Some Mechanistic Insights into the Action of Facilitating

Agents on Gas Permeation through Glassy Polymeric

Membranes
Md Oayes Midda and Akkihebbal K. Suresh
Dept. of Chemical Engineering, Indian Institute of Technology, Bombay, Mumbai 400076, India

DOI 10.1002/aic.15873
Published online August 4, 2017 in Wiley Online Library (wileyonlinelibrary.com)

Incorporation of facilitating agents is one of the promising strategies being researched in recent years to cross the
Robeson bounds for gas separations using polymeric membranes. The ways in which such inclusions modify the perfor-
mance of membranes are not always clear. Here, we study the performance of two glassy membranes, Polyfurfuryl alco-
hol and Polysulfone, in O2/N2 and CO2/N2 separations, with Cobalt phthalocyanine in insoluble and solubilized forms
as the facilitating agent. The results show that in general, three effects are important: (1) a barrier effect, (2) a facilita-
tion effect, and (3) morphological effects on the polymer matrix due to an incompatibility between the particles and the
polymer. These results provide some insight into the action of facilitating agents in soluble and insoluble form, when
used as membrane additives. V C 2017 American Institute of Chemical Engineers AIChE J, 64: 186–199, 2018

Keywords: composite membrane, poly(furfuryl alcohol), polysulfone, cobalt phthalocyanine, facilitated transport, gas
separation

Introduction ammonia synthesis, Claus process, catalyst regeneration in

Membrane based separation technology has a significant
potential in the process industry to reduce equipment size,
operating cost, energy utilization, and waste generation.1,2 The
industrial application of membrane science and technology
has come after a long history in laboratory studies. Today, it is
widely accepted as among the best available for water and
wastewater treatments, having shown significant improve-
ments in energy efficiency.3–5 With that history in the back-
ground, membranes are being considered with ever increasing
interest for gas separation, especially in the context of the cur-
rent focus on the environmental impact of industrial processes
and climate change. While the work of last three decades has
resulted in considerable improvements in membrane based gas
separations, challenges remain. Major breakthroughs have
been achieved for hydrogen separation.6 For certain other sep-
arations such as CO2 separation, separations of hydrocarbon
gases and organic vapors from off-gas streams, and so forth,
membrane based technologies are often competitive with
existing technologies.7 Air separation however, remains a
major area in which other technologies such as cryogenic dis-
tillation and pressure swing adsorption still remain the pre-
ferred options. Partial separations leading to oxygen enriched
air (30–50 vol % O2) have a number of industrial1,2,8–10 (e.g.,
Additional Supporting Information may be found in the online version of this
article.
Correspondence concerning this article should be addressed to A. K. Suresh at
aksuresh@iitb.ac.in and aksuresh@che.iitb.ac.in.
C 2017 American Institute of Chemical Engineers
V renewable saccharidic sources.
FCC, cement kilns, etc.) and medical11–13 (e.g., oxygen masks,
oxygen tents, incubators, and hyperbaric chambers) applica-
tions, and membrane based technologies do have a potential
here.
Polymeric materials exhibit a trade-off between selectivity
and permeability, which limits their application in gas sepa-
rations. As their publication, Robeson’s “upper bounds”14–16
for the industrially important gas separations, have provided
the benchmarks for membrane materials research.7,17,18
Efforts have been made to improve the performance of mem-
brane materials through the incorporation of various addi-
tives. Facilitating agents, which selectively promote the
permeation of the desired component in the mixture, have
been particularly attractive. However, in addition to facilita-
tion, other factors, such as polymer-additive compatibility,
often come into play and it can be difficult to predict the
effect of such incorporation in the absence of insights into
these various mechanisms. In this work, we have studied
binary separations made up from oxygen, nitrogen and car-
bon dioxide, using cobalt phthalocyanine in native and solu-
bilized forms, in an effort to understand the different ways in
which such additives influence membrane behavior. An
examination of the Robeson plots for the target separations
shows that in general, materials which perform at or near the
upper bound tend to be glassy polymers. We have, therefore,
chosen two glassy polymers, Polysulfone (PSf), and Poly(fur-
furyl) alcohol (PFA) as the membrane materials for this
study. The former has been widely studied with much data
available in the literature for comparison, while the latter has
recently attracted attention45–47 as it can be synthesized from

186 January 2018 Vol. 64, No. 1 AIChE Journal

 Table 1. Permeability and Selectivity of PSf Composite Membranes with Different Particulate Additives

Polymer Additives (%) P(O2) P (CO2) S(O2/N2) S (CO2/N2) Reference

PSf (Udel 3500) 0 5.97 24.8 35
1% GO-30% ZIF-301 23.8 60.7
2% GO-24% ZIF-301 21.8 60.3
3% GO-18% ZIF-301 17.7 65.8
4% GO-12% ZIF-301 15.05 68.6
5% GO-6% ZIF-301 11.8 70.8
PSf 0 5.55 29.23 36
10% F-MS 5.6 29.47
20% 6.23 29.67
30% 6.79 30.59
40% 8.46 33.31
PSf (Udel 3500) 0 5.9 24.3 37
8% MCM-41 12.6 36
PSf (Udel 3500) 0 1.6 5.9 4.7 24.3 38
8% HZS 2.3 7.2 6.9 41.7
PSf (Udel 3500) 0 1.6 5.9 4.7 24.3 39
16% ZIF-8 2.6 13 8.3 18
16% HKUST-S1C 1.7 8.4 8 38
PSf (Udel 3500) 0 0.84 3.9 4.94 22.94 40
5% SWNT 1.16 5.12 5.04 22.26
10% SWNT 1.23 5.19 5.34 22.56
15% SWNT 1.11 4.52 5.04 20.54
PSf (Udel P-1700) 0 1.4 5.5 5.6 22 41
5% fumed silica 1.75 6.9 5.6 22
10% fumed silica 1.96 8.25 5.3 22.3
15% fumed silica 3.36 11 5.1 16.7
20% fumed silica 5.18 17 4.5 14.8
PSf (Ultason S 6010) 0 1.5 6 5.9 20 42
7.5% MIL-101 (Cr) 2.6 14 5.1 24
14% MIL-101 (Cr) 4.5 23 5.2 23
19% MIL-101 (Cr) 5.8 32 5.8 26
24% MIL-101 (Cr) 7 36 5.4 27
PSf 1.4 5.6 5.6 22.4 43
PSf (Udel, BP-AMOCO) 0 1.3 5.9 44
15% zeolite A 1.5 6.4
25% zeolite A 1.8 7.7
PSf (Udel, AMOCO) 1.29 5.5 5.7 25 45
PSf (Udel P-1700) 0 2.6 6.5 1.86 4.64 46
10% 13X MS 1.4 6.1 5.6 23.46
20% 13X MS 1.6 6.1 5 19.1
[Unit of permeability is in Barrer].
1 Barrer 5 10210 cm3(STP).cm/cm2.s.cmHg.

Literature 40 wt % CoPc content). Kuraoka et al.24 reported an increase

Among the methods which have been explored to improve
the performance of native PSf membranes, a particularly dom-
inant theme in recent years has been the incorporation of par-
ticulate additives. Table 1 gives a summary of the literature on
such incorporation in PSf membranes for the two major gas
separations of interest here, O2/N2 and CO2/N2. O2/N2 selec-
tivities of the order of 5–6 and CO2/N2 selectivities of 20–24
are reported for native PSf membranes. With some exceptions
(e.g., MOFs and graphene oxide for CO2/N2 separations), the
improvements in selectivity have been modest, and this is
especially true for O2/N2 separations because of the small dif-
ference in kinetic diameters (3.46 Å for O2 vs. 3.64 Å for N2).
One, therefore, looks for additives with particular affinity
towards O2 (usually the more permeable component). Thus,
for example, several Co(II) compounds have been investigated
as additives in various membranes, and Table 2 provides a
summary. Transition metal macrocyclics such as pthalocya-
nines and porphyrins have been of particular interest. The
reversible O2 binding capacity of cobalt phthalocyanine
(CoPc), leads to facilitated transport by a hopping mecha-
nism.19–22 Preethi et al.23 studied the O2/N2 separation perfor-
mance of CoPc-imidazole composite membranes and reported
very high selectivity as well as permeability (as high as 56 for
in selectivity, but a decrease in permeability with CoPc sup-
ported porous glass. Formation of a superoxide adduct
between O2 and CoPc has also been reported.25–27 Shoji
et al.28 showed a continuous increase in selectivity with Co(II)
porphyrin complex loading, in a Nafion membrane. Increased
selectivity and decreased permeability have been seen by
Chen and Lai29 for polycarbonate membrane and Co(SalPr)
complex; whereas Ruaan et al.30 reported increases in both
selectivity and permeability for the same membrane material.
Both increased selectivity and permeability have also been
seen by Nishide et al.21 and Tsuchida et al.31 Nishide
et al.20,22,32,33 report selectivities as high as 12 with the use of
metal porphyrins in membranes. In general, the potential of
CoPc has not been explored to the same extent as metal por-
phyrins, although the two classes of compounds share struc-
tural similarities. Affinity-based additives have shown promise
in the case of CO2/N2 separations as well. Hosseinkhani
et al.,34 used cobalt acetate tetrahydrate as a carrier complex
incorporated in sulfonated ethylene-propylene-diene terpoly-
mer (EPDM) membranes, and reported a sevenfold increase in
CO2 permeability and a threefold increase in CO2/N2 selectiv-
ity (also see Table 1 for results with particles functionalised
with 4-Aminophenazone39)

AIChE Journal January 2018 Vol. 64, No. 1 Published on behalf of the AIChE DOI 10.1002/aic 187
 Table 2. Reported Data on Improvement in O2/N2 Selectivity by the Addition of Co(II) Metal Complexes
in Different Glassy Polymers

Polymer/porous support; Co(II) Complex P S Pressure Temp

Complex (soluble/disperse form) (wt %) (O2) (O2/N2) (bar) (8C) Reference
OIm; CoPc (soluble) 10 20 4 – – 23
20 55 35
40 83.7 56
Porous glass; CoPc (encapsulated) without CoPc 49.7 GPU* 0.93 1.57 25 24
with CoPc 7.97 GPU* 2.9
Nafion membrane; CoTPP (soluble) 0 – 2.1 1 25 28
5 3.2
10 6.5
20 8.5
Nafion membrane; CoFPP (soluble) 0 – 2.1 28
5 5
10 10
20 14
Polycarbonate; Co(SalPr) (dispersed) 0 1 5 3 35 30
3 1.65 6.92
Polycarbonate; Co(SalPr) (dispersed) 0 0.37 8 3 5 29
3 0.33 15
MCAPE; cobalt(II) chelated membrane (dispersed) 0 2.4 2.5 2 30 47
5 5.1 4.9
7.2 6.6 6.4
12.3 8.5 8
14.5 9.1 8.4
Methylimidazole; CoP complex (dispersed) 0 6.4 3.2 5 mmHg 25 21
2.5 9.8 5.7
4.5 23 12
POMPy; CoS (dispersed) 0 1.95 2.3 10 mmHg 35 31
0.6 2.56 3.5
2.5 2.65 4.8
8 3.12 6.5
12 1.47 15
*Reported values are of permeance in GPU. The reference only reports these values without mentioning the thickness of the membrane.

It is seen from the above that while the incorporation of par-
ticulate additives and facilitating agents often results in an
increase in selectivity, the effect on permeability is sometimes
positive and sometimes negative. On the whole, the mecha-
nisms which are brought into play by the incorporation of
additives are not clear; the variety of results seen suggest more
than one mechanism at work.
Materials and Methods
Material used
Cylindrical small plate of polysulfone polymer (Udel P-
3500) was kindly gifted by Advanced Solvay Polymers (USA)
and was used to prepare the membranes. Reagent grade chlo-
roform and dimethylformamide (DMF) supplied by Merck
(Germany) were used as solvents without any further purifica-
tion. Cobalt phthalocyanine (b-form, 97% dye content) was
procured from Sigma-Aldrich. For the synthesis of PFA mem-
branes, reagent grade FA (98%, Sigma-Aldrich), sulfuric acid
(98%, Sigma-Aldrich) and absolute ethanol (Merck) were
used without any further purification as polymeric precursor,
acid catalyst and solvent, respectively. O2, N2, CO2, and He
gases with 99.99% purity were supplied by Med gas n
Equipment.
Synthesis of soluble tert-butyl CoPc compound
A tert-butyl derivative of cobalt phthalocyanine was pre-
pared to solubilize the phthalocyanine in the solvents used for
membrane synthesis. The procedure of making tert-butyl
cobalt phthalocyanine was as described in the work of Kai-
pova et al.48 A mixture of 4-tert-butylphthalonitrile (0.46 mM,
0.10 g), Co(OAc)2 (0.154 mM, 0.027 g) and a catalytic
amount of diazabicycloundecene (DBU) in n-pentanol (1 mL)
were heated to 1408C with stirring for 24 h under N2 atmo-
sphere. Then, the reaction mixture was cooled to room temper-
ature and allowed to precipitate by adding methanol.
Methanol was used several times for washing the precipitate
and filtered off. The intense blue colour powder formed after
drying is tert-butyl cobalt phthalocyanine (tBu-CoPc).
Preparation of PFA and CoPc-PFA membranes
Since solution casting methods resulted in membranes with
very poor fluxes, PFA membranes, both pure and CoPc
impregnated, were prepared by a spin coating technique in an
effort to reduce the membrane thickness. The PFA coating
was formed on a support of highly porous commercial ultrafil-
tration PSf membrane by the following procedure. A piece of
dried PSf membrane (50 3 70 mm2) was fixed on to a glass
slide using a double-sided tape to prevent the membrane from
rolling up and also to avoid sticking to the glass slide after
polymerization. This was then coated with a PFA precursor
solution (prepared by mixing FA, sulfuric acid and ethanol) in
a spin coater (1000 rpm for 60 s). The coated support was then
heated at 808C overnight for FA polymerization and solvent
evaporation. Typically, in the fabrication of PFA-250 mem-
brane, a mixture with a FA/H2SO4 molar ratio of 250 was pre-
pared by adding 10 g (0.1 mol) of FA into a solution
containing 0.0397 g (0.004 mol) of H2SO4 and 10 g (0.217
mol) of ethanol drop wise.49
CoPc-PFA composite membranes were prepared using the
same procedure, except that the required amount of CoPc

188 DOI 10.1002/aic Published on behalf of the AIChE January 2018 Vol. 64, No. 1 AIChE Journal
 Figure 1. Experimental gas permeation setup.
[Color figure can be viewed at wileyonlinelibrary.com]
powder was added in the FA-ethanol solution and stirred mag-
netically for 5 hrs followed by 30 min of ultrasonication. The
resulting CoPc-FA ethanol suspension was immediately mixed
with sulfuric acid diluted in ethanol under magnetic stirring
and then spin coated on the PSf membrane followed by heat-
ing at 808C overnight as described earlier. While the concen-
tration of CoPc in the casting solution has been used in
designating the loading in the different composite membranes,
the actual CoPc content of the membranes has been deter-
mined separately, as discussed in a subsequent section.
Preparation of PSf and CoPc-PSf membranes
PSf membranes were synthesized by solution casting
method described elsewhere.38–40 PSf was degassed under
vacuum at 808C for 24 h to remove adsorbed moisture. Then,
a viscous solution was prepared by dissolving 1.2 g polymer
in 6 mL chloroform (13 wt % of polymer) followed by 24 h of
magnetic stirring. The solution was cast on a glass plate using
Doctor’s blade (Sheen instruments, UK) and kept at room tem-
perature in a partially closed desiccator for 24 h to slow down
the natural evaporation. After that the films were completely
dried in vacuum at 808C for 24 h. Similarly, to synthesize dis-
persed CoPc-PSf membranes, the required weight of CoPc
was degassed as described above and magnetically stirred in
6 mL chloroform for 24 h to make a stable dispersion; and
then stirred again for 24 h after adding 1.2 g of polymer. This
solution was cast on a glass plate and cured as before.
In the case of PSf membranes with soluble CoPc (tBu-
CoPc), membranes synthesized as above with chloroform sol-
vent showed defects. Defect free membranes could however
be prepared using DMF as the solvent instead of chloroform,
with the following procedure. The required amount of tBu-
CoPc was dissolved in 4mL DMF and then stirred for 24 h
after adding 0.8 g of polymer. Thereafter, the viscous solution
was cast on a glass plate inside an oven (maintained at 458C
and kept for 15 mins). The glass plate was dried again consec-
utively at 608C and 708C for 15 mins each. Finally, the mem-
brane was formed after heating the glass plate at 1508C for
AIChE Journal January 2018 Vol. 64, No. 1 Published on behalf of the AIChE
12 h to completely remove the solvent. With this procedure,
moisture trapping by DMF could be avoided, and defect-free
membranes produced.
Membrane characterization methods
All the synthesized native and composite membranes were
characterized by morphological analysis and thermal analysis.
Microscopic observations were performed by scanning elec-
tron microscopy to evaluate the membrane thickness and mor-
phology. The (SEM) images were acquired on a JEOL JSM-
7600F microscope (Jeol Corp. Ltd., Tokyo, Japan). Both the
surface and cross-sectional samples were sputtered with plati-
num and the images were collected by E-SEM operated at
5–20 kV in environmental mode. Cross-section sample of
PFA membranes were prepared by freeze fracture in liquid
nitrogen, while in the case of PSf membranes, such cross sec-
tions were made by cutting the membrane with a very sharp
and fine blade, since the freeze-fracture technique did not
work well with these composite membranes.
The glass transition temperature (Tg) of pure and composite
membranes were determined by DSC analysis (STA instru-
ments, NETZSCH PC-409, Germany). The temperature was
increased from 100 to 3008C at a rate of 38C/min for two con-
secutive runs in N2 flow and the Tg was measured from middle
point of the slope transition in the DSC curve based on the sec-
ond run. TG studies were performed in the same instrument
from 30 to 10008C at a heating rate of 108C/min by placing 6–
8 mg sample in an 85 lL alumina pan.
The membranes were also characterized using Fourier trans-
form infrared spectroscopy (FTIR). FTIR spectra were
recorded on a 3000 Hyperion Bruker Microscope with Vertex
80 FTIR system (Germany) spectrometer.
A schematic diagram and image of the gas permeation setup
is shown in Figure 1 which was used to measure membrane
parameters (permeability and selectivity). The setup was simi-
lar to the one described by David et al.50 The setup can be
used to study both pure as well as mixed gas permeation
through membranes. Brooks-make calibrated mass flow
DOI 10.1002/aic 189

Figure 2. Schematic diagram of the double O-ring
membrane test cell.
[Color figure can be viewed at wileyonlinelibrary.com]
controllers (MFC) were used to maintain the gas flow rate and
feed composition. The flow rate range of these MFCs was 0 to
100 cm3 (STP) min21. A Tescom-make back pressure regula-
tor (BPR) was used on the retentate line to maintain the feed
side pressure (pressure can be varied from 0 to 10 bar). Perme-
ate side was at atmospheric pressure. A helium sweep was
used to remove the permeated gas. The sweep gas flow rate
was controlled using an MFC (range 0 to 50 cm3(STP)
min21). The permeate gas composition determined by an
online gas chromatograph fitted with a thermal conductivity
detector and two columns, (a) molecular sieve 5A, and (b)
Porapak-Q. The membrane test cell itself contains two com-
partments sealed by O-rings as shown in Figure 2. The thin
flat sheet membrane was supported by a porous metallic plate,
the exposed area of the circular flat sheet membrane being
4.91 cm2.
The gas permeability was calculated using Eq. 1
Qd
P5 (1)
ADp
Where Q is the permeate gas flow rate, d is the membrane
thickness, A is the exposed area of membrane and Dp is the
(partial) pressure gradient across the membrane. The permeate
flow rate (Q) is the product of the gas concentration (mol/m3
or m3/m3) as measured by the GC and the helium sweep gas
flow rate.
Results and Discussion
Characterization of membranes with and without
dispersed CoPc
Here, we describe the characterization of the additives stud-
ied in this work and of the membranes with and without the
additives. Table 3 shows the structure of the polymers as well
as the images of as-synthesized pure and composite mem-
branes (with CoPc) from the two different glassy polymers.
Table 3. The Two Polymers Used in This Work and Images of Membranes Made from Them with and without CoPc [Color
table can be viewed at wileyonlinelibrary.com]
190 DOI 10.1002/aic Published on behalf of the AIChE
Morphological studies using SEM
SEM images of CoPc powder are shown in Figures 3a, b.
The length of the long thin needle shaped particles varied
from 10 to 20 mm, with the thickness being in the range 1.7 to
2.4 mm. Figures 4a–d show surface images of CoPc-PFA com-
posite membranes for different loadings (wt %) of CoPc and
Figures 4e–f show the cross-sectional images of 3% CoPc-
PFA composite membranes. These images show that CoPc
crystals are essentially unmodified on incorporation in the
membrane. The thickness of the skin layer on PSf support
made by spin coating was checked at different points along
the radius of the same sample, and the PFA layer thickness
varied from 1.7 to 2.07 mm. This is comparable to the thick-
ness of CoPc needles, which are seen to by embed nearly par-
allel to the surface in the micrographs. For permeability
calculation, a thickness of 2 mm (closer to the upper limit of
the range measured) has been assumed, because the actual
thickness of the PFA layer might be higher owing to the pene-
tration of PFA solution inside the porous PSf layer.
Figures 5a–e represent the surface images of pure PSf mem-
brane and CoPc-PSf composite membranes for different CoPc
loadings. While the thickness of these membranes is much
more than that of the needles, a large number of CoPc particles
are seen on, or embedded fairly close to, the surface in these
images, with the density increasing with the particle loading
as expected. The dispersion of CoPc particles on the surface is
fairly homogeneous. Figures 6a–e show the cross-sectional
images of pure PSf and PSf-CoPc composite membranes. The
thickness of pure PSf membrane is seen to be about 20 mm. A
slightly higher gap had to be maintained in the Doctor’s blade
for the casting of CoPc impregnated polymer so that the result-
ing membranes were defect-free. It was observed that the
thickness of composite membrane increased with increase in
CoPc content irrespective of maintaining the same gap. The
thickness of the composite membranes (as measured from
cross sectional images) is reported in Table 9. The cross-
sectional images do show the evidence for the presence of par-
ticles, but probably to a lesser extent than the surface region.
FTIR studies
Structural characterizations of CoPc, as well as the pure and
composite membranes using FTIR are shown in Figure 7. In
spectrum “a” for CoPc, sharp intense peaks associated with
different bond orientations may be distinguished: 731 cm21
(C-H out of plane deformation), 780 cm21 (C–N in-plane
stretching vibration), 912 cm21 (Metal ligand vibration),
1087 cm21 (C–H in-plane deformation), 1120 cm21 (C–H
in-plane bending), 1166 cm21 (C–N in-plane bending),
1288 cm21 (C–N stretching in isoindole), 1331 and 1423 cm21
January 2018 Vol. 64, No. 1 AIChE Journal
Figure 3. SEM images of CoPc particles (a) lower mag and (b) higher mag. (scale bar 5 1 mm).
[Color figure can be viewed at wileyonlinelibrary.com]

(C–C stretching in isoindole), 1521 cm21 (C 5 N stretching),
and 1605 cm21 (C 5 C macrocycle ring deformation).51 The
spectra “b” and “d,” for pure PSf and PFA membranes, respec-
tively, clearly show the peaks expected from their structure.
Incorporation of CoPc does not change the signature of the
polymer as seen from spectra “b-e.” In spectra “b” and “c,” the
peak at 1160 and 1241cm21 corresponds to the vibration of dia-
ryl sulfone (Ar-SO2-Ar) and diaryl ether (Ar-O-Ar) groups pre-
sent in PSf monomer unit. The peaks at 1494 and 1582 cm21
represent the vibration of aromatic C 5 C in PSf molecule.52,53
The bands at 2970 and 3058 cm21 belong to the asymmetric and
symmetric stretching vibration of –CH3 group.54 In spectra “d”
and “e,” the broad band at 3237 cm21 is ascribed to the O-H
stretching. The peak at 1241 cm21 corresponds to the stretching
of C-O-C bond. The bands at 551, 841, 1100, 1241, 1486, and
1582 cm21 in the PFA spectra are associated with furan rings.
TGA analysis of CoPc-PFA composite membranes
During the preparation of CoPc-PFA composite mem-
branes, as the particle-polymer solution was coated by spin
coating, it is not safe to infer the CoPc wt % in membrane
from that in the solution used. The actual CoPc wt % was,
therefore, determined by thermogravimetry on the delami-
nated PFA samples. Figure 8 shows the TGA mass loss curves
for the different membranes obtained at a heating rate of 108C/
min up to 6008C in N2 atmosphere. The reasons of choosing
this condition are: a significant weight loss of the pure poly-
mer (TGA with pure PFA up to 8008C showed that about 95%
of the mass loss occurs by 6008C) and no weight loss of pure
CoPc within the temperature range (CoPc starts to degrade
above 6008C), the difference in residual mass between differ-
ent membranes is attributable to the amount of CoPc in the
membrane. CoPc wt % in membrane was also cross-checked
with EDAX data, which is reported in Table 4 along with the
result from TGA studies. TGA and EDAX data are in reason-
able agreement, and show that the actual concentration of
CoPc is less than what is expected on the basis of the concen-
tration in solution.
TGA analysis of CoPc-PSf composite membranes
The TGA analysis of CoPc-PSf composite membranes was
conducted in an air atmosphere up to 10008C. This change in

Figure 4. ESEM images of CoPc-PFA membranes (a) PFA surface, (b) 3%CoPc-PFA, (c) 7%CoPc-PFA, (d) 9%CoPc-
PFA; (e) x-section of 3%CoPc-PFA, (f) x-section at higher magnification.

AIChE Journal January 2018 Vol. 64, No. 1 Published on behalf of the AIChE DOI 10.1002/aic 191
 Figure 5. Surface images of (a) pure PSf, (b) 5%CoPc-PSf, (c) 10%CoPc-PSf, (d) 15%CoPc-PSf,
and (e) 20%CoPc-PSf.

procedure and conditions (from what were used with PFA
membranes) was necessitated since the decomposition of PSf
membranes was incomplete under the previously used condi-
tions. Therefore, the corresponding TG curves (shown in Fig-
ure 9) were taken in an oxidizing atmosphere up to 10008C to
ensure the stability of TGA curves and the conversion of CoPc
into cobalt oxide. In general, the membranes showed two
apparent weight losses: one at around 425–5308C and the other
at 540–7408C. The first weight loss (around 50 wt %) might be
attributed to pyrolysis processes, releasing SO2, benzene, phe-
nol, toluene, styrene, xylene, and so forth.37 The second
weight loss (around 47 wt %) is the result of complete degra-
dation of the polymer chain. The residual mass when CoPc
was subjected to thermogravimetry under the same conditions,

Figure 6. X-sectional images of (a) pure PSf, (b) 5%CoPc, (c) 10%CoPc, (d) 15%CoPc, and (e) 20%CoPc composite
membranes.
[Color figure can be viewed at wileyonlinelibrary.com]

192 DOI 10.1002/aic Published on behalf of the AIChE January 2018 Vol. 64, No. 1 AIChE Journal
 Table 4. Actual CoPc Content in PFA Composite
Membranes
%CoPc content %CoPc content
Membrane (based on TGA) (based on EDAX)
PFA-5%CoPc 3.11 3.03 6 0.5
PFA-10%CoPc 6.95 5.21 6 0.6
PFA-15%CoPc 9.06 11.48 6 0.9

higher than the pure membrane, which implies CoPc impreg-

Figure 7. FTIR spectra of powder CoPc, pure and com-
posite membranes.
[Color figure can be viewed at wileyonlinelibrary.com]
corresponds to Co2O3. Therefore, from the residual mass of
TGA curves, exact CoPc content of the membranes were back
calculated. CoPc wt % in membrane was cross checked with
EDAX data. All results are reported in Table 5. Once again,
the TGA and EDAX results are comparable, but the values for
PSf are closer to what is expected on the basis of the concen-
trations in the solutions used than in the case of PFA.
DSC Analysis of CoPc-PSf Composite Membranes
Phase transition of polymer from glassy to rubbery state
occurs at the glass transition temperature, much earlier than
polymer decomposition temperature. The glass transition tem-
perature (Tg) was measured from DSC analysis. The DSC
analyses of all the membranes were conducted by heating the
sample up to 1008C and then to 3008C at 38C/min for two con-
secutive runs. The polymer glass transition temperature (Tg)
was taken from middle point of the slope transition in the DSC
curve based on the second run. It is a good idea to heat the
sample a second time because the first heating freezes any pos-
sible metastable states.55,56 Figure 10 shows the variation in
glass transition temperature (Tg varies from 186 to 188.58C)
with CoPc wt %. Tg of composite membranes are only slightly
nation does not significantly affect the polymer properties.
In similar manner, the Glass transition temperature (Tg) of
pure PFA was determined to be 1458C by DSC analysis, which
is close to the value reported in the literature.57
Volume fraction of CoPc in the composite membranes
For explaining the experimental results with composite
membranes (in which CoPc particles are dispersed in the poly-
mer matrix) on the basis of available theories, we need to
know the volume fraction of the particles in the membrane.
This was determined by independently determining the densi-
ties of the CoPc particles and the native polymer membrane,
using Eq. 2
 
particle wt %
particle density
u5   (2)
particle wt % ð1002particle wt %Þ
particle density 1 polymer density
where the particle wt % is determined from TGA studies as
described in previous section. The polymer density was deter-
mined as follows. A known weight of the polymer was placed
in the pycnometer, and soaked in diesel (chosen because both
the polymers show negligible swelling in diesel) by filling the
pycnometer. The weight of the filled pycnometer gives the
weight of diesel. Using the density of diesel (measured in the
same pycnometer) this weight was converted to volume. The
polymer density was then calculated as
mpol mpol
qpol 5 5  (3)
Vpol Vpycnometer 2 mdiesel
qdiesel
The particle density was also similarly determined. The densi-
ties so measured are shown in Table 6. Based on TG and den-
sity studies, the physical characteristics of the membranes
were determined as shown in Table 7.

Figure 8. Thermograms of CoPc-PFA composite Figure 9. Thermograms of CoPc-PSf composite

membranes. membranes.

AIChE Journal January 2018 Vol. 64, No. 1 Published on behalf of the AIChE DOI 10.1002/aic 193
 Table 5. CoPc Content in PSf Composite Membranes
Verified by Different Techniques
CoPc in Solution (wt %CoPc Content %CoPc Content
CoPc/wt Polymer) Based on TGA Based on EDAX
5%CoPc 4.48 4.49 6 0.5
10%CoPc 9.36 10.45 6 0.7
15%CoPc 13.44 14.8 6 0.9
20%CoPc 19.51 19.36 6 1
Performance of PFA and dispersed CoPc-PFA
composite membranes
The performance of PFA and CoPc-PFA composite mem-
branes with pure gases (O2 and N2) is shown in Table 8 and
Figure 11. The permeabilities are quite high in general,
although the selectivities are not, being in the range of 2–3.
Our figures for the permeabilities of oxygen and nitrogen in
the pure PFA membrane may be compared with those reported
by He et al.,58 of 3.33 Barrer for oxygen and 2.67 Barrer for
nitrogen. Our permeabities (as well as the selectivity) are
higher; differences in the preparation method may account for
this (He et al.49 found the FA to acid ratio to influence the per-
meation property of the membrane in H2/N2 separation; fur-
ther, our membranes were made by a spin-coating technique
while theirs were made by a hand-casting technique). Both
oxygen and nitrogen permeabilities show a decreasing trend
with CoPc loading (the permeability for oxygen is almost con-
stant up to a loading of 3 wt % CoPc). However, the decrease
in the permeability of nitrogen is more pronounced, the net
result being a continuous increase in membrane selectivity
from 1.6 for pure PFA membrane to 2.64 for the highest CoPc
loading studied, a 65% increase. These results may be com-
pared with the literature studies reported in Table 2. While
most papers report an increase in selectivity with particle load-
ing, a decrease in O2 permeability such as observed for PFA in
this study has only been reported by Chen and Lai 29 for poly-
carbonate membrane. As the CoPc is insoluble and the par-
ticles are nonporous, the observed trends are suggestive of a
barrier effect as the loading is increased. The barrier effect is
less pronounced for oxygen probably because of facilitation
by the surface molecules on the particles, as the loading
increases and the average distance between CoPc sites
decreases (as this is the distance the oxygen molecules have to
Table 6. Density of Polymers and Powder CoPc
Density (g/cc)
Diesel 0.91
PFA Membrane 1.50
PSf Membrane 1.31
CoPc Particle 1.69
“hop”). The facilitation, however, is not very effective in the
insoluble state of the CoPc, and, in any case, not significant
enough to counteract the barrier effect. The trends observed
can thus be qualitatively explained as being due primarily to a
barrier effect of the particles, with some facilitation coming
into play as the loading is increased. Cussler et al.59 have mod-
eled the barrier effect due to impermeable flakes and lamellae
in several idealized configurations. For the case of randomly
placed flakes, the model gives
Pm lb2 /2
511 (4)
PC 12/
where m is a geometric factor which may be calculated for our
case by fitting our data to Eq. 4. Such a procedure gives a
value of 1.869 for l, and the fit of the model is shown by
dashed lines in Figure 11. The fit is better for oxygen than for
nitrogen. As this model does not take any facilitation into
account, the selectivity improvement seen in the experiments
would not be explained by the model. While the fit and selec-
tivity predictions could be improved by fitting different values
of l to oxygen and nitrogen, the precepts of the model are not
consistent with such an assumption; such a sophistication was
also not considered warranted by the limited amount of data
available here.
Figure 12 represents the performance of these membranes
in relation to the Robeson’s bounds. It is seen that the perfor-
mance of the membrane in general moves closer to the bound
as the CoPc loading is increased.
Performance of PSf and dispersed CoPc-PSf composite
membranes
Table 9 gives a summary of the experimental results on
PSf-CoPc composite membranes. Gas permeability and selec-
tivity values are tabulated with the percent decrease or
increase (with respect to the native membrane) shown in
parenthesis. In addition to air separation data, the table also
shows some data on CO2/N2 separation, which will be dis-
cussed in the succeeding paragraphs. All the permeability and
selectivity values for the pure PSf (without CoPc) membranes
compare well with the literature values quoted in Table 1.
With the O2/N2 system, it is seen that the PSf membranes in
general have a better selectivity but a lower permeability as
compared to the PFA membranes. The selectivity shows a
marginal increase with loading. The permeabilities for both

Table 7. Particle Volume Fraction of Different CoPc-PSf

Composite Membranes
CoPc wt % CoPc wt % Volume
in Solution (Measured by TGA) Fraction (/)
1 1 0.008
2 2 0.016
5 4.5 0.039
10 9.4 0.082
Figure 10. Variation in Tg of PSf membranes with CoPc 15 13.4 0.119
loading. 20 19.5 0.176

194 DOI 10.1002/aic Published on behalf of the AIChE January 2018 Vol. 64, No. 1 AIChE Journal
Table 8. O2/N2 Separation Performance of PFA Composite
Membranes with CoPc Loading at 6 Bar and 308C (percent
change from the value for native membrane is shown in
parenthesis)
CoPc P (O2) P (N2) S
wt % (Barrer) (Barrer) (O2/N2)
0 14.80 9.2 1.61
3.11 15.33 (3.6%) 8.66 (–5.9%) 1.77 (10%)
6.95 13.88 (–6.2%) 6.39 (–30.5%) 2.17 (34.9%)
9.06 11.93 (–19.4%) 4.53 (–50.8%) 2.64 (63.8%)
oxygen and nitrogen are lower with CoPc incorporation, but
the trends are different from what was seen for PFA. The per-
meabilities first decrease and then increase as the loading is
increased, with a clear minimum at a loading of 5%. The vari-
ation in permeability is less pronounced for N2; the values for
oxygen increase almost to the level of the native membrane as
the loading is increased. Figure 13 shows the variation in per-
meability and selectivity with CoPc wt %. In Figure 15, these
results are juxtaposed against the Robeson upper bound, and it
is seen that 10% loading represents an optimum in terms of
approach to the bound.
Metal pthalocyanins and porphyrins are molecules inspired
by hemoglobin. Hemoglobin shows a reversible binding abil-
ity not only with oxygen but also with CO2. Since CO2/N2 sep-
aration is also an industrially important problem which we are
addressing in our lab, we thought it would be interesting to see
how the CoPc-PSf membranes perform on this separation as
well. The work of Hosseinkhani et al.,34 which argues a facili-
tated transport of CO2 transport through incorporation of a
cobalt complex (cobalt acetate tetrahydrate) has been dis-
cussed earlier. The reversible binding ability is explained by
four- or five-coordinated square complex formation. This
square complex formation is reported by Tsuchida et al.31 and
Nishide at al.,21 mainly for facilitated O2 transport through
CoPc or CoP impregnated membranes, but has been seen in
CO2 transport as well.
Results of permeation studies on the CO2/N2 system are
summarized in Table 9 and Figure 16. The changes in perme-
ability and selectivity follow nearly the same trend as for
O2-N2 system, but overall, the results are even more encourag-
ing than for O2/N2 separations, with permeability values for
CO2 exceeding that for native membrane at high loadings, and
a maximum improvement in selectivity of the order of 33%.
Figure 11. Effect of CoPc loading on PFA membrane
performance.
AIChE Journal January 2018 Vol. 64, No. 1 Published on behalf of the AIChE
Figure 12. O2/N2 separation performance of PFA com-
posite membranes with respect to Robeson
upper bound.
The comparison with Robeson’s limits (Figure 17) also under-
lines this observation.
Studies in the literature attribute any decrease in permeabil-
ity on particle incorporation in membranes to a simple barrier
effect (as seen above in this work also, for PFA membranes)
or to polymer rigidification around the particle (which in turn
contributes to a barrier effect). Thus, Li et al.60,61 observed a
decreased permeability and an increased selectivity on incor-
poration of zeolite 5A in their polyether sulfone (PES) mem-
branes. Similar results have also been reported by Suer et al.62
for 13X-zeolite-PES membrane, and by Mahajan et al.63 for
4A zeolite-polyimide membranes. While CoPc does have a
reversible binding ability with both oxygen and carbon diox-
ide, with the CoPc being in insoluble form, a “hopping” of
bound molecules from one site to another only becomes signif-
icant when the sites are not too far apart, that is, at higher load-
ings. Therefore, the permeability data for low loadings (5% or
less) was fitted with the models for barrier membrane as
explained in the previous section (Eq. 4) for randomly placed
impermeable flakes. The fitted value of the geometric factor
(l) for randomly placed particles is 11.78. The fitted curves
are represented by dashed lines in Figures 13,14,16. Cussler
et al.59 have also modeled the case of regularly placed flakes,
which predicts the decrease in permeability in terms of two
parameters, an aspect ratio for the flakes and an aspect ratio
for the pores. Using the value for the former from the SEM
micrographs and fitting the value of the latter gave a slightly
better fit to the data than Eq. 4. These results are not shown
here as a random placement of flakes was considered more
realistic.
As the CoPc loading is increased, it is seen that the perme-
abilities increase. The increase in permeability between load-
ings of 5 and 20% is in the order CO2 > N2 > O2. This
ordering suggests that facilitation is unlikely to be the sole
mechanism, as nitrogen certainly is not influenced by such a
mechanism. A combination of facilitation (if any) and mor-
phological effects arising out of an incompatibility between
the particulate phase and the polymer matrix (the SEM studies
of Figure 6 do suggest such possibilities) are likely to be the
cause here. A simple way to model this increase is to use the
Maxwell equation for the effect of a “permeable” particle
incorporation in the membrane. This assumes that having a
particle such as CoPc (with any associated void spaces created
in the matrix due to incompatibility between the polymer and
DOI 10.1002/aic 195
 Table 9. Membrane Performances of CoPc-PSf Composite Membranes at 6 Bar and 308C

Membrane
Membrane Tg (8C) thickness (mm) P (O2) P (N2) P (CO2) S (O2/N2) S (CO2/N2)
PSf 186.1 20 1.53 0.327 7.04 4.68 21.5
1% CoPc 187.2 28.1 1.37 (–10.5%) 0.281 (–14.2%) 6.11 (–13.2%) 4.88 (4.3%) 21.7 (1.2%)
2% CoPc 187.3 28.4 1.32 (–13.7%) 0.266 (–18.8%) 5.75 (–18.3%) 4.97 (6.2%) 21.6 (0.6%)
5% CoPc 187.4 30.02 1.26 (–17.5%) 0.225 (–31.4%) 5.07 (–27.9%) 5.62 (20.3%) 22.6 (5.1%)
10% CoPc 187.4 31.84 1.41 (–7.9%) 0.232 (–29%) 6.07 (–13.8%) 6.06 (29.6%) 26.1 (21.4%)
15% CoPc 187.8 33.89 1.43 (–6.5%) 0.256 (–21.9%) 7.35 (4.4%) 5.58 (19.2%) 28.7 (33.5%)
20% CoPc 188.4 34.6 1.45 (–3.9%) 0.287 (–12.3%) 7.7 (9.9%) 5.12 (9.5%) 26.9 (25.3%)
Parenthesis values represent percent increase or decrease in permeability or selectivity value.

the particles) is equivalent to having a dispersed phase of
higher permeability in the polymer matrix. According to the
Maxwell model
 21
PC a1Ap
511ð11AÞ/ 2/ (5)
Pm a21
where the parameter Ap depends on the shape of particle
(Ap 5 1 for transverse cylinder and 2 for spherical particles)
and a is the permeability ratio of dispersed phase to continu-
ous phase. As, the CoPc particles are needle shaped as seen
from SEM image, the A value has been taken as 1 (for trans-
verse cylinder) and a estimated so as to provide a best fit to
the experimental data of CO2, O2, and N2. The value of a for
CO2, O2, and N2 is 22.2, 2.75, and 3.99 respectively. The fit of
Eq. 5 is shown in Figures 13,14,16 for the rising part of the
permeability curve.
Performance of soluble CoPc-PSf composite membranes
The results reported above show that in general, any facili-
tation due to CoPc incorporation is not much in evidence
when the CoPc is in the form of insoluble needles, any facilita-
tion being limited by the fact that it is only the surface mole-
cules of the CoPc particles that can contribute in this fashion.
It was therefore felt that, if the CoPc could be molecularly dis-
persed by solubilizing it, better results could be expected.
Here, we present the characterization and performance results
with tBu-CoPc, a soluble derivative of CoPc, synthesized with
this objective. PSf having shown better performance in the
earlier described experiments, it was chosen as the membrane
material for these studies. Details of characterization of the
synthesized tBu-CoPc and the soluble tBu-CoPc-PSf compos-
ite membranes are available in the Supporting Information.
The O2 and N2 separation performance of all these mem-
branes (prepared using DMF) was studied at a feed pressure of
6 bar, and the results are shown in Table 10 and Figure 18.
Figure 18 compares the effect of CoPc loading in dispersed vs.
in soluble form, on O2 permeability and O2/N2 selectivity. It is
seen that, while the O2 permeability decreases with increasing
CoPc wt % at low loadings of dispersed CoPc, it increases
continuously within the studied range for soluble CoPc. Table
10 shows that the presence of solube CoPc has no significant
effect on the permeability of nitrogen. As a result, the O2/N2
selectivity increases with tBu-CoPc loading, and the increase
is larger than in the case of CoPc particles.
These results, therefore, indicate that the presence of molec-
ularly dispersed tBu-CoPc molecules facilitates the transport
of oxygen as expected, leaving that of nitrogen essentially
unchanged. Nishide et al.64 have studied the facilitated O2
transport through soluble cobalt porphyrin dispersed in polyvi-
nylidene dichloride membrane using an extended dual-mode
transport model represented by Eq. 6.
= =
CH bDH CC DC K
P5kD DD 1 1 (6)
11bp 11Kp
Here, the first term is due to the diffusion of dissolved gas
molecules through polymer matrix, the concentration of the
dissolved gas being governed by Henry’s law. The second
term is due to the surface diffusion of adsorbed gas, the
adsorption being governed by the Langmuir isotherm. These
two terms govern the transport in the native polymer. In the
presence of a facilitating agent, the third term is included, and
represents the effect of additional sorption-type sites contrib-
uted by the agent for the particular species whose transport it
facilitates (oxygen in the present case). We have used this

Figure 13. O2 separation performance of PSf mem- Figure 14. N2 separation performance of PSf mem-
branes with CoPc wt %. branes with CoPc wt %.

196 DOI 10.1002/aic Published on behalf of the AIChE January 2018 Vol. 64, No. 1 AIChE Journal
Figure 15. O2/N2 separation performance of CoPc-PSf Figure 17. CO2/N2 separation performance of CoPc-
composite membranes with respect to PSf composite membranes with respect to
Robeson upper bound. Robeson upper bound.

model for the case of tBu-CoPc dispersed in PSf, in the fol- the parameters for nitrogen transport through the native PSf
lowing manner. First, we include the third term only for oxy- membrane are also compared with the data in Table 10 and
gen and not for nitrogen whose transport is not influenced by Figure 18.
the presence of the facilitating agent. Assuming the additional
sites for oxygen contributed by tBu-CoPc to be proportional to Conclusions
its volume fraction, we write C0C 5a/L in Eq. 6. Denoting aC 5
In recent years, there has been much interest in the use of
aDC we finally get
particulate additives and facilitation agents to improve the per-
C0H bDH aC K/L formance of polymeric membranes in gas separation. This
P5kD DD 1 1 (7)
11bp 11Kp work is focussed on the mechanisms that come into play with
such incorporations, and the complex ways in which they
The values of the parameters were determined as follows. The interact to modify the performance of the membrane. In gen-
value of kD, b and C0H were calculated for each of oxygen and eral, three effects have been recognized—a barrier effect and a
nitrogen by fitting the experimental sorption isotherm data structural modification of the polymer matrix when the
published by Kim and Marand;65 then the values of DD and
DH were calculated by fitting our own experimental data (not
Table 10. Experimental and Calculated Data of Solubilized
reported here) on pure gas permeabilities as a function of par-
CoPc-PSf Membranes
tial pressure. For oxygen, the value of equilibrium constant
(K) was calculated from the DH and DS value of the reversible P (O2) P (N2) S (O2/N2)
reaction reported by Preethi et al.23 and the estimated value of Exp Cal Exp Cal Exp Cal
K is 11.94. The value of aC was then calculated for oxygen by PSf 1.62 1.51 0.321 0.325 5.03 4.63
fitting the data of permeability at different loading from this PSf-1% tBu-CoPc 1.58 1.61 0.288 0.325 5.49 4.96
work, reported below. The fit of Eq. 7 is represented by the PSf-2% tBu-CoPc 1.74 1.72 0.29 0.325 5.99 5.29
solid line in Figure 18. The fitted value of aC (for O2) is 4.93e- PSf-3% tBu-CoPc 1.82 1.83 0.294 0.325 6.2 5.61
09. The fit of Eq. 7 to the data is seen to be satisfactory. The
selectivity predictions based on the fitted value of aC and

Figure 18. Comparison of membrane performance

Figure 16. CO2 separation performance of PSf mem- between dispersed and soluble CoPc-PSf
branes with CoPc wt %. membranes

AIChE Journal January 2018 Vol. 64, No. 1 Published on behalf of the AIChE DOI 10.1002/aic 197
additives are insoluble or partially soluble, and a facilitation b = sorption affinity toward gas molecules
effect, which occurs whether the particles are insoluble or sol- C0H = maximum sorption uptake
uble. CoPc-PFA and CoPc-PSf were the candidate systems DD, DH = diffusion coefficient for Henry and Langmuir mode
respectively
used in the study. CoPc particles are insoluble in the formula- DC = diffusion coefficient of gas molecules by facilitation through
tion and remain dispersed in the polymer matrix at all loadings fixed carrier complex
tested, down to 1%. Incorporation of CoPc into the polymeric K = equilibrium constant
matrix improves the selectivity for CO2 and O2 over N2, and uL = particle loading (wt %)
in general moves the membrane performance closer to the
Robeson upper bounds for these mixtures. However, in dis-
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Manuscript received Apr. 13, 2017, and revision received June 30, 2017.
DOI 10.1002/aic 199