Zwitterionic silica copolymer based crosslinked organicinorganic hybrid

polymer electrolyte membranes for fuel cell applications{

Tina Chakrabarty, Ajay K. Singh and Vinod K. Shahi*
Received 27th May 2011, Accepted 19th November 2011
DOI: 10.1039/c1ra00228g
Zwitterionic (ZI) copolymers (consisting of sulfonic acid and amine groups) with plenty of
Si(OCH)
3
groups similar to stems, branches and fruits of vines from a bionic aspect, were
synthesized as a cross-linking agent. Organicinorganic hybrid zwitterionic membranes (ZIMs),
with high flexibility, charge density and conductivity, was prepared using poly(vinyl alcohol)
(PVA). Developed ZIMs with dual acidic and basic functional groups, exhibited high stabilities,
water retention ability and cation selectivity. The ZIMs (especially Si70%) were designed to
possess all the required properties (water uptake: 40.6%; ion-exchange capacity: 1.52 equiv. g
21
;
electro-osmotic flux: (2.34 6 10
25
cm s
21
A
21
); and conductivity: 9.67 6 10
22
S cm
21
. ZIMs were
designed to possess all of the required properties of a proton-conductive membrane, namely,
reasonable swelling, good mechanical, dimensional, and oxidative strength, flexibility, and low
methanol permeability along with good proton conductivity due to zwitterionic functionality.
Moreover, Si70% and a Nafion117 membrane exhibited comparable DMFC performance. Also,
investigation on a multi-ionic organicinorganic hybrid ZIM as polymer electrolyte membranes
(PEMs) will give rise to a new developing field in materials and membrane science.
Introduction
PEMs with high conductivity, low methanol crossover and cost,
are greatly desired for direct methanol fuel cells (DMFCs) in
order to reduce ohmic losses and enhance their efficiencies
during operation.
14
Perfluorosulfonic acid membrane (Nafion)
is a reference membrane for DMFC because of its high
electrochemical properties as well as excellent chemical resis-
tance.
2,5
Nafion membranes show high methanol crossover, and
become dry under conditions of high temperature (above 80 uC)
or low humidity rather quickly due to the loss of water from the
membrane.
513
Thus, widespread efforts were dedicated to
develop inorganicorganic composites based on a modified
Nafion membrane.
1417
PEMs with high proton conductivity at
intermediate temperatures under anhydrous or low-humidity
conditions, environmental affability with low methanol cross-
over, and production cost have attracted much interest recently
for problem solving in current technologies.
7,1822
For the
development of cheaper PEMs, fluorine-free materials with
properties comparable to those of Nafion, based on sulfonated
aromatic polymers, irradiation graft polymers, and cross-linked
and blend polymers, were successfully proposed.
2329
Only a few reports are available for ZI based hybrid
nanostructured PEMs.
3035
The acidbase composite PEMs
with high proton conductivity under anhydrous conditions, such
as poly(benzimidazole)phosphoric acid or sulfuric acid,
36,37
poly(vinylphosphonic acid) heterocycle,
38
and ionic liquids,
39
were reported. However, the proton-conductive pathway can be
controlled by a suitable molecular assembly between acidic and
basic moieties by introducing these functional groups in the same
molecule for high proton conductivity, water retention, and low
methanol permeability.
4042
For developing ZIMs, organicinorganic hybrid materials
are a suitable option, because of the synergistic advantages of
organic and inorganic segments (e.g., structural durability,
dielectric, ductility, processability, thermal and mechanical
stability).
4345
To enhance strength and compatibility,
preparation methods for organicinorganic hybrid functional
materials were explored over the last decade.
46,47
Incorporation of an inorganic ion exchange filler into an
organic matrix showed the leaching out due to the lack of
chemical bonding between two segments.
4749
In another sol
gel process of alkoxysilane-functionalized polymers followed
by cross-linking with conventional agents, (aldehydes and
small alkoxysilanes), a low content of organic groups and lack
of any functional group are disadvantageous for homogenous
and conductive PEMs.
50
To overcome these problems earlier
we reported 3-(3-(triethoxysilyl)propylamino)propane-1-sul-
fonic acid, a zwitterionomer cross-linking agent, which
contained one number of each sulfonic acid and amine groups
Electro-Membrane Processes Division, Central Salt and Marine Chemicals
Research Institute, Council of Scientific & Industrial Research (CSIR),
G. B. Marg, Bhavnagar, 364002, Gujarat, India.
E-mail: vkshahi@csmcri.org; vinodshahi1@yahoo.com;
Fax: +91-278-2567562/2566970; Tel: +91-278-2569445
{ Electronic Supplementary Information (ESI) available. See DOI:
10.1039/c1ra00228g/
RSC Advances
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per molecule.
51
In our continuous effort, we tried to improve
numbers of functional groups (sulfonic acid and amine groups)
on the zwitterionomer for achieving highly stable and
conductive ZIMs with appreciable numbers of ion-exchange
sites in the membrane matrix.
Herein, a multi-ionic silicon based copolymer (3,3-dimethoxy-
7-(4-sulfonatobutyl)-2-oxa-7,10-diazonia-3-silatetradecane-
7,10-diium-14-sulfonate) was prepared as an organicinorganic
hybrid zwitterionomer cross-linking agent using 3-(2-amino
ethyl amino)propyl trimethoxysilane (AAPTMS) and 1,4-
butanesultone via a ring opening reaction. Interestingly, the
structure of multi-ionic silicon based ZI cross-linking agent may
be similar to vines from a bionic aspect. The flexible main chain
is comparable with the stem of a vine, functional groups (sulfonic
and amine) are like fruit, and Si(OCH
3
)
3
groups look like
branches. A multi-ionic ZI precursor with plenty of Si(OCH
3
)
3
groups has the ability to cross-link with PVA in the presence of
TEOS. Structural features of prepared ZIM (long main chain
with many branched chains avoids organicinorganic phase
separation and enhances membrane flexibility; plenty of acid and
basic groups balance membrane fixed charge concentration and
water retention ability) are expected to result in a highly stable
and conductive PEM.
Experimental section
Materials
AAPTMS, TEOS, 1,4-butanesultone (distilled under vacuum),
and Nafion117 (perfluorinated membrane) were purchased from
Sigma Aldrich Chemicals and were used as received.
Tetrahydrofuran (THF; Qualigens Fine Chemicals, Mumbai,
India) was distilled and kept dry over molecular sieves. PVA
(MW, 125 000; degree of polymerization, 1700; degree of
hydrolysis, 88%), and all other chemicals, reported in this
manuscript were obtained from SD Fine Chemicals (Mumbai,
India) of AR grade and used without further purification. In all
experiments, double-distilled water was used.
Preparation of zwitterionomer
Zwitterionomer precursor, 3,3-dimethoxy-7(4-sulfonatobutyl)-
2-oxa-7,10-diazonia-3-silatetradecane-7,10-diium-14-sulfonate,
was synthesized from 1,4-butanesultone and AAPTMS. In a
general synthesis method, AAPTMS in THF was stirred under a
nitrogen atmosphere, followed by the drop wise addition of 1,4-
butanesultone, (dissolved in THF) at 60 uC. The reaction mixture
was refluxed at 50 uC under stirring in a nitrogen atmosphere for 1
h, and then the solvent was evaporated. The obtained solid mass
was dried in a vacuum oven at 40 uC for 24 h, and yielded a dark
yellow coloured solid product.
CHNS: calcd (C, 38.85; H, 7.74; N, 5.66; S, 12.96); obsd (C,
38.81; H, 7.70; N, 5.64; S, 12.93).
Preparation of a cross-linked organicinorganic hybrid ZIM
PVA (10 wt%) was dissolved in hot deionized water under
constant stirring. An appropriate amount of synthesized ZI
precursor was dissolved in deionized water at pHy2, separately,
and mixed with PVA solution, in the presence of a fixed amount
of TEOS (20 wt% to PVA). The obtained solution was stirred for
8 h at room temperature. The solgel process was achieved by
acid hydrolysis (pH: 2), and obtained gel was transformed as thin
film on a cleaned glass plate. Film was dried in ambient
conditions for 24 h and further at 70 uC for 12 h under IR lamp.
The obtained transparent membrane was peeled off for further
cross-linking with a formal solution (HCHO + H
2
SO
4
) for 3 h at
60 uC. Prepared membranes were designated as SiX, where X is
the wt% of zwitterionomer in the membrane matrix, and varied
between 5070 wt% of PVA content.
Fourier transform infrared (FTIR) and NMR characterization
FTIR spectra of dried membrane samples were obtained using
an attenuated total reflectance (ATR) technique with a Spectrum
GX series 49387 spectrometer in the range 4000600 cm
21
. The
IR spectrum for a synthesized zwitterionomer was obtained by
the KBr pellet method.
1
H NMR spectra was used to
characterize the synthesized zwitterionic material recorded by
FT NMR (Bru ker, 200 MHz) Brucker DPX-200 in a d
6
-DMF
solvent.
Thermal and mechanical strength analysis
Thermal stabilities of the prepared zwitterionomer membranes
were obtained by thermo-gravimetric analysis (Mettler Toledo
TGA/SDTA851
e
with Star
e
software) under nitrogen atmo-
sphere with 10 uC min
21
heating rate between 50 to 600 uC.
Differential scanning calorimetry (DSC) measurements were
achieved by Mettler Toledo DSC822
e
thermal analyzer with
Star
e
software. The dynamic mechanical strength of zwitterio-
nomer membranes were analysed by Mettler Toledo dynamic
mechanical analyzer (DMA) 861
c
instrument with Star
e
software
under nitrogen atmosphere with 10 uC min
21
heating rate
between 30 to 300 uC. Details about the estimation of cross-
linking density is given in the ESI,{ Fig. S1.
Microscopic characterization
Silica distribution in the membrane phase was studied by a
JEOL 1200EX transmission electron microscope (TEM). The
JEOL 1200EX transmission electron microscope with a
tungsten electron source operated at an accelerating voltage
up to 120 kV. Scanning electron microscopy (SEM) images
were recorded by Leo microscope (Kowloon, Hong Kong)
after gold sputter coatings on dried membrane samples (1 and
0.1 Pa). Composition of silica and other elements, were
detected by energy-dispersive X-ray (EDX) measurements,
using a LEO VP1430 and an Oxford Instruments (Oxfordshire,
UK) INCA.
Ion-exchange capacity (IEC)
Detailed methods for estimation of membrane IEC is included in
the ESI,{ Fig. S2.
Water uptake, state of water, and membrane stabilities
Detail about methodology used for estimation of water uptake
and state of water is given in the ESI{(Fig. S3). Methods used for
dimensional, oxidative and hydrolytic stabilities studies of
developed membranes are included in the ESI{ (Fig. S4).
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Membrane conductivity studies
Conductivity of ZIMs (at different relative humidity (RH)) was
measured by four-probe Ac impedance spectroscopy using a
potentiostat/galvanostat frequency response analyzer (Auto Lab,
Model PGSTAT 30). Prior to measurement, the membrane
samples were soaked in deionized (DI) water for 24 h and rinsed
repeatedly to remove the last trace of free acid or base. The
membranes were mounted between two platinum electrodes (4.0
cm
2
), which were then placed in DI water to ensure 100% RH.
Direct current (DC) and sinusoidal alternating currents (AC)
were supplied to the respective electrodes for recording the
frequency at a scanning rate of 1 mA s
21
within a frequency
range 10
6
to 1 Hz. Membrane conductivity (k
m
) was estimated
from the following equation.
k
m
~
d
RA
(1)
Where d is the distance between electrodes, A is the cross-
sectional area of membrane and R is the membrane resistance
obtained from AC impedance data (the real part of the
impedance at high frequency, i.e. intercept of the impedance
semicircle with the Z-axis on the complex plane).
Electro-osmotic permeability measurements
Electro-osmotic permeability for different ZIMs was measured
in a two-compartment membrane cell (effective membrane area:
20.0 cm
2
), in equilibration of 0.01 M HCl solutions. Both the
compartments were kept under constant agitation by means of a
mechanical stirrer. A known potential was applied across the
membrane using Ag/AgCl electrodes, and subsequently volume
flux was measured by observing the movement of liquid in a
horizontally fixed capillary tube of known radius. The current
flowing through the system was also recorded with the help of a
digital multimeter. Several experiments were performed to obtain
reproducible values.
Methanol permeability
The methanol permeability of the composite membranes was
determined in a diaphragm diffusion cell, consisting of two
compartments (50 cm
3
) separated by a vertical membrane with a
20 cm
2
effective area. The membrane was clamped between both
compartments, which were stirred during the experiments.
Before the experiment, the membranes were equilibrated in a
watermethanol solution for 12 h. Initially, one compartment
(A) contained a 30 or 50% (v/v) methanolwater mixture and the
other (B) contained double distilled water. Methanol flux arises
across the membrane as a result of the concentration difference
between the two compartments. The increase in the methanol
concentration with time in compartment B was monitored by
measuring the refractive index using a digital refractometer
(Mettler Toledo RE40D refractometer). The methanol perme-
ability (P) was finally obtained by the equation:
P ~
1
A
C
B
(t)
C
A
(t {t
0
)
V
B
l (2)
where A is the effective membrane area, l the thickness of the
membrane, C
B
(t) the methanol concentration in compartment B
at time t, C
A
(t 2 t
0
) the change in the methanol concentration in
compartment A between time 0 and t, and V
B
the volume of
compartment B. All experiments were carried out at room
temperature, and the uncertainty of the measured values was less
than 2%.
Membrane electrode assembly (MEA) and DMFC performance
Gas diffusion electrodes (three-layer structure) were prepared
by: (i) wet proofing of carbon paper (Toray Carbon Paper,
thickness: 0.27 mm, wet proofed with 15 wt% PTFE solution by
brush painting method); (ii) coating of gas diffusion layer
(GDL) on to the carbon paper; (iii) coating of catalyst layer on
to the GDL.
27
The GDL (25 cm
2
) was fabricated by coating of
slurry (0.95 mg cm
22
) containing carbon black (Vulcan
XC72R) and PTFE dispersion on carbon paper. The anode
was made by coating slurry consisting catalyst (20 wt% Pt +
10 wt% Ru on carbon), 5 wt% Nafion ionomer solution,
isopropanol, and Millipore water (catalyst ink) on GDL had a
loading of 1 mg Pt and 0.5 mg Ru. The cathode was obtained by
coating the Pt catalyst ink with the same loading. Electrodes
were cold pressed with the membrane and cured at 60 uC for
12 h, followed by hot pressing at 130 uC for 3 min at 1.2 MPa.
Obtained MEA was clamped in single cell (FC25-01 DM fuel
cell).
The currentvoltage polarization curves were recorded with
the help of MTS-150 manual fuel cell test station (ElectroChem
Inc., USA) with controlled fuel flow, pressure and temperature
regulation attached with electronic load control ECL-150
(ElectroChem Inc., USA). The measurements were performed
in the air mode of operation at 10 psi pressure with a fixed
concentration of methanol fed at the anode side with pressure
7 psi at 70 uC for a representative membrane.
Results and discussion
Synthesis of multi-ionic silicon based copolymer and ZIM
Multi-ionic ZI silica precursor was synthesized by 3-(2-amino
ethyl amino) propyl trimethoxysilane (AAPTMS) and 1,4-
butanesultone via a ring opening reaction under heating
conditions, Fig. 1. Because of the exothermic reaction, tempera-
ture was carefully monitored because of the volatile nature of the
solvent (THF). Bands observed at 1039 cm
21
in the FTIR
spectrum confirmed sulfonate groups, while hydrated sulfonic
acid groups in multi-ionic ZI silica precursor absorbed at
14711163 cm
21
(Fig. 2). This indicates that both functional
groups were present in the ZI silica precursor.
52,53
A sharp peak
observed at 1643 cm
21
and a broad absorbance between
30252500 cm
21
, also confirmed the presence of a substituted
quaternary ammonium group. The ZI silica precursor shows
strong intensity bands at 1211 cm
21
which confirmed the
presence of SiOR groups. The ZI silica precursor was
zwitterionic in nature confirmed by the presence of two sharp
peaks at 604 and 525 cm
21
. The ZI silica precursor was
characterized by
1
H-NMR in D
2
O solution as shown in Fig. 3. A
triplet peak observed ca. 4.5 ppm indicates that the butanesul-
tone ring was opened and formed sulphonic acid groups.
Without ring opening this peak was not observed. The other
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proton signals are clearly represented in Fig. 3. The ZI silica
precursor was further characterized by
13
C NMR in D
2
O
solution and signals were observed at 10.56, 13.37, 21.01,
23.72, 24.23, 26.41, 31.68, 32.34, 48.38, 50.18, 51.63, 55.45,
60.59, 62.07 ppm and shown in (Fig. 4A). X-Ray diffraction
pattern data show that the ZI silica precursor is an amorphous
powder shown in (Fig. 4B). On the basis of spectral and
elemental analysis data the structure of ZI silica precursor was
confirmed and is shown in Fig. 1.
ZIMs were prepared by condensation polymerization of a ZI
silica precursor by an acid catalyzed solgel process in aqueous
media using PVA (Fig. 1). The obtained gel was transformed
into a thin film and cross-linked by HCHO in the presence of
acid at 60 uC for 3 h. Cross-linking occurs in two steps: (i)
formation of hemiacetal by reacting HCHO with OH groups of
PVA; (ii) further reaction of hemiacetal with the OH of PVA
and formation of acetal. Membranes lose their transparent
nature in wet conditions after cross-linking, but retain it in dry
conditions. The stable nature of ZIMs was achieved by
molecular level tailoring of the solgel process, in which organic
and inorganic segments were joined covalently.
The silica precursor and water forms a single phase solution in
the acid catalyzed solgel process, and solution-to-gel transition
was responsible for the silica (SiO
2
) network attached to the
organic matrix. The reaction mechanism proceeds through
bimolecular nucleophilic substitution and the nature of the
catalyst affects the membrane properties. Because of rapid
protonation of OR or OH substituents, directly attached to the
Si atom, sufficient numbers of interconnected SiOSi bonds
formed a three-dimensional cluster or a gel.
54
Linear and weakly
cross-linked polymer clusters formed in acid catalyzed solgel
reaction because of steric crowding. The obtained membrane
showed good mechanical, thermal and electrochemical proper-
ties. Presence of SO
3
H groups was confirmed because of a sharp
intensity absorption band near 11001037 cm
21
and multi
headed bands in the region of 14601360 cm
21
(Fig. 5).
Quaternary ammonium groups in ZIM were confirmed by peaks
between 16401540 and 30002800 cm
21
. A medium intensity
broad peak between 34003300 cm
21
indicated the presence of
quaternary ammonium salt in the ZIM phase.
53
Formation
of a cyclodiether part (COC) and cross-linked membrane
structure was confirmed by an absorption band between 1170
1030 cm
21
. Absorption band for about 10401150 cm
21
confirmed SiOSi and SiOC groups in the membrane matrix,
as a result of condensation reaction between hydrolyzed silanol
(SiOH) groups.
55,56
The structural features for multi-ionic ZI silica precursors are
similar to a vine from a bionic aspect. The main chains are
comparable to the stems of vine, while branched chains are like
branches of a vine, and are beneficial for the flexibility of the
Fig. 1 Scheme for the synthesis of ZI silica cross-linking agent and its structural similarity from a bionic aspect.
1952 | RSC Adv., 2012, 2, 19491961 This journal is The Royal Society of Chemistry 2012
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Fig. 2 FTIR spectra for a multi-ionic ZI silica precursor.
Fig. 3
1
H NMR of a multi-ionic ZI silica precursor.
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Fig. 4 Multi-ionic ZI silica precursor (A)
13
C NMR in d
6
-DMSO (B) XRD.
Fig. 5 ATR-FTIR spectrum for Si70% ZIM.
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cross-linked ZIMs. Multi-ionic ZI silica precursors contain
plenty of acidic and basic functional groups (SO
3
H and
N
+
(CH
3
)
3
Cl
2
). Functional groups were comparable to the
fruits of vine with controllable charge density, while Si(OCH
3
)
3
groups were similar to acetabulas of vines with high cross-linking
abilities.
Microscopic characterizations
High contents of organic moiety (PVA) and a relatively larger
amino propyl group were responsible for the formation of the
worm-like structure. In case of the membrane, 50 nm fine slices
were obtained with the help of a microtome cutter. The TEM
images show a worm like arrangement in membrane matrix and
silica particles are equally distributed in the membrane shown in
Fig. 6. SEM images of representative ZIMs (Si50% and Si70%)
are present in the ESI{ (Fig. S1). Excellent compatibility between
organic and inorganic phases suggests that the multi ionic ZI
silica precursor is an effective cross-linking agent for PVA,
because cross-linking occurred through covalent and hydrogen
bonds. Some aggregations on the membrane surface were
observed because accelerated hydrolysis of silica precursor, with
increase in ZI silica precursor content. Absence of phase
separation, cracks or holes on the membrane surface suggested
a homogeneous and dense nature of ZIM.
Thermal and mechanical stabilities
TGA curves for ZIMs in the H
+
state show similar weight loss
patterns (Fig. S2, ESI{). Three weight loss steps attributed to
water loss (loose and bound) at 50160 uC (5 to 8% of the initial
weight), defunctionalisation at 260370 uC (1218% of initial
weight), and membrane matrix degradation beyond 400 uC. Si
70% membrane showed comparatively minimum weight loss, for
which a high degree of cross-linking was responsible. Further-
more, high thermal stabilities of developed ZIMs indicate
advantages of covalently bonded functional groups and cross-
linking.
DSC thermogram for ZIMs (Fig. S3, ESI{) showed 118.35,
117.78, 109.59 and 107.81 uC first endothermic peaks (T
g
) and
second endothermic peaks at 174.1, 176.2, 179.4 and 231.4 uC
for Si50%, Si55%, Si60%, Si70% membranes, respectively.
Incorporation of a multi-ionic ZI silica precursor in the polymer
matrix had a profound effect on T
g
values. Variation in T
g
values
may be explained because of a plasticizing effect of the binder
(PVA) and alteration in its ordered arrangement with an increase
in ZI silica precursor content in the membrane matrix. This
observation indicates a highly cross-linked structure for ZIM at
elevated temperature. Here, it is interesting to note that T
g
for
pristine PVA is 78 uC.
57
Mechanical properties of the membranes (modulus and
strength) were analyzed by DMA curves (Fig. S4, ESI{).
Elongation of ZIMs increased with ZI silica precursor content,
and Si50% showed maximum stress tolerance which may be
explained in terms of the enhanced cross-linked nature of Si50%
membrane. Hydroxyl groups of PVA contributed towards
hydrogen bonding and stiffness of the polymer chain. With the
decrease in number of hydroxyl groups (because of its
involvement in either branching or cross- linking), the hydrogen
bonding was attenuated and thus the chain stiffness was reduced.
In addition, SiOH groups formed inter and intra molecular
cross-linked structures with PVA and a high content of ZI silica
precursor in polymer matrix produced agglomerates. Cross-
linking density, determined by DMA studies (Fig. 4S, ESI{), and
decreased with ZI silica content in the membrane matrix.
Variation in cross-linking density may be explained by formation
of cohesive domains in the ZIM matrix. This seems to be more
predominant than cross-linking with a plasticizer. Thus it is
necessary to optimize the ZI silica content in the membrane
matrix and cross-linking density for achieving better mechani-
cally stable ZIMs.
Oxidative, hydrolytic and acidbase stabilities
Stability and durability for membranes under stressed conditions
are important to explore their practical applications in electro-
chemical processes. Membrane oxidative stability was evaluated
by its treatment in Fentons reagent (3% aq. H
2
O
2
+ 3 ppm
FeSO
4
) at 80 uC for 1 h and recording oxidative weight loss
percent (W
ox
) (Table 1). The Si50% membrane exhibited the
Fig. 6 TEM image of a ZI-60 membrane (a) low magnification (b) high magnification.
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lowest weight loss, which increased with ZI silica content in the
membrane matrix. Because of cross-linking, hydrophilic
domains turned compact and
?
OH and
?
OOH radicals (short
life time) cannot penetrate inside the siloxane containing
domains. Thus, Si70% membrane with low cross-linking density
exhibited high weight loss. Methylene groups in PVA are
sensitive to free radical attack and cause chain degradation.
ZIMs were also subjected to an accelerated hydrolytic stability
test at 120 uC and 100% RH for 24 h. Hydrolytic stability test
results showed increased weight loss with a ZI silica precursor
(Table 1) and membranes retained their transparency, flexibility
and toughness.
Acidbase stability for developed ZIMs were tested for 5 h
equilibration in acid (HCl) and base (NaOH) solutions of
different concentrations and resulting weight loss data are
presented in (Fig. 5S, ESI{). Data confirmed the stabilities of
ZIMs in 5 M HCl and 7 M NaOH, as weight loss under these
conditions was less than 3%. Weight loss for the Si70%
membrane was comparatively high under acidic and basic
conditions, and may be because of more ZI content and thus a
posses a high level of functionality.
Stability of ZIMs (containing sulfonic acid and amine groups)
in strong alkaline solution is highly concerning,
58
because
quaternary ammonium groups are relatively unstable in alkaline
solutions due to direct nucleophilic substitution and Hofmann
elimination.
59
Prepared ZIMs were immersed in 5 mol L
21
NaOH solution for 100 h to investigate stability of alkaline
functional groups. Ratios of IEC
t
(IEC of base treated ZIM at
time t) and IEC
0
(IEC of untreated ZIM) were recorded, Fig. 7.
All lines drop rapidly in 025 h (first stage), then attain a level in
0100 h (second stage). It seems ZIMs contain some quaternary
ammonium groups, which undergo Hofmann elimination under
the treatment with a strong base. Estimated from IEC
0
and IEC
t
at 25 h, the percentage of unstable quaternary ammonium
groups was found to be 15.4%, 10.6%, and 2.9% for Si70%, Si
60%, and Si50%, respectively. Presence of this group may be
attributed to insufficient cross-linking because of high swelling
or water uptake (Si70% membrane). After the degradation of
these components, loss in membrane IEC was nearly constant.
This study reveals the membrane stability under strong alkaline
media against Hofmann degradation, and their suitability for
electro-membrane processes. The formation of base in the
cathode compartment occurs because of reductive water
splitting.
Water uptake, dimensional changes and water retention capability
Membrane water uptake has a profound effect on its proton
conductivity, mechanical and dimensional properties.
60
Presence
of water molecules in the membrane phase facilitates the
dissociation of functional groups and is essential for high
membrane conductivity. On the other hand, high water volume
fraction in the membrane phase reduces its dimensional and
thermal stabilities along with ionic concentration in the
membrane phase. Water uptake values (Q
w
) increased with ZI
content for ZIMs (Table 1), because of the enhanced hydrophilic
nature of the membrane matrix. Water uptake profiles for
different ZIM at elevated temperature were also studied, and
increased linearly up to 80 uC. In this case, the extent of
plasticization and hydrophilic nature of the matrix play an
important role for water uptake. At low extent of plasticization
(high ZI content) the flexible polymer network permits larger
water uptake.
61
Membrane water uptake values significantly depend upon the
void porosity of the membrane. Fig. 6S, ESI{ shows the effect of
void porosity on the water uptake properties. The results
revealed that with the increase in membrane void porosity water
uptake values increase. Total number of water molecules per
ionic site (l
w
) (Table 1) data also support a highly cross-linked
and hydrophilic membrane matrix at high ZI content. The lowest
number of water molecules per ionic site for Si70% membrane
revealed its highly cross-linked structure with small void volume.
The water vapor sorption and water diffusion properties of
ZIMs affect their conductivity and applicability for electro-
chemical processes. Furthermore, the water retention capability
of membranes is helpful to assess their suitability for desired
applications. Water retention capability of ZIMs was illustrated
in (Fig. 8A) (M
t
/M
o
)t (time) curves, and deswelling kinetics of
the developed membranes was calculated. The value of k
(constant) was derived from (M
t
/M
o
)t
1/2
curves (Fig. 8B) based
on Higuchis model for water desorption kinetics:
Table 1 Water uptake
a
(Q
w
), number of water molecules per ionic site (l
w
), swelling in water (W
v
), oxidative, hydrolytic weight loss
b
(W
OX
& W
HS
respectively), and water diffusion coefficient (D) values for different ZIMs
Membrane code Q
w
(wt%) l
w
/SO
3
2
W
v
(vol%) W
OX
(wt%) W
HS
(wt%) D/10
26
(cm
2
s
21
)
Si50% 28.0 20.9 26.0 5.3 5.9 3.26
Si55% 31.4 17.8 28.0 7.8 8.4 2.42
Si60% 35.9 16.5 32.3 8.3 9.5 1.87
Si70% 40.6 14.9 34.9 9.3 10.9 1.31
a
Uncertainty in the measurements of 1 : 0.1%.
b
Uncertainty in the measurements of 2 : 0.01 mg.
Fig. 7 Alkaline resistance of different ZIMs: ratios IEC
t
/IEC
0
over the
immersion time in 5 mol L
21
NaOH at room temperature.
1956 | RSC Adv., 2012, 2, 19491961 This journal is The Royal Society of Chemistry 2012
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M
t
=
M
0
~ {kt
1
=
2z1 (3)
where M
0
and M
t
are the initial amount of water and remaining
water in polymer matrix at given time and k is a constant.
The obtained straight lines for different ZI contents were fitted
to Higuchis model, and suggested a diffusion controlled water
desorption mechanism. The water desorption rate was reduced
with ZI content, thus ZI acted as a water binder in the membrane
matrix and is responsible for formation of hydrophilic channels
and cross-linked chains. Water diffusion coefficients (D) across
ZIMs were also evaluated from a best-fit normalized mass
change (Table 1) and were found to decrease significantly with
ZI content in the membrane matrix. Thus ZI acted as a water
release barrier and enhanced the membrane water retention
capacity.
State of water
In a membrane matrix, the presence of water may be classified
into three types: (i) free water (with the same temperature and
enthalpy of melting as bulk water); (ii) freezing bound water
(weakly bound with polar or ionic groups of the polymer and
shows change in temperature and enthalpy in comparison with
bulk water and can be detected by DSC); and (iii) non-freezing
bound water (very strong interaction with polar or ionic groups
and shows no phase transition). According to Eikerlings
theory,
62
the charged membrane possessed two types of water:
bound and bulk water. Bound water is necessary for the
solvation of ionic groups, whereas bulk water fills the void
volume. Low temperature DSC studies and water uptake values
were used to determine the state of water in the membrane phase.
DSC thermograms were recorded from 250 to +50 uC (Fig. 3S,
ESI{) as a broad endothermic peak of hydrated ZIMs. Enthalpy
of melting (DH
m
), melting temperature (T
m
), the full width at
half-maximum of the melting peak (DT
m
), freezing water (l
f
),
bound water (l
b
) and bound water degree (x) were estimated
from DSC curves and presented in Table 2. Increase in DH
m
with
ZI content was attributed to low freezing and less bound water
percentage of the ZIMs.
Freezing water (l
f
) for ZIM was obtained by total melting
enthalpy by integrating melting curves peak area (Fig. S3, ESI{).
Also, bound water percentage (l
b
) was obtained by subtracting
freezing water content from total water in the membrane matrix.
The degree of bound water in percentage (x = l
b
/l
w
) was
estimated by the ratio of number of bound water molecules and
total water. Free water increased with ZI content in the
membrane matrix, while bound water reduced because of the
enhanced availability of ionic sites for binding. Reduction in
bound water with ZI content may be attributed to strong
interactions between ionic groups and water molecules which
effectively predominates over the siloxane network.
IEC and surface charge concentration
IEC indicates density of dissociable ionic groups in the
membrane matrix, which are responsible for ion conduction
across the membrane. ZIM contains both types of functional
groups: acidic (SO
3
2
H
+
) and basic (quaternary ammonium),
which contribute towards IEC. Acidic and basic IEC values for
different ZIMs were estimated by the titration method (Table 3).
Fig. 8 Water desorption profile for ZIMs: (A) isotherm at 40 uC; (B)
Higuchis model fit of the deswelling behavior.
Table 2 State of water: enthalpy of melting (DH
m
), melting temperature (T
m
), full width at half-maximum of the melting peak (DT
m
), glass transition
temperature (T
g
), total number of water molecules per ionic site (l
t
), number of free water molecules per ionic site (l
f
), number of bound water
molecules per ionic site (l
b
), and degree of bound water (x) for different ZIMs
Membrane DH
m
(J g
21
) T
m
a
(uC) DT
m
b
(uC) T
g
l
t
l
f
l
b
x
c
(%)
Si50 5.35 25.3 9.99 118.35 20.9 1.20 19.70 94.26
Si55 7.81 24.1 12.33 117.78 17.8 1.32 16.48 92.58
Si60 10.74 23.4 14.1 109.59 16.5 1.48 15.02 91.14
Si70 14.72 21.1 14.8 107.81 14.9 1.62 13.28 89.73
a
Melting temperature of free and loosely bound water.
b
Full width at half-maximum of the melting peak.
c
Bound water degree x (%) = l
b
/l
t
.
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Both types of IEC increased with ZI content in the membrane
matrix, and confirmed the good zwitterionomer nature of the
membrane. Here, it is interesting to note that the Si70%
membrane showed 1.512 m equiv./gm IEC for acidic functional
groups (SO
3
2
H
+
), while world-wide used acidic Nafion-117
membrane showed 0.910 m equiv./gm, IEC. Similarly, Si70%
membrane showed 0.827 m equiv./gm alkaline IEC, whereas
Neosepta membrane showed 1.201.40 m equiv./gm alkaline
IEC.
62
IEC studies confirmed the highly charged and zwitter-
ionic nature of developed ZIMs.
Surface charge concentrations (X
m
) for different ZIMs were
estimated by the following equation.
X
m
~
t IEC r
d
Q
w
(4)
Where t is membrane void porosity, r
d
is the density of the dry
membrane, and Q
w
is the volume fraction of water in the
membrane matrix. From acidic and basic IEC values, X
m
values
for acidic and basic functional groups for different ZIMs were
also included in Table 3. Data support the schematic structure of
ZIM (Fig. 1) and confirmed the presence of strongly dissociable
functional groups (sulfonic acid and quaternary ammonium) in
the membrane matrix.
Conductivity of ZIMs
Conductivity of ZIMs (k
m
) was measured under 100% relative
humidity at 30 uC (Table 4), increased with ZI content in the
membrane matrix and thus has a high concentration of
functional groups. With enhanced ZI content in the membrane
matrix, high Q
w
values affect hydrogen bonding and thus
membrane conductivity, because of increased surface charge
concentration. Results support that charged sites of ZIMs
enhanced the hydrophilic nature of the matrix and promoted
exchange of ions, which helped for conduction. Fig. 9 shows the
variation of k
m
with enthalpy of melting (DH
m
) in equilibration
with 0.5 M NaCl solution. DH
m
depends on the free water
content in the membrane matrix responsible for membrane
conductivity. High extent of free water in the membrane phase
provides easy conduction of counter-ions. Thus, for highly
conductive membrane, designing a precursor with high extent of
free water is necessary. The designed ZI precursor contains two
acidic and basic functional groups in a molecule and provides a
highly charged matrix with appreciable free water content.
Knowledge of a membranes water retention capacity is also
helpful to assess the membrane conductivity at high temperature.
Membrane conductivity values at high temperatures (30 to
100 uC) under 100% RH are presented as an Arrhenius plot (Fig.
S5, ESI{) for the estimation of activation energy (E
a
), using the
following expression,
ln k
m
~{
E
a
RT
(5)
Where R is the universal gas constant (8.314 J mol
21
K
21
),
and T is the absolute temperature. E
a
values increased with the
ZI content in the membrane matrix (Table 4), and varied
between 3.644.29 kJ mol
21
. As a reference Nafion 117
membrane showed 6.52 kJ mol
21
activation energy. It seems
ion transport across ZIMs followed a conduction mechanism
similar to Nafion 117 (Grotthus type conduction mechanism).
Membrane conductivity (Si50% and Si70%) depends on its
relative humidity (Fig. 10). Conductivity decreased with a
decrease in the RH (%) of membranes. At 100% RH, the Si
70% membrane showed 0.0967 S cm
21
conductivity, which was
reduced to 0.043 S cm
21
at 25% RH. Furthermore, these ZIMs
(especially Si70%) retained conductivity under relatively low
hydrated conditions.
Electroosmotic permeability studies
Electro-osmotic transport of mass (solvent) across charged
membranes revealed their mass electro-driven mass transport
properties and equivalent pore radius. Electro-osmotic flux
across ion exchange membranes occurred due to: (i) the
availability of ionic sites in the membrane matrix and (ii) the
existence of an electrical potential at the membranesolution
Table 3 Acidic and basic IECs by titration methods (IEC
tit
), and their surface charge concentration (X
m
) for different ZIMs
Membrane Code
Acidic functional groups Basic functional groups
IEC
tit
a
(m equiv./gm) X
m
(m mol dm
23
) IEC
tit
a
(m equiv./gm) X
m
(m mol dm
23
)
Si50% 0.743 0.931 0.424 0.531
Si55% 0.983 1.222 0.568 0.706
Si60% 1.212 1.606 0.734 0.972
Si70% 1.512 2.004 0.827 1.096
a
Uncertainty in the measurement was: 0.001 m equiv./g.
Table 4 Membrane conductivity
a
(k
m
), electroosmotic permeability (J
E
), and activation energy (E
a
), for different ZIMs
Membrane code k
m
/10
22
(S cm
21
)
a
J
E
/10
25
(cm s
21
A
21
)
b
E
a
(kJ/mol) r (nm)
Si50% 5.97 1.07 3.64 15.33
Si55% 7.01 1.16 3.79 16.88
Si60% 8.42 1.34 4.04 18.74
Si70% 9.67 2.34 4.29 19.23
Nafion 117 9.56 14.01 6.52
a
Uncertainty in the measurement was: 0.01 6 10
22
S cm
21
.
b
Uncertainty in the measurement was: 0.01 6 10
25
cm s
21
A
21
.
1958 | RSC Adv., 2012, 2, 19491961 This journal is The Royal Society of Chemistry 2012
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interface called zeta potential.
63,64
Knowledge of ion and
solvent transport rates across the membranes under electro-
driven conditions is necessary for intelligently designing a
better membrane for desired electro-membrane processes.
65
Electro-osmotic flux across ZIMs in equilibration with 0.02 M
NaCl solution (Fig. S6, ESI{) was used for the estimation of
electro-osmotic drag (b) (implies that every coulomb of
electricity will exert a drag sufficient to carry b cm
3
of water
through 1 cm
2
of the membrane area). Equivalent pore radius
(r) for membranes was estimated from the Katchalsky and
Curran approach:
63
r~
8gFb
f
0
1w

1
=
2
(6)
where F is the Faraday constant, g denotes the coefficient of
viscosity of the permeate, and f
0
1w
is the frictional coefficient
between the counter-ion and water in free solution, which can
be defined as f
0
1w
= RT/D
i
, (where D
i
is the diffusion coefficient
of the single ion (i) in the free solution, R is the gas constant,
and T is absolute temperature). The ionic diffusion coefficient
(D
i
) at a given electrolyte concentration was obtained from
ionic conductivity data.
57
Equivalent pore radii (r) for ZIMs
suggest their dense nature and increased with ZI content in the
membrane matrix (Table 4). This information also supports our
earlier observations that in ZIMs, hydrophilic, charged and free
water content increased with ZI content. Thus it is necessary to
optimize the ZI content for desired electro-membrane applica-
tion for ZIMs.
Methanol permeability and selectivity parameter
ZIMs showed extremely low methanol permeability transmission
[(0.952.31) 6 10
27
cm
2
s
21
] compared with the Nafion117
membrane (13.10 6 10
27
cm
2
s
21
) (Fig. 11(A)). The mass-
transport behavior for a hydrated ZIM depends on its degree of
swelling, water uptake, and bulk microstructure. Methanol
permeability values increased with ZI content in the membrane
matrix. Incorporation of silica containing ZI precursor into the
Fig. 10 Conductivity of ZIMs (Si70% and Si50%) at different RH.
Fig. 9 Variation of k
m
with DH
m
in equilibration with 0.5 M NaCl
solution for different ZIMs and (inset) variation in membrane
conductivity with different loading of zwitterionomer.
Fig. 11 (A) Methanol permeability (P) and (B) selectivity parameter (SP) values as function of ZI content in the membrane matrix for different ZIMs
and Nafion 117 membrane.
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polymer membranes dramatically altered the membrane trans-
port properties because of alteration in the free void volume and
ionic clusters. Thus, understanding the relationship between
the polymer structure and membrane performance, in terms
of permeability and selectivity, enables the tailoring of the
membrane structure for specific purposes. Permeation of liquid/
gas molecules through the polymer membrane occurs via the
diffusion mechanism, and the permeability of the penetrant
(methanol) is the product of its solubility and diffusivity. The
penetrant diffusivity is dependent on the free void volume in the
membrane, the size of the penetrant molecules, and the
segmental mobility of the polymer chain.
To directly compare the applicability of ZIMs for DMFC, the
ratio of the proton conductivity and methanol permeability (k
m
/
P) data was used as the selectivity parameter (SP). SP values for
nanocomposite and N117 membranes are also presented in
Fig. 11(B). The Si50 membrane exhibited the highest SP value
(6.28 6 10
5
S cm
23
s) among the prepared ZIMs. The SP value
decreased with ZI content in the membrane matrix. In similar
conditions, the N117 membrane showed an SP value of 0.73 6
10
5
S cm
23
s. It was also noticed that, with an increase in the
operating temperature, SP values for ZIMs were also increased.
This observation may be attributed to the relatively low
methanol permeability of ZIMs. These results can be explained
on the basis of the lack of significant interactions between
methanol and functional groups. Ionized groups hydrate
strongly and excluded organic solvents (salting-out effect), which
is an essential feature of the polyelectrolyte membranes.
Furthermore, higher SP values of these membranes indicate a
great advantage for DMFC applications.
DMFC performance
DMFC performance for representative PEMs (Si50% and Si
70%) was tested in a single cell and compared with Nafion117
membrane at 70 uC (Fig. 12). The Si70% membrane showed
0.95 V open circuit voltage (OCV), while Nafion exhibited
0.497 V, under similar experimental conditions. The current
densities at a potential of 0.20 V for Si70%, and Nafion117 (79.5
and 73.6 mA cm
22
, respectively) indicated a comparable DMFC
performance of ZI and Nafion117 membranes. Good performance
of the Si70% membrane was observed due to extremely low
methanol permeability in spite of its lower proton conductivity. Si
70% membrane showed 16.1 mW cm
22
maximum power density,
whereas for Nafion117showed 13.7 mW cm
22
. These results
indicated suitability of ZIMs for DMFC applications.
Conclusions
Multi-ionic silicon copolymer via ring opening reaction was
developed as cross-linking agent for preparing stable zwitterionic
organicinorganic hybrid membranes. The prepared ZI silica
precursors contain sulfonic acid and amine groups (two number
each per molecule), which rendered its ZI nature because of
proton transfer. The structure of the ZI silica precursor is similar
to a vine from a bionic aspects with a long main chain, and
branched chains with large numbers of sulfonic acid, amine and
Si(OCH
3
)
3
groups. All these are desired properties for designing
a stable, homogeneous, and flexible ZIM by a solgel process in
aqueous media using a suitable water soluble plasticizer (PVA).
Developed membranes showed good stability, flexibility, water
uptake, and retention capacity. Incorporation of ZI in the
membrane matrix improved the thermal stability of ZIMs, which
were thermally stable up to 200 uC in a dry nitrogen atmosphere.
Among the developed ZIMs, Si70 exhibited a higher acidic IEC
value (1.512 m equiv g
21
), water uptake (40.6%), and proton
conductivity (9.67 6 10
22
S cm
21
). Comparable conductivity for
Si70 membrane with Nafion 117 membrane, confirmed the
suitability of ZIMs for fuel cell applications. Reported data are
promising to design highly conducting acidbase composite
systems. Furthermore, relatively lower methanol permeability
and SP values of these membranes make them applicable for
DMFC. The acidbase composite material may have potential
applications not only for the DMFC operated at intermediate
temperatures under anhydrous (water-free) or extremely low
humidity conditions but also for novel electrochemical devices,
where water activity is not required.
Acknowledgements
Financial assistance received from the Department of Science
and Technology, New Delhi (Govt. of India), by sponsoring
project no. SR/S1/PC/06/2008 is gratefully acknowledged.
Instrumental support received from Analytical Science
Division, CSMCRI, is also gratefully acknowledged.
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