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Zr-MOFs-incorporated thin film nanocomposite

Pebax 1657 membranes dip-coated on
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Cite this: J. Mater. Chem. A, 2018, 6,

12380 polymethylpentyne layer for efficient separation of
CO2/CH4†
Mohammad Mozafari, Reza Abedini and Ahmad Rahimpour*

Received 23rd May 2018
Accepted 29th May 2018
DOI: 10.1039/c8ta04806a
rsc.li/materials-a
Using thin film nanocomposite (TFN) membranes is an effective method to obtain high CO2/CH4 separation
performance as compared to traditional mixed matrix membranes (MMMs). In this study, high CO2
permeable TFN membranes comprising coated Pebax as a CO2-philic layer filled with Zr-MOFs over the
highly permeable polymethylpentene (PMP) support with substantial free volume and desired thermal
stability were fabricated to achieve efficient CO2/CH4 separation. A series of pure CO2 and CH4 gas
permeation tests were carried out to evaluate the influence of Zr-MOFs on the gas transport properties
of the as-synthesized TFN membranes. The use of amine-functionalized UiO-66 intensified the
interaction between the polymer phase and embedded MOFs that led to improvement in the CO2/CH4
selectivity. The results obtained from FESEM and TGA/DSC analyses confirmed that the TFN membranes
showed superior compatibility between the polymer and filler without non-selective voids at the
polymer/filler interface. Moreover, the pure gas separation performance of the TFN membranes was
examined under various feed pressures within the range of 2–7 bar. The CO2/CH4 separation improved
as the feed pressure increased, such that the CO2 permeability of 393.8 barrer and CO2/CH4 selectivity
of 39.8 were achieved for TFN membranes containing 1.5 wt% UiO-66-NH2 at a feed pressure of 7 bar.
Further, the mixed gas separation experiments revealed reasonable CO2 permeability and CO2/CH4
selectivity for TFN membranes under both dry and humid conditions.

depend on economics, production rates, and operating condi-

1. Introduction
The worldwide energy demand is increasing with every passing
day, and natural gas, mainly CH4, can have a remarkable
contribution towards fullling this requirement. Nevertheless,
the presence of CO2 and other acid gases (i.e., H2S and SO2) in
natural gas reduces the energy content and makes the gas
streams become corrosive, which in turn, restricts the
compression and transportation of natural gas through pipe-
lines. Therefore, removing CO2 from CH4 is essential in many
industries such as natural gas sweetening, landll gas puri-
cation, and biogas upgrading. Moreover, the emission of CO2,
which is a primary greenhouse gas, is increasing, resulting in
climate change and constrain in global economic growth.
Hence, carbon dioxide separation/capture may be the best
solution to control the emission of this greenhouse gas.1–4
The main techniques of CO2 separation includes absorption,
adsorption, distillation, and membrane separation, which
Department of Chemical Engineering, Babol Noushirvani University of Technology,
Shariati Ave., Babol 4714871167, Iran. E-mail: ahmadrahimpour@nit.ac.ir
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c8ta04806a
tions. Low energy demand, ease of operation, process exibility,
and lower environmental impact make membrane technology
superior to other conventional gas separation methods.5–7
Different types of membranes have been extensively used for
several industrial applications. Inorganic membranes have
exhibited great separation performance with better chemical
and thermal stabilities as compared to polymeric materials.
However, high fabrication costs as well as the lack of process-
ability restrict the implementation of inorganic materials in
large-scale applications. In contrast, polymeric membranes
have advantages including lower fabrication cost and better
scalability.8–10 Nevertheless, polymeric membranes suffer from
intrinsic trade-off between permeability and selectivity, which is
represented by the Robeson's upper bound.11–14 Owing to the
characteristics of polymeric materials and inorganic llers,
MMMs have been introduced to merge the advantages of both
polymeric and inorganic materials with the potential of over-
coming the Robeson's boundary condition.13,15,16 The advan-
tages of inorganic llers such as molecular sieves,17,18 carbon
nanotubes,19 zeolite,20,21 covalent organic frameworks (COF),22
and metal–organic frameworks (MOFs)23–25 in the fabrication of
MMMs have been evaluated through numerous studies. Among

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Paper
the different types of llers, MOFs with three-dimensional
porous structure comprising metal clusters and organic
linkers have gained more attention to be embedded within
polymer materials. MOFs-embedded polymers have shown
a high selective adsorption affinity to a specic gas or penetrant
due to appropriate interactions between them, highly tunable
properties, and large surface area.26,27 UiO-66 is a zirconium(IV)-
based MOF. It has a cubic crystal structure, in which each
Zr6O4(OH)4 octahedral cluster is bridged to twelve 1,4-dicar-
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boxybenzene linkers. UiO-66 particles exhibit high thermal and
chemical stabilities and outstanding CO2 adsorption as
compared to other MOFs.28,29 In recent years, applying TFN
membranes comprising selective thin lms supported by
a porous layer have appeared as a promising method for
favorable separation.30,31 Two distinctive rubbery and glassy
polymeric materials are used to separate CO2 from various gas
streams. Glassy polymers are high selective materials and
usually favored to fabricate gas separation membranes as
compared to rubbery polymers. However, glassy polymers
demonstrate weak resistance to plasticization caused by
condensable gas permeation (i.e., CO2) and thus, their usage is
restricted in some applications.32 Highly permeable water-
swellable polymers (WSPs) such as chitosan,33 poly(ether
block amide) (Pebax),34,35 and poly(vinyl alcohol)36 are consid-
ered as promising materials for separating CO2 from gas
streams. Since water oen exists in industrial gases including
CO2, the fast selective permeation of other forms of CO2 such as
HCO3
can be obtained by means of WPS membranes owing to
membrane swelling.37,38
Pebax is a WSP comprising crystalline polyamide (PA) and
polyethylene oxide (PEO) segments. Changes between the
weight fractions of PA and PEO yield different grades of Pebax
polymers. Pebax® 1657 (40 wt% PA and 60 wt% PEO) exhibited
substantial CO2 permeation owing to the high affinity between
the polar penetrants and PEO so segments.39,40 Moreover,
a exible PEO segment can effectively interact with inorganic
llers, leading to appropriate compatibility at the polymer/ller
interface. Moreover, excellent mechanical/thermal properties of
the resulting membrane can be expected due to the existence of
a hard PA segment in the Pebax structure.41–43
The TFN membranes comprise a thin highly permeable
polymer, and MOFs are a suitable choice to diminish the
challenges of polymer/ller compatibility that nally leads to
improvement in the selectivity while maintaining high perme-
ability.13,25,44–46 PMP is a polyolen that has attracted consider-
able attention as a highly permeable membrane due to its
intrinsic characteristics such as high free volume (0.28), low
density, and excellent chemical and thermal resistances.
Consequently, PMP with such distinctive properties is a prom-
ising material to be used as a support layer in the fabrication of
TFN membranes.5
In this study, TFN membranes with thin Zr-MOFs-embedded
Pebax layers were fabricated over a porous PMP support by
means of dip-coating along with the solvent evaporation
method. Moreover, amine-functionalized UiO-66 was used to
intensify the interaction with carbonyl groups in the Pebax
polymer, which can be effective to avoid non-selective pathway
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Journal of Materials Chemistry A
creation. The effects of various Zr-MOFs loading within the
Pebax selective layer coupled with different feed pressures on
the CO2/CH4 separation of the as-synthesized TFN membranes
were evaluated and discussed.
2. Experimental
2.1. Materials
PMP with medium molecular weight (Fig. 1(a)) was obtained from
Sigma-Aldrich. Pebax® 1657 powder was purchased from Arkema
(Paris, France, Fig. 1(b)). Zirconium tetrachloride (ZrCl4), 1,4-
dicarboxybenzene, and 2-amino-1,4-dicarboxybenzene were
supplied by Sigma-Aldrich. Formic acid, cyclohexane, and dime-
thylformamide (DMF) were purchased from Merck. The polyester
nonwoven sheets were supplied by AWA Paper & Technology
Company, Inc., with a basis weight, ventilation rate, and porosity
of 45 g m
2, 100 cm3 cm
2 s
1, and 4.2 cfm 
2, respectively.
2.2. Zr-MOFs synthesis
To synthesize UiO-66 particles, ZrCl4 (8.98 mmol, 2.12 g) and
formic acid (10 mL) were dissolved in 50 mL DMF.1,47,48 Sepa-
rately, a solution of 1,4-dicarboxybenzene (8.98 mmol, 1.34 g)
and 50 mL DMF was prepared. The ZrCl4 and 1,4-dicarbox-
ybenzene solutions were mixed together and the obtained slurry
was decanted to a Teon-lined autoclave aer 30 min of stirring.
Aer heating at 120  C for 24 h, UiO-66 particles as a white
powder were formed, and then separated by centrifugation,
followed by washing with methanol to remove the residual
DMF. The nal powder was dried overnight in a vacuum oven at
100  C. To synthesize UiO-66 with an amine functional group
(UiO-66-NH2), the same process was performed with the
following modication: 1,4-dicarboxybenzene was replaced
with 2-amino-1,4-dicarboxybenzene (8.98 mmol, 1.62 g).
2.3. Fabrication of support PMP membrane
A certain amount of PMP (8 wt%) was dissolved in cyclohexane
to prepare the casting solutions with admissible viscosity. The
solution was placed in an oil bath at 60  C under mechanical
stirring for 24 h. The homogeneous solutions were degassed
overnight in a stationary manner to remove any air bubbles. The
solution was cast over a polyester nonwoven fabric with thick-
ness of 150 mm. The cast lm was immersed into an ethanol
coagulation bath for solvent/non-solvent exchange. Aer 1 h,
Fig. 1 Chemical structure of (a) PMP and (b) Pebax 1657. (c) Schematic
representation of the TFN membrane fabrication.
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the non-solvent was replaced with pure ethanol to continue the
demixing process for two days. Then, the as-fabricated porous
PMP support was placed under ambient conditions overnight
for non-solvent evaporation. To ensure complete non-solvent
evaporation, the PMP support was allowed to dry in a vacuum
oven at 60  C for 12 h. Some characteristics of the PMP support
layer obtained from a gas permeation test are provided in ESI
(Section S1.1†).
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the wavenumber range of 400–4400 cm
1. The thermal prop-
erties of the particles and membranes were evaluated by means
of thermal gravimetric analysis (TGA, TGA/DSC 1 Mettler
Toledo, USA). The samples were heated in the temperature
range from 20  C to 800  C under nitrogen atmosphere at the
rate of 10  C min
1. The morphology and quality of the ller
dispersion affect the separation properties of the as-synthesized
TFN membranes. Thus, the exact surface and cross-section
morphological studies of the membranes were performed by

2.4. Fabrication of TFN membranes means of a eld emission scanning electron microscope
(FESEM, MIRA3TESCAN-XMU, Czech Republic) at 15 kV.
A colloidal solution was prepared by dispersing the as-
Moreover, the EDX prole and mapping analysis of the
synthesized Zr-MOF (UiO-66 and UiO-66-NH2) in an ethanol/
membranes were obtained using FESEM.
water mixture (70/30 wt%) at a certain concentration and
sonicated to avoid particles aggregation. The dried Pebax
(4 wt%) was added into the colloidal solution under reux 2.6. Gas permeation experiment
condition with stirring at 80  C for 4 h to yield a homogeneous A constant pressure/variable volume system (Fig. 2) was used to
solution. As depicted in Fig. 1(c), the TFN membrane was determine the permeability of pure CO2 and CH4 gases and
fabricated by immersing the PMP support membrane into the mixture gas of CO2/CH4 (50 : 50 vol%/vol%) through neat TFC
homogenous Pebax/Zr-MOF solution for 5 min. and TFN membranes at 25  C. The gas was introduced onto the
The Pebax/Zr-MOF-coated PMP membrane was then placed
in a vacuum oven at 55  C for 40 min to evaporate the solvent.
The abovementioned procedure was replicated four times in
order to obtain desirable thickness of the Pebax thin layer over
the PMP support. Finally, the resultant TFN membrane was
dried at 55  C for 10 h. The compositions of each casting
solution containing Pebax and Zr-MOFs are shown in Table 1.

2.5. Zr-MOF and membrane characterization

The X-ray diffraction (XRD, X'Pert PRO MPD, Netherlands)
analysis was carried out with Cu Ka radiation at 1.54 Å, 40 kV,
and 40 mA at room temperature to evaluate the crystalline
structure of Zr-MOFs. The data were recorded at a scanning rate
of 0.02 and counting time of 20 s from 2q ¼ 2–50 . The
simulated powder diffraction patterns of UiO-66 were computed
using the Materials Studio soware. Nitrogen adsorption/
desorption studies of Zr-MOFs were conducted by using
BSORP-mini II (Japan) at 77 K. The data were calculated in
a relative pressure (P/P0) region of 0.01 to 1.0. Prior to the study,
the samples were heated at 120  C to remove any moisture. The
Fig. 2 Schematic representation of the gas permeation setup: (1)
functional groups and chemical structure of Zr-MOFs were pressure regulator, (2) valve, (3) humidifier, (4) water knockout, (5)
studied by means of Fourier Transform Infrared spectroscopy pressure transmitter, (6) temperature transmitter, (7) permeation cell,
(FTIR, Thermo Scientic, USA). The spectra were recorded in and (8) digital mass flow meter.

Table 1 Casting solution composition of each TFN membrane

Polymer (4 wt%)
Solvent (wt%)
Membrane Pebax Zr-MOF ethanol/water (70/30 wt%) Code

PMP/Pebax 100 0 96 PP
PMP/Pebax_UiO-66 99.5 0.5 96 PPU-0.5
PMP/Pebax_UiO-66 99 1 96 PPU-1
PMP/Pebax_UiO-66 98.5 1.5 96 PPU-1.5
PMP/Pebax_UiO-66 98 2 96 PPU-2
PMP/Pebax_UiO-66-NH2 99.5 0.5 96 PPUN-0.5
PMP/Pebax_UiO-66-NH2 99 1 96 PPUN-1
PMP/Pebax_UiO-66-NH2 98.5 1.5 96 PPUN-1.5
PMP/Pebax_UiO-66-NH2 98 2 96 PPUN-2

12382 | J. Mater. Chem. A, 2018, 6, 12380–12392 This journal is © The Royal Society of Chemistry 2018
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Paper Journal of Materials Chemistry A

membrane cell under specic pressure where the downstream

was under atmospheric conditions. Aer stabilizing the system,
the ow rate of the penetrated gas was recorded by means of an
electronic ow meter (General Purpose Mass Flow Meter,
Apasco, Iran). The permeation experiments for each membrane
with various contents of Zr-MOF were performed and replicated
three times and the average value was reported. The gas
permeability was reported in terms of barrer (1 barrer ¼ 1 
10
10 cm3 (STP) cm cm
2 s
1 cmHg
1), which was calculated
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using the following equation:

QL
P¼ (1)
DPA
where Q is the volumetric ow rate of gas (cm3 s
1) at standard
temperature and pressure (STP), L is the membrane thickness
(cm), DP is the pressure difference of gases on both the sides of
the membrane (cmHg), and A is the effective membrane area
(cm2). The ideal CO2/CH4 selectivity was calculated as below:
PCO2 DCO2 SCO2
a¼ ¼  (2)
PCH4 DCH4 SCH4
Fig. 3 (a) X-ray diffraction pattern of Zr-MOFs is similar to the simu-
where PCO2 and PCH4 denote the permeability values of pure CO2 lated pattern. (b) Nitrogen adsorption/desorption isotherm of particles
at 77 K. (c) FTIR spectra of UiO-66 and UiO-66-NH2.
and CH4, respectively. The permeability of the mixed gas was
calculated by using eqn (1). The gas mixture selectivity was
measured using eqn (3). which would effectively improve the CO2 permeability as
yA =yB compared to CH4.52
aA=B ¼ (3) FTIR analysis of Zr-MOFs was performed to detect the func-
xA =xB
tional groups, as shown in Fig. 3(c). Two bands appeared at 672
where y and x are the volumetric fractions of the permeate and and 760 cm
1, which can be assigned to the asymmetric and
feed gas, respectively. The permeate gas was analyzed by means symmetric stretching of O–Zr–O bonds, respectively. The peaks
of a gas chromatography apparatus (GC-2552 TG, Iran) equip- ranging from 1380 to 1440 cm
1 are related to the symmetric
ped with a thermal conductivity detector (TCD). The CO2/CH4 stretching of COO groups. Additionally, the bands in the range of
mixture gas feed was humidied by water in order to measure 1560–1590 cm
1 are attributed to the asymmetric stretching of
the separation performance under humid conditions (saturated COO groups.53 The two peaks at 1261 and 1321 cm
1 are assigned
moisture). to the symmetric and asymmetric stretching of C–N. The char-
acteristic band at 1629 cm
1 contributes toward the N–H
bonding vibration of amine groups.54 A broad and strong peak
3. Results and discussion detected in the range of 3100–3600 cm
1 correspond to the
3.1. Characterization of Zr-MOFs presence of a hydrogen bond in the absorbed moisture and
amine groups in the MOF ligands. Due to the overlap between
Fig. 3(a) shows the X-ray diffraction pattern of the as-prepared
these peaks, it is not entirely possible to distinguish them.55–57
Zr-MOFs. The reections tting to the crystallographic planes
The morphology of the as-synthesized Zr-MOFs at high
of (111), (002), (022), (004), (115), and (006), assigned to UiO-66
magnication is shown in Fig. 4(a and b). FESEM images
and UiO-66-NH2, correspond to the diffraction peaks at 2q ¼
revealed that the size of Zr-MOFs particles is approximately 60–
7.49, 8.63, 12.18, 17.20, 22.37, and 25.86, respectively. All the
80 nm. Particle size obtained through TEM analysis (Fig. 4(c))
aforementioned diffraction peaks of the particles are in good
conrms the FESEM results.58
agreement with the previously reported peaks in the litera-
ture.49,50 In addition, the XRD patterns of the as-synthesized Zr-
MOFs are in agreement with the obtained simulated pattern 3.2. TFN membranes characterization
from the Materials Studio soware. Choosing materials with high tendency to separate CO2 from
The nitrogen adsorption/desorption isotherm presented in gas streams is required to attain favorable TFN membranes with
Fig. 3(b) conrmed the type-I isotherm, demonstrating the
micropore structure for the as-synthesized Zr-MOFs, as cate-
gorized by IUPAC.51 The physical properties of the particles Table 2 BET analysis of UiO-66 and UiO-66-NH2
obtained from the BET analysis are listed in Table 2. The BET
Sample SBET (m2 g
1) Vtotal (cm3 g
1) Dp (nm)
surface area, total pore volume, and pore size of UiO-66-NH2
were lower than those for UiO-66. This reduction is due to the UiO-66 1189 0.5089 1.7365
imposition of amine groups into vacuity of the micropores, UiO-66-NH2 800 0.3471 1.6911

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A, 2018, 6, 12380–12392 | 12383

Journal of Materials Chemistry A
Fig. 4 FESEM image of nanosized (a) UiO-66 and (b) UiO-66-NH2. (c)
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TEM image of UiO-66-NH2 particles.
high separation performance. Moreover, the reciprocal chem-
ical affinity for MOF-polymer pair is needed to achieve desirable
interfacial adhesion. Poor interfacial adhesion between MOFs
and polymer chains creates interfacial voids, resulting in sieve-
in-a-cage morphology. Unfortunately, the non-selective pene-
trant permeation induced by these voids leads to a decline in
the desired selectivity.1,59 One diagnostic that can be used to
understand the quality of interfacial interactions between
MOFs and the polymer is to investigate the required energy in
order to dissociate the MOFs/polymer composite matrix. It is
clear that higher required energy indicates the existence of
a desirable interaction. Therefore, the amount of heat per unit
mass of TFN membranes as the required energy to dissociate
the membrane consisting polymer and llers was collated. The
numeric value of this energy (J g
1) was computed through the
area under the differential scanning calorimetry curve, as
shown in Fig. 5(a).
The results of the determined energy for each ller, PP, and
some selected TFN membranes are listed in Table 3. The ob-
tained results revealed that the net energy required to dissociate
the membranes was more than the summation of the energy
required to individually dissociate each polymer and ller. This
nding indicated that an appropriate interaction between the
polymer phase and ller was created; thus, extra energy is
needed to dissociate the TFN membranes. The required energy
to dissociate the bonds resulting from the interaction between
the composed materials is calculated as follows:
DE ¼ EM
(Ed + Ec) (4)
Fig. 5(a) DSC thermograms of TFN membranes. (b) TGA curve of
UiO-66, UiO-66-NH2, and TFN membrane containing various
amounts of UiO-66 and UiO-66-NH2.
12384 | J. Mater. Chem. A, 2018, 6, 12380–12392
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Table 3 Energy required for the dissociation of TFN membranes
Membrane EM (J g
1) DE (J g
1)
PP 6356.4 0
PPU-0.5 18 341.4
13 620.8
PPU-2 34 743.8 2781.1
PPUN-0.5 73 031.1 32 961.5
PPUN-1.5 77 377.9 37 307.7
where EM, Ed, and Ec are the required energy for TFN
membranes, dispersed phase, and continuous phase, respec-
tively, and DE is the energy required to break the interaction
created between the polymer and Zr-MOFs.
The measured energy for UiO-66, UiO-66-NH2, and PP
membrane were 25 605.7 J g
1, 33 713.3 J g
1, and 6356.4 J g
1,
respectively. According to the data presented in Table 3, DE for
the TFN membrane containing 0.5 wt% UiO-66 was negative
due to the rigidication between the polymer and nano-
particles.60 This may be justied through the permeability
reduction in this MOF loading. In contrast, the positive values
of DE in other TFN membranes indicated a favorable interac-
tion between Zr-MOFs and membrane matrix, which can lead to
selectivity improvement. As evident from Table 3, the interac-
tion between the polymer and modied Zr-MOF intensied
owing to the amine group of UiO-66-NH2. As shown in Fig. 6, the
–NH2 groups can effectively interact with the carbonyl group of
PA or the oxygen of PEO in Pebax and can cause an increase in
the required energy up to 73 031.1 and 77 377.9 J g
1 for PPUN-
0.5 and PPUN-1.5, respectively.
TGA analysis was used to study the effect of Zr-MOF llers on
the thermal stability of the TFN membrane. Thermograms
acquired for UiO-66, UiO-66-NH2, and membranes are revealed
in Fig. 5(b). The primary weight loss for both Zr-MOFs in the
range of 25–110  C can be ascribed to the loss of adsorbed water
within the pores. The secondary weight loss at around 270–
400  C is imputed to the loss of residual solvent. As shown in the
gure, the TGA curve for UiO-66-NH2 was different as compared
to UiO-66, with one extra stage in the temperature range of 315–
Fig. 6 Diagram of proposed interaction between –NH2 groups,
carbonyl group, and oxygen in the Pebax structure (red: O, blue: N,
white: H, gray: C).
This journal is © The Royal Society of Chemistry 2018

Paper
400  C, which corresponds to amine group degradation. The
nal weight loss was the same for both the Zr-MOFs, which can
be attributed to the dicarboxybenzene ligand decomposition at
around 400  C. Moreover, the TGA curves of PP and TFN
membranes with 0.5 and 1.5 wt% of UiO-66 and UiO-66-NH2 are
shown in Fig. 5(b). The TGA curves of all the membranes consist
of three stages, namely, residue solvent evaporation, polymer
chains decomposition, and nally, carbonization. The thermal
decomposition of the TFC membrane initiates at 300  C, but it
begins at a lower temperature of around 295  C for TFN
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membranes containing Zr-MOFs. It is expected that the
decomposition temperature of the membranes increased as the
MOFs loading increases owing to the polymer/ller interac-
tion.61,62 Nevertheless, the opposite trend occurs for TFN
membranes, where the decomposition temperatures decline
upon adding the MOFs. This behavior ascribes to the lower
Fig. 7 FESEM surface images of (a) PP, (b) PPU-0.5, (c) PPU-1.5, (d)
PPUN-0.5, and (e) PPUN-1.5.
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Journal of Materials Chemistry A
thermal decomposition of Zr-MOFs as compared to the
membranes, as reported by Venna et al. for Matrimid MMMs
embedded by UiO-66-NH2.61
FESEM analysis was carried out to investigate the
morphology of membranes, quality of ller dispersion, and
features of polymer/MOF interface. Fig. 7 and 8 illustrate the
surface and cross-sectional images of the TFN membranes at
various loading rates of Zr-MOFs at the Pebax thin layer,
respectively. As shown in Fig. 7(a), the membrane surface has
a smooth characteristic.
According to Fig. 7(b–e), the Zr-MOFs particles are clearly
observed as dispersed within the membrane surface. As shown
in the gure, Zr-MOFs contribution to the membrane surface
increased by increasing the Zr-MOFs loading with a uniform
feature. Nevertheless, the agglomeration of some amount of
nanoparticles on the membrane surface can be seen (as shown
Fig. 8 FESEM cross-sectional image of (a) PP, (b) PPU-0.5, (c) PPU-1.5,
(d) PPUN-0.5, and (e) PPUN-1.5.
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by yellow circles in Fig. 7), which is possibly shaped by the

particles precipitated from the Pebax solution over the thin
selective layer supported by PMP.
As shown in Fig. 8, cross-sectional images of the selective
Pebax layer of TFN membranes display a defect-free and
uniform structure. Good interfacial interaction and desired
dispersion of nanosized particles are observed at each MOF
loading (Fig. 8(b–e)). However, few aggregates of MOFs with
sizes of around 300–400 nm can be seen. As MOF loading is
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increased within the Pebax matrix up to 2 wt%, unfavourable

clusters of Zr-MOFs were observed. The aggregation of MOFs
can lead to the formation of non-selective voids, which reduce
the separation performance of the resulting membranes. In
fact, it can be concluded that the MOF loading rate of 2 wt% is
the percolation point, where the extra inclusion of MOF can Fig. 10 Low-magnification FESEM cross-sectional images of (a) TFC
result in the decline of membrane selectivity. membrane and (b) TFN membranes containing Zr-MOFs.
The cross-sectional pattern of a TFN membrane changed to
the grooved feature by the incorporation of Zr-MOFs at high
loading of 1.5 wt%, which may be due to the interaction penetrant. The thicknesses of the support PMP and selective
between the polymer and llers.63 From the high-magnication Pebax layers were around 20 mm and 2.5–3.5 mm, respectively.
FESEM images (Fig. 8(c and e)), the grooved pattern intensied
upon embedding modied Zr-MOF due to the existence of 3.3. Pure gas permeation
interactions between the amine group and polymer chains,
which increases the stress concentration at the polymer/ller Pure CH4 and CO2 gas permeations of neat TFC membrane and
interfaces.64–66 As a result, there is no visible “sieve-in-a-cage” TFN membranes containing various contents of UiO-66 and
morphology around the llers, and therefore, the MOFs are well UiO-66-NH2 were determined at temperature of 25  C and feed
surrounded by the polymer chains. pressure of 5 bar; the obtained results are depicted in Fig. 11(a).
SEM-EDX analysis was used to conrm the existence of Zr- The results indicated that the permeability of CO2 was signi-
MOFs in the membrane. The obtained results of SEM-EDX cantly higher than that of CH4 for all the membranes. CO2 with
analysis for PP, PPU-0.5, and PPUN-1.5 are displayed in Fig. 9. lower kinetic diameter and higher condensability than CH4
The detected zirconium (Zr) in Fig. 9(b) conrmed the existence showed superior permeability as compared to CH4.67 In addi-
of Zr-MOF within the Pebax matrix. In addition, the mapping tion, the existence of interaction among the amide group of PA
analysis (Fig. 9(c and e)) of TFN membranes indicated appro-
priate dispersion of UiO-66-NH2 throughout the Pebax selective
layer.
The entire cross-sectional structure of the TFN membrane is
shown in Fig. 10. As shown in the gure, the Pebax selective
layer was well inhered on the PMP support membrane and
formed a defect-free boundary. The thickness of the Pebax layer
is much lower as compared to the PMP layer and hence, Pebax
can be used as a highly permeable and selective layer for CO2

SEM-EDX (a, b, d) and SEM-mapping (c, e) analyses: (a) PP
Fig. 9
membrane, (b, c) PPUN-0.5, and (d, e) PPUN-1.5.
Fig. 11 (a) Pure gas permeability of CH4 and CO2 and (b) ideal CO2/
CH4 selectivity of neat TFC and TFN membranes containing different
Zr-MOF loading values at 25  C and 5 bar, and (c) gas permeance (the
data are average of three measurements).

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Paper
and quadrupole carbon dioxide (molecular alignment as well as
hydrogen bonding) leads to higher CO2 permeation.68
Typically, embedding porous llers into polymeric materials
can change the permeation characteristics of the resultant TFN
membrane by the following major mechanisms.
(1) Elongation and tortuosity of the permeation pathway for
larger penetrant due to the presence of llers.61
(2) Permeability decline owing to the rigidied polymer
chains at the polymer/ller interface.60
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(3) The selective adsorption and sieving of gases by porous
llers that hinder the larger penetrants to diffuse within the
pores.69
(4) The extra fractional free volume (FFV) of the TFN
membranes upon the inclusion of llers enhances the pene-
trant permeability, particularly for smaller penetrants.5
According to Fig. 11(a), CH4 permeability decreased upon the
inclusion of both UiO-66 and UiO-66-NH2 into the Pebax thin
layer. Zr-MOFs, with low tendency to adsorb CH4, elongate the
net CH4 pathway to transport through the membrane. It should
be mentioned that the pore size of Zr-MOF is larger than the
CH4 molecular size,67 but the MOFs actually separate the gases
through selective sorption, and the pore ow through MOFs
cavities plays a negligible role.70 Thus, based on the weak
affinity between Zr-MOFs and CH4 penetrant, the CH4 perme-
ability decreased by 22% and 32% for both UiO-66- and UiO-66-
NH2-based TFN membranes, respectively. TFN membranes
comprising UiO-66-NH2 showed lower CH4 permeability as
compared to UiO-66-based TFN membranes. The smaller pore
size of UiO-66-NH2 may be the main reason for the higher
reduction in CH4 permeability. Despite CH4, the net effect of the
aforementioned mechanisms leads to improved CO2 perme-
ability. The selective sorption of Zr-MOFs and the interaction
between polar CO2 and the functional group of Pebax as well as
the smaller molecular size of carbon dioxide are responsible for
the increased CO2 permeability. As shown in Fig. 11(a), the
permeability of carbon dioxide declined at higher UiO-66-NH2
loading (2 wt%). The CO2 permeability reduction at the highest
loading of UiO-66-NH2 can be assigned to the effect of ller on
the crystalline PA and so PEO segments. The presence of UiO-
66-NH2 in the PA segment can enhance the permeability due to
amide chain interruption and FFV increment, while embedding
the llers in the so PEO segment leads to chain rigidication,
as shown by the FESEM images (Fig. 8(e)), thus hindering CO2
permeation.
Fig. 11(b) demonstrates the CO2/CH4 selectivity for neat TFC
and TFN membranes. The PP membrane presented ideal CO2/
CH4 selectivity of 15.9, while all the TFN membranes showed
improved selectivity upon Zr-MOF inclusion. As the UiO-66 and
UiO-66-NH2 loading increased to 2 wt%, the ideal CO2/CH4
selectivity increased to 30.3 and 35.4, respectively, at pressure of
5 bar.
According to eqn (6), the overall selectivity is the multipli-
cation of diffusivity selectivity and solubility selectivity. The
diffusivity selectivity is an excellent function of the relative
molecular size of penetrants and sieving nature of the associ-
ated polymer, while the solubility selectivity affects the pene-
trant condensability and competitive sorption of gases in the
This journal is © The Royal Society of Chemistry 2018
View Article Online
Journal of Materials Chemistry A
membrane matrix. The CO2/CH4 selectivity enhancement upon
the inclusion of Zr-MOF can be attributed to the following
reasons.
(1) Presence of llers and increase in the FFV of polymers by
chain disruption improves the diffusion of each penetrant.
Nevertheless, CO2 with smaller molecular size permeates more
than CH4.
(2) The embedded Zr-MOF intensies the sorption properties
of TFN membrane with respect to condensable CO2. Therefore,
the interaction between carbon dioxide and the polar group of
Pebax joined with the MOF affinity would improve the selec-
tivity towards carbon dioxide.
(3) The effective interaction between Zr-MOF and polymer
chain would prevent the formation of possible non-selective
voids at the polymer/ller interface.
The data presented in Fig. 11(b) demonstrates that the TFN
membranes embedded with amine-modied UiO-66 exhibited
superior CO2/CH4 selectivity than those containing UiO-66,
particularly at the ller loading rate of 1.5 and 2 wt%. The R–
NH2 group of amine-modied MOF can reversibly interact with
polar CO2 to form carbonate. Therefore, CO2 permeability gets
enhanced and consequently, the CO2/CH4 selectivity increases.
Moreover, the –NH2 groups would increase compatibility
between the Pebax chain and ller, as presented in Fig. 6, which
would intensify chain rigidication around the MOF, and thus
signicantly decrease the non-selective permeation in the
interfacial regions. In addition, according to the BET results,
the smaller pore size of UiO-66-NH2 (induced by additional
–NH2 group) as compared to UiO-66 can hinder the CH4
permeation.
The normalized CO2 and CH4 permeabilities at feed pressure
of 5 bar and temperature of 25  C are illustrated in Fig. 11(c).
This gure demonstrates that the permeability of CO2 was
signicantly higher than that in CH4 for all the membranes.
Due to lower kinetic diameter and higher condensability of CO2
molecules, the CO2 permeability was superior to CH4 perme-
ability. Moreover, embedding UiO-66 and UiO-66-NH2 particles
into the Pebax matrix can further improve the CO2 permeability.
The TFN membrane with UiO-66-NH2 showed better CO2
permeability due to the higher tendency of UiO-66-NH2 to
adsorb CO2 molecules and good interaction between the poly-
mer chains and –NH2 groups. Therefore, there is reasonable
consistency between the data presented in barrer and GPU.
The effect of feed pressure on gas permeability and CO2/CH4
selectivity was investigated for neat TFC and TFN membranes,
and the results are displayed in Fig. 12. For all the membranes,
CO2 permeability showed an increasing trend, while the CH4
permeability decreases with an increase in the feed pressure. As
shown in the gure, the CO2 permeability for PPU-2 and PPUN-
1.5 membranes increased from 316.7 and 313.2 barrer to 369.3
and 393.8 barrer, respectively, as the feed pressure increased
from 2 to 7 bar. Moreover, the CH4 permeability showed
a reverse trend and decreased from 19.2 and 17.4 barrer to 11.8
and 9.9 barrer as the feed pressure increased from 2 to 7 bar.
The concentration of condensable CO2 within the polymer
matrix increases at higher applied feed pressure, resulting in
permeability enhancement induced by plasticization. Moreover,
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Journal of Materials Chemistry A Paper

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Fig. 12 The effect of pressure increasing on the separation performance of membranes.

the CO2 sorption by MOF increases by applying higher feed hinders CO2 permeation. Thus, the trend of gas permeability
pressure, which improves CO2 permeability. On the contrary, data in terms of pressure revealed that the higher affinity of Zr-
the opposite trend was observed for CH4 due to its larger size. MOFs to CO2 penetrant would overcome the decrease in CO2
Although higher pressure intensies the plasticization effect, it diffusion induced by polymer chain compactness. Therefore,
can cause compaction of the polymer chains, and consequently CO2 permeability enhancement is expected at elevated feed
restrict penetrant diffusion. Since CH4 permeates through the pressures due to higher CO2 sorption caused by Zr-MOFs.
membrane with dominant diffusion, its permeability reduces as
the feed pressure increases. The overall permeability is the
multiplication of the diffusion coefficient and the solubility
coefficient. According to the dual sorption model, the diffusion
coefficient decreases before the occurrence of CO2-induced
plasticization because of the compactness of the polymer
chains. Moreover, based on the CO2 adsorption isotherm of Zr-
MOFs reported in the previous literature,1,71 the amount of CO2
adsorption can be increased by increasing the pressure. Hence,
the CO2 molecules pass through the membrane by a combina-
tion of sorption and condensation mechanisms. Alternatively,
the concentration of condensable CO2 within the polymer
matrix is increased at higher applied feed pressure, resulting in
permeability enhancement induced by plasticization. In fact,
beyond the plasticization pressure, there is a competition for
CO2 sorption between Zr-MOFs and Pebax chain compactness.
The former leads to higher CO2 permeability, while the latter Fig. 13Mixed gas performances of different membranes under dry
and humid conditions at 25  C and 5 bar.

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Paper Journal of Materials Chemistry A

Table 4 The comparison of CO2/CH4 separation performance of MOF-based MMMs with the results obtained in this study

Condition
Loading PCO2 PCH4 Thickness
Polymer Filler (wt%) P (bar) T ( C) (barrer) (barrer) a ¼ PCO2/PCH4 (mm) Ref.

Pebax 2533 ZIF-8 15 6 25 508.6 56 10.4 40–60 75

Copolyimide NH2-MIL-53 10 3 25 56.9 1.6 35.8 50 47
PMP NH2-MIL-53 30 2 30 226.3 10.1 22.3 60–70 5
Matrimide 5218 ZIF-8 20 4 22 19.7 1.1 18.6 40–70 76
PSF UiO-66-NH2 40 3 35 45.5 1.8 24.3 65 1
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6FDA-ODA MOF-199-NH2 10 2 35 26.6 0.4 59.7 20–40 77

Matrimide MOF-5 10 2 35 11.1 0.2 51.3 35 46
PSF Mn(HCOO)2 5 — — 6.4 0.4 15.1 — 78
PSF Cu3(BTC)2 5 — — 7.8 0.3 20.2 — 78
PMP/Pebax UiO-66 2 7 25 369.3 11.8 31.3 25 This work
PMP/Pebax UiO-66-NH2 1.5 7 25 393.4 9.9 39.8 25 This work
PMP/Pebax UiO-66 2 7 25 212.6a — 22.6 25 This work
PMP/Pebax UiO-66-NH2 1.5 7 25 245.3a — 29.4 25 This work
PMP/Pebax UiO-66 2 7 25 242.5a,b — 26.4 25 This work
PMP/Pebax UiO-66-NH2 1.5 7 25 278.4a,b — 33.7 25 This work
a
Mixed gas permeability. b Humid state.

Upon increasing the feed pressure, the selectivity of the PP
membrane increased from 8.9 at a pressure of 2 bar to 20.5 at
pressure of 7 bar. In addition, it was observed that the CO2/CH4
selectivity of the PPU-2 membrane increased from 16.6 to 31.3.
For the PPUN-1.5 membrane, the CO2/CH4 selectivity was
enhanced from 18 at a pressure of 2 bar to 39.8 at a pressure of 7
bar.
3.4. Mixed gas permeation
The dry and humid mixed gas separation performances of the
selected membranes (i.e., PP, PPU-2, and PPUN-1.5) were eval-
uated at temperature of 25  C and pressure of 5 bar; the results
are illustrated in Fig. 13. For both TFC and TFN membranes, the
CO2/CH4 selectivity is lower than the relevant ideal selectivity.
This difference can be attributed to the competitive permeation
of CO2 and CH4 gases through the thin Pebax layer.72 Further-
more, the presence of CH4 in the throughput of membranes,
which occupy the free volume of the polymer, cause a reduction
in the CO2 sorption and condensation.5 The incorporation of Zr-
MOFs in the Pebax matrix improved the CO2 separation
performance.
Additionally, the results of humid mixed gas separation
performances of TFC and TFN membranes at saturation mois-
ture revealed that the CO2 permeability enhanced from 216.9
barrer for the PP membrane to 224.1 and 269.9 barrer for the
PPU-2 and PPUN-1.5 membranes, respectively. Also, the CO2/

Fig. 14 Comparison of the performance of TFN membranes with Robeson's upper bound at different pressures. (a) Pure gas permeation and (b)
mixed gas permeation.

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Journal of Materials Chemistry A
CH4 selectivity of TFC and TFN membranes increased under the
humid conditions as compared to dry conditions.
This demonstrates that Pebax-based membranes as WSP
materials can facilitate the CO2 permeation behavior under
humid conditions.73 Moreover, an improvement in the mixed
gas separation properties by Zr-MOFs loading can be attributed
to the CO2-philic and hydrophilic properties of Zr-MOFs.74 The
results of the effect of pressure on the performance of
membranes for gas mixture separation under dry and humid
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conditions are plotted in Fig. S2 and S3,† respectively. The
trends of CO2 permeability and selectivity of membranes for
mixed gas under both dry and humid conditions were similar to
those of pure gas considering the fact that CO2 permeability and
CO2/CH4 selectivity for mixed gas were lower than pure gas CO2
permeability and ideal selectivity.
3.5. Gas separation performance comparison of MOF-
modied membranes
The ability of various MOF-based MMMs for CO2/CH4 separa-
tion is listed in Table 4. According to the presented data, the
separation characteristics of MMMs depend strongly on the
nature of the polymer and MOFs. All the studies indicated that
as MOFs are added into the polymer matrix, the corresponding
CO2/CH4 selectivity improved, but each study illustrated a trade-
off relationship between permeability and selectivity. According
to the obtained results in this study, TFN membranes incor-
porated with low content of Zr-MOFs exhibited high perme-
ability as well as extraordinary selectivity.
Fig. 14a and b illustrate the performance of PP, PPU-2, and
PPNU-1.5 membranes for CO2/CH4 separation as compared to
Robeson's upper bound. The bounds in Fig. 14(a) and
b demonstrate that the selectivity enhancement is subjected to
permeability decline and vice versa, which is known as the
Robeson's trade-off. It can be seen that the performance of
PPNU-1.5 membrane at pressures higher than 3 bar crossed the
prior bound, and in the case of 7 bar, it approached the present
bound. The overall trend of CO2 permeability versus CO2/CH4
selectivity revealed the behavior opposite to that of the Robe-
son's bound trade-off.
4. Conclusions
TFN membranes comprising selective Zr-MOFs-incorporated
Pebax thin layer supported by highly permeable PMP showed
improved CO2 separation performance as compared to
conventional MMMs. Incorporating UiO-66 and UiO-66-NH2
into the polymeric matrix of Pebax selective layer causes the
increase in CO2 permeability and CO2/CH4 selectivity due to the
preferential CO2 adsorption and strong interfacial interaction
between Zr-MOFs and polymer chains. Ideal CO2/CH4 selectivity
of TFN membranes increased from 15.9 to 35.3 at 5 bar by
increasing UiO-66-NH2 loading up to 2 wt%. Moreover, the
permeability and selectivity of TFN membranes were improved
by applying higher feed pressures from 2 to 7 bar. The as-
synthesized TFN membranes containing Zr-MOFs improve the
real selectivity and CO2 permeability for CO2/CH4 mixed gas
12390 | J. Mater. Chem. A, 2018, 6, 12380–12392
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Paper
under dry and humid conditions. The results indicated that
using amine-modied UiO-66 led to better performance for TFN
membranes as compared to neat UiO-66-incorporated TFN
membranes. In addition, the characterization studies
conrmed that good Zr-MOF dispersion within the Pebax
matrix was obtained. The results of the DSC analysis approved
the formation of appropriate polymer/ller interfaces. In addi-
tion, the probability of creation of non-selective voids at the
interfaces decreased.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This project was nancially supported by Babol Noshirvani
University of Technology (7/5/95-13682). The authors would like
to thank Mr Saeed Khoshhal for his kind help to calculate the
required energy for dissociation.
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