrafast molecular sieving through graphene
oxide membranes, Science 343 (2014) 752–754.
[147] Z.P. Smith, B.D. Freeman, Graphene oxide: a new platform for high-
performance gas- and liquid-separation membranes, Angew. Chem. Int. Ed.
53 (2014) 10286–10288.
[148] B. Zornoza, B. Seoane, J.M. Zamaro, C. Téllez, J. Coronas, Combination of MOFs
and zeolites for mixed-matrix membranes, ChemPhysChem 12 (2011) 2781–
2785.
[149] N.A.H.M. Nordin, A.F. Ismail, A. Mustafa, R. Surya Murali, T. Matsuura,
Utilizing low ZIF-8 loading for an asymmetric PSf/ZIF-8 mixed matrix
membrane for CO2/CH4 separation, RSC Adv. 5 (2015) 30206–30215.
[150] H.B. Tanh Jeazet, S. Sorribas, J.M. Román-Marín, B. Zornoza, C. Téllez, J.
Coronas, C. Janiak, Increased selectivity in CO2/CH4 separation with mixed-
matrix membranes of polysulfone and mixed-MOFs MIL-101(Cr) and ZIF-8,
Eur. J. Inorg. Chem. 2016 (2016) 4363–4367.
[151] S. Sorribas, B. Zornoza, C. Téllez, J. Coronas, Mixed matrix membranes
comprising silica-(ZIF-8) core-shell spheres with ordered meso-
microporosity for natural- and bio-gas upgrading, J. Membr. Sci. 452 (2014)
184–192.
[152] J.A. Thompson, J.T. Vaughn, N.A. Brunelli, W.J. Koros, C.W. Jones, S. Nair,
Mixed-linker zeolitic imidazolate framework mixed-matrix membranes for
aggressive CO2 separation from natural gas, Microporous Mesoporous Mater.
192 (2014) 43–51.
[153] S. Basu, A. Cano-Odena, I.F.J. Vankelecom, MOF-containing mixed-matrix
membranes for CO2/CH4 and CO2/N2 binary gas mixture separations, Sep.
Purif. Technol. 81 (2011) 31–40.
[154] W.S. Chi, S.J. Kim, S.J. Lee, Y.S. Bae, J.H. Kim, Enhanced performance of mixed-
matrix membranes through a graft copolymer-directed interface and
interaction tuning approach, ChemSusChem 8 (2015) 650–658.
[155] W.S. Chi, S. Hwang, S.J. Lee, S. Park, Y.S. Bae, D.Y. Ryu, J.H. Kim, J. Kim, Mixed
matrix membranes consisting of SEBS block copolymers and size-controlled
ZIF-8 nanoparticles for CO2 capture, J. Membr. Sci. 495 (2015) 479–488.
[156] Y. Ban, Z. Li, Y. Li, Y. Peng, H. Jin, W. Jiao, A. Guo, P. Wang, Q. Yang, C. Zhong,
W. Yang, Confinement of ionic liquids in nanocages: tailoring the molecular
sieving properties of ZIF-8 for membrane-based CO2 capture, Angew. Chem.
Int. Ed. 54 (2015) 15483–15487.
[157] L. Diestel, X.L. Liu, Y.S. Li, W.S. Yang, J. Caro, Comparative permeation studies
on three supported membranes: Pure ZIF-8, pure polymethylphenylsiloxane,
and mixed matrix membranes, Microporous Mesoporous Mater. 189 (2014)
210–215.
[158] Y. Dai, J.R. Johnson, O. Karvan, D.S. Sholl, W.J. Koros, UltemÒ/ZIF-8 mixed
matrix hollow fiber membranes for CO2/N2 separations, J. Membr. Sci. 401–
402 (2012) 76–82.
[159] M.S. Boroglu, A.B. Yumru, Gas separation performance of 6FDA-DAM-ZIF-11
mixed-matrix membranes for H2/CH4 and CO2/CH4 separation, Sep. Purif.
Technol. 173 (2017) 269–279.
[160] L. Hao, K.S. Liao, T.S. Chung, Photo-oxidative PIM-1 based mixed matrix
membranes with superior gas separation performance, J. Mater. Chem. A 3
(2015) 17273–17281.
[161] T.H. Bae, J.S. Lee, W. Qiu, W.J. Koros, C.W. Jones, S. Nair, A high-performance
gas-separation membrane containing submicrometer-sized metal-organic
framework crystals, Angew. Chem. Int. Ed. 49 (2010) 9863–9866.
[162] Y. Ban, Y. Li, Y. Peng, H. Jin, W. Jiao, X. Liu, W. Yang, Metal-substituted zeolitic
imidazolate framework ZIF-108: gas-sorption and membrane-separation
properties, Chem. Eur. J. 20 (2014) 11402–11409.
[163] M. Sarfraz, M. Ba-Shammakh, Combined effect of CNTs with ZIF-302 into
polysulfone to fabricate MMMs for enhanced CO2 separation from flue gases,
Arab. J. Sci. Eng. 41 (2016) 2573–2582.
[164] H. Zhu, L. Wang, X. Jie, D. Liu, Y. Cao, Improved interfacial affinity and CO2
separation performance of asymmetric mixed matrix membranes by
incorporating postmodified MIL-53(Al), ACS Appl. Mater. Interfaces 8
(2016) 22696–22704.
[165] H. Zhu, X. Jie, L. Wang, G. Kang, D. Liu, Y. Cao, Effect of MIL-53 on phase
inversion and gas separation performance of mixed matrix hollow fiber
membranes, RSC Adv. 6 (2016) 69124–69134.
[166] R. Abedini, M. Omidkhah, F. Dorosti, Highly permeable poly(4-methyl-1-
pentyne)/NH2-MIL 53 (Al) mixed matrix membrane for CO2/CH4 separation,
RSC Adv. 4 (2014) 36522–36537.
[167] A. Sabetghadam, B. Seoane, D. Keskin, N. Duim, T. Rodenas, S. Shahid, S.
Sorribas, C.L. Guillouzer, G. Clet, C. Tellez, M. Daturi, J. Coronas, F. Kapteijn, J.
Gascon, Metal organic framework crystals in mixed-matrix membranes:
impact of the filler morphology on the gas separation performance, Adv.
Funct. Mater. 26 (2016) 3154–3163.
[168] N. Tien-Binh, H. Vinh-Thang, X.Y. Chen, D. Rodrigue, S. Kaliaguine, Polymer
functionalization to enhance interface quality of mixed matrix membranes
for high CO2/CH4 gas separation, J. Mater. Chem. A 3 (2015) 15202–15213.
[169] J.O. Hsieh, K.J. Balkus Jr, J.P. Ferraris, I.H. Musselman, MIL-53 frameworks in
mixed-matrix membranes, Microporous Mesoporous Mater. 196 (2014) 165–
174.
[170] E.A. Feijani, A. Tavasoli, H. Mahdavi, Improving gas separation performance of
poly(vinylidene fluoride) based mixed matrix membranes containing metal-
organic frameworks by chemical modification, Ind. Eng. Chem. Res. 54 (2015)
12124–12134.
[171] B. Zornoza, A. Martinez-Joaristi, P. Serra-Crespo, C. Tellez, J. Coronas, J.
Gascon, F. Kapteijn, Functionalized flexible MOFs as fillers in mixed matrix
membranes for highly selective separation of CO2 from CH4 at elevated
pressures, Chem. Commun. 47 (2011) 9522–9524.
[172] T. Rodenas, M. Van Dalen, E. García-Pérez, P. Serra-Crespo, B. Zornoza, F.
Kapteijn, J. Gascon, Visualizing MOF mixed matrix membranes at the
nanoscale: towards structure-performance relationships in CO2/CH4
separation over NH2-MIL-53(Al)@PI, Adv. Funct. Mater. 24 (2014) 249–256.
[173] X. Dong, Q. Liu, A. Huang, Highly permselective MIL-68(Al)/matrimid mixed
matrix membranes for CO2/CH4 separation, J. Appl. Polym. Sci. 133 (2016)
43485.
[174] Q. Xin, J. Ouyang, T. Liu, Z. Li, Z. Li, Y. Liu, S. Wang, H. Wu, Z. Jiang, X. Cao,
Enhanced interfacial interaction and CO2 separation performance of mixed
matrix membrane by incorporating polyethylenimine-decorated metal-
organic frameworks, ACS Appl. Mater. Interfaces 7 (2015) 1065–1077.
[175] M.W. Anjum, B. Bueken, D. De Vos, I.F.J. Vankelecom, MIL-125(Ti) based
mixed matrix membranes for CO2 separation from CH4 and N2, J. Membr. Sci.
502 (2016) 21–28.
[176] J. Kim, J. Choi, Y. Soo Kang, J. Won, Matrix effect of mixed-matrix membrane
containing CO2-selective MOFs, J. Appl. Polym. Sci. 133 (2016) 42853.
[177] N. Tien-Binh, H. Vinh-Thang, X.Y. Chen, D. Rodrigue, S. Kaliaguine,
Crosslinked MOF-polymer to enhance gas separation of mixed matrix
membranes, J. Membr. Sci. 520 (2016) 941–950.
[178] C. Duan, G. Kang, D. Liu, L. Wang, C. Jiang, Y. Cao, Q. Yuan, Enhanced gas
separation properties of metal organic frameworks/ polyetherimide mixed
matrix membranes, J. Appl. Polym. Sci. 131 (2014) 8828–8837.
[179] H. Gong, T.H. Nguyen, R. Wang, T.H. Bae, Separations of binary mixtures of
CO2/CH4 and CO2/N2 with mixed-matrix membranes containing Zn(pyrz)2/
SiF6 metal-organic framework, J. Membr. Sci. 495 (2015) 169–175.
[180] S. Castarlenas, C. Téllez, J. Coronas, Gas separation with mixed matrix
membranes obtained from MOF UiO-66-graphite oxide hybrids, J. Membr.
Sci. 526 (2017) 205–211.
[181] N. Jusoh, Y.F. Yeong, K.K. Lau, A.M. Shariff, Transport properties of mixed
matrix membranes encompassing zeolitic imidazolate framework 8 (ZIF-8)
nanofiller and 6FDA-durene polymer: optimization of process variables for
the separation of CO2 from CH4, J. Cleaner Prod. 149 (2017) 80–95.
[182] E.A. Feijani, H. Mahdavi, A. Tavasoli, Poly(vinylidene fluoride) based mixed
matrix membranes comprising metal organic frameworks for gas separation
applications, Chem. Eng. Res. Des. 96 (2015) 87–102.
[183] T. Rodenas, M. Van Dalen, P. Serra-Crespo, F. Kapteijn, J. Gascon, Mixed matrix
membranes based on NH2-functionalized MIL-type MOFs: influence of
structural and operational parameters on the CO2/CH4 separation
performance, Microporous Mesoporous Mater. 192 (2014) 35–42.
[184] B. Seoane, V. Sebastián, C. Téllez, J. Coronas, Crystallization in THF: the
possibility of one-pot synthesis of mixed matrix membranes containing MOF
MIL-68(Al), CrystEngComm 15 (2013) 9483–9490.
[185] X. Guo, H. Huang, Y. Ban, Q. Yang, Y. Xiao, Y. Li, W. Yang, C. Zhong, Mixed
matrix membranes incorporated with amine-functionalized titanium-based
metal-organic framework for CO2/CH4 separation, J. Membr. Sci. 478 (2015)
130–139.
[186] R. Lin, L. Ge, H. Diao, V. Rudolph, Z. Zhu, Ionic liquids as the MOFs/polymer
interfacial binder for efficient membrane separation, ACS Appl. Mater.
Interfaces 8 (2016) 32041–32049.