Energy 88 (2015) 202e208

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Energy
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A study of inuence on nanocomposite membrane of sulfonated

TiO2 and sulfonated polystyrene-ethylene-butylene-polystyrene
for microbial fuel cell application
Sivasankaran Ayyaru, Sangeetha Dharmalingam*
Department of Mechanical Engineering, Anna University, Chennai 600 025, India

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 14 August 2014
Received in revised form
26 March 2015
Accepted 2 May 2015
Available online 27 June 2015

Microbial fuel cell (MFC) is a device that uses bacteria as a catalyst to oxidize various substrates for
simultaneous electricity generation and wastewater treatment. In the present work, (sulfonated TiO2
(S-TiO2)/polystyrene ethylene butylene polystyrene) SPSEBS nanocomposite membranes were prepared
by solution casting. The IEC (ion exchange capacity), water uptake, proton conductivity and MFC performance of the composite membranes were explored. SPSEBS-S-TiO2 membrane (7.5%) exhibited the
highest IEC value, water uptake and proton conductivity capacity. The results revealed that the incorporation of sulfonated TiO2 improved the proton conductivity of the SPSEBS membrane effectively and
exhibited the highest peak power density of 1345 17 mWm
2 for SPSEBS-S-TiO2 7.5%, when compared
to 695 7 mWm
2 and 835 8 mWm
2 obtained for SPSEBS and SPSEBS-TiO2 membranes respectively
in a (single chambered microbial fuel cell) SCMFC. In comparison to previously reported work with
Naon (300 10 mWm
2) in MFCs, the composite membrane delivered more than 4-fold higher power
density. The oxygen mass transfer coefcient (KO) of nanocomposite membranes decreased with
incorporation of the sulfonated TiO2 which in turn increased the (columbic efciency) CE.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Microbial fuel cell
Nanocomposites
Metal oxides
Proton conductivity
Sulfonated TiO2
Proton exchange membrane

1. Introduction
The problem of global climate change caused by greenhouse
gases and environmental pollution has forced researchers and
manufacturers to search for alternative sources of energy.
[1]. In order to reduce the impact on environment and to
stimulate sustainability, new energy efcient and renewable energy systems are being considered effectively [2]. Number of
research and development programmes has been focused in this
area; especially on MFCs. Microbial Fuel cells are very promising
energy conversion devices that produce electricity from various
organic matters [3e5]. Single-chamber, airecathode MFCs have the
greatest potential for practical applications due to their simple
design and the direct use of oxygen in air [6]. The main challenges
for improving MFC (Microbial fuel cell) performance are increasing
power, increasing the recovery of electrons from the substrate
(Coulombic efciency; CE), and reducing material costs [7] in a way
that allows for scalable designs.

* Corresponding author. Tel.: 91 44 2235 7763; fax: 91 44 22357744.

E-mail address: sangeetha@annauniv.edu (S. Dharmalingam).
http://dx.doi.org/10.1016/j.energy.2015.05.015
0360-5442/ 2015 Elsevier Ltd. All rights reserved.

An ideal proton exchange membrane used in MFC should

facilitate the transfer of protons from anode to cathode while at the
same time it should inhibit the transfer of other materials such as
the fuel (substrate) and the electron acceptor (oxygen). Naon is
the widely used (proton exchange membrane) PEM in MFCs,
despite the existence of a number of problems associated with it
such as high cost, oxygen leakage, substrate loss, cation transport
(other than protons) [8e12]. The oxygen diffusion into the anode
compartment from cathode is a serious problem in an MFC, which
consumes electrons in the anode compartment, thereby reducing
the columbic yield and increases the substrate loss either by aerobic
respiration by facultative bacteria, or inhibits the growth of obligate
anaerobes [13]. To overcome these drawbacks we must choose an
alternate PEM.
Metal oxides have been extensively investigated as inorganic
additives in proton conducting membranes used as ionic separators
in polymer electrolyte membrane fuel cells (PEMFCs) [14,15]. In the
research of higher temperature proton-exchange membrane with
adequate performances at low (relative humidity) RH, various
compounds, such as SiO2, TiO2 and ZrO2, have been added to a
Naon matrix [16e20]. However, the excessive incorporation of
these nonconductive inorganic compounds in PEM normally results

S. Ayyaru, S. Dharmalingam / Energy 88 (2015) 202e208

in a decrease of proton conductivity. It was overcome by the

addition of metal oxides, in the form of nano or submicrometric
particles, which improved the water retention and the thermomechanical stability of the membranes [22].
In most cases the metal oxide composite membrane showed
better performance at high temperatures only. But at low temperature the PEM with fully humidied metal oxide could not
improve the proton conductivity than the pristine membrane. This
hygroscopic property could not always lead to a desired performance improvement under fully humidied condition. Most researchers thought that the proton conductivity of the composite
membranes under fully humidied condition was remarkably
reduced due to incorporating with these non-proton-conductive
hygroscopic metal oxides [18,21e25]. As far as MFC is considered, it operates at ambient temperature (30  C) under fully wet
condition. Here we need to increase the proton conductivity at
room temperature and wet condition. So the objective of increased
PEM conductivity can be achieved by adding proton conductive
acidic additives like sulfonated groups grafted metal oxide
(SeTiO2particles).
Always the hydrated membrane form gives better performance,
because the water molecules create a path for transport of protons.
But in case of high temperature the water molecules get evaporated
from the membrane. To retain the hydrated form of the membrane
at high temperature the metal oxides have been used. Sulfonated
groups of TiO2 not only create a path for proton transport but also
act as vehicle due to its negative charge. Whereas both metal oxide
(eOH group metal oxide) and water molecule can only create a path
for proton transport but cannot act as vehicle due to their neutral
charge.
Other types of very interesting compounds, to be effectively
used as membrane additives, consists of solid electrolytes such as
(heteropolyacids) HPAs [26]. Their conductivity is of the same order
of magnitude as that of mineral acids, around 0.02e0.1 S cm
1 at
room temperature, but the high afnity for polar media makes
them easily soluble [27]. Similar to HPAs, the sulfated metal oxides
have become subjects of intensive studies, being more stable than
other solid super acids. In general, the incorporation of inorganic
solid acids in conventional Naon-type membranes is of primary
interest, having the dual function of improving water retention as
well as providing additional acidic sites [28]. However, almost all of
these composite membranes reported in literatures were prepared
with Naon for HT-PEMFC only. In case of MFC, Naon has its own
drawbacks; hence we have selected SPSEBS as the base polymer
due its low cost and excellent properties [11,12]. In our previous
work with SPSEBS in MFC, it was found that SPSEBS procured 106%
higher performance than commercial Naon due its higher proton
conductivity and lower oxygen permeability [11]. In this paper,
SPSEBS-S-TiO2nanocomposite membranes were prepared for low
temperature MFC. The crystal structures of the composite membranes were characterized by (X-ray powder diffraction) XRD.
Proton conductivity was obtained from the electrochemical
impedance spectroscopy and single chamber-microbial fuel cell
performance of composite membranes was evaluated.
2. Materials and methodology
2.1. Preparation of sulfonated TiO2
TiO2 nanoparticles (25 nm) were purchased from Adrich, USA.
The sulfonated TiO2 was prepared using sulphuric acid according to
the method reported by Wang L et al. [29] Chang-Chun Ke et al. [30]
Chiu-Hsun Lin et al. [31]. One gram of TiO2 nanoparticles was added
to 15 ml of 0.5 M sulphuric acid under ultrasonication for 1 h. The
nal SeTiO2white powder was obtained by drying the solution at

203

100  C for 24 h. Sulfonation of TiO2 was conrmed by FTIR and

SEM-EDX in our previous work [32].
2.2. Preparation of nanocomposites
Sulfonated TiO2 with different content (0, 2.5, 5, 7.5,and 10 wt%)
was added into the SPSEBS/THF (tetrahydrofuran) solution, then
stirred mechanically and then degassed by ultrasonication. 7.5 wt%
of pure TiO2 with SPSEBS/THF matrix was prepared for comparison
purpose. The prepared mixture was slowly poured onto a glass dish
in an amount that would give a thickness of 180 5 mm for the
formed nanocomposite membrane. The glass dish was then
allowed to evaporate the solvent slowly. The membranes which
were thus obtained were designated as SPSEBS, SPSEBS-S-TiO2
2.5%, SPSEBS-S-TiO2 5%, SPSEBS-S-TiO2 7.5%, and SPSEBS-S-TiO2 10%
according to the weight percentage of the ller added.
2.3. Instrumental characterization
2.3.1. FT-IR spectrum analysis
FT-IR spectrum of the nanocomposite membranes was recorded
from 500 to 4000 cm
1 using an Alpha Bruker FTIR spectrometer
for conrming the increase in eSO3H functionality with respect to
increase in ller (SeTiO2) concentration.
2.3.2. Morphology observation
The membrane surface of the various composite membranes
was observed by means of JEM-5600LV (scanning electron microscope) SEM. All specimens were dried and coated with a thin layer
of gold before observation.
2.3.3. X-ray diffraction (XRD)
The XRD spectrum of membrane samples were recorded using
X Pert Pro diffracto meter. The scanning angle was 1e80 with
scanned at a rate of 1 min
1.
2.4. Water uptake
Water uptake properties of the nanocomposite membranes
were measured at room temperature. The (water uptake) Wut was
calculated from the (wet weight) Wwet and the (dry weight)
Wdry of the membranes using the following equation:
Wut (Wwet e Wdry) / Wdry  100%

(1)

The dry weight (Wdry) of the membrane was obtained after

drying the membranes in vacuum oven at 100  C for 12 h, and the
wet weight (Wwet) was obtained after removing the excess liquid
water from the soaked membrane surface through dipping in
deionized water for 24 h.
2.5. The ion exchange capacity
The (ion exchange capacity) IEC of nanocomposite was determined by the back-titration method. 1.0 g of the sample was soaked
in 20 ml of 0.5 M H2SO4 overnight to ensure that all the eSO3H
groups were exchanged with H ions. Then the H-formed sample
was washed with distilled water till the pH value was 7. The composite membrane was immersed in saturated potassium chloride
solution overnight, to allow replacement of protons with K ions.
Protons released from the membrane were neutralized by 0.01 N
sodium carbonate solutions. Phenolphthalein was used as the
indicator. The IEC was calculated using the following formula.

204

IEC

S. Ayyaru, S. Dharmalingam / Energy 88 (2015) 202e208

Titre value in ml  Normality of Na2 CO3

meq=g
weight of dry polymer membranein g

(2)

2.6. Membrane conductivity measurement

The conductivity of each composite membrane was measured
using ac impedance spectroscopy. An applied voltage of 10 mV and
a frequency range of 1 MHze100 Hz were employed using a
potentiostat (BioLogic VSP, France) electrochemical system. The
sample was soaked in water at ambient temperature (30  C) for
24 h and then sealed between two electrodes with an area of
0.62 cm2. The impedance measurement was then carried out. The
conductivity values were calculated using Eq. (3)

s L/RA

(3)

Where s is the proton conductivity of the membrane (S/cm), L is the

membrane thickness (cm), R is the membrane resistance (U) and A
is the area of the electrode (cm2) [29,31].
2.7. MFC studies
2.7.1. MFC construction and operation
The anode electrode used was 30 wt.% wet proofed carbon cloth.
The cathode was prepared using a carbon cloth having 0.5 mg cm
2
platinum coating as a catalyst. The MEA was prepared by sandwiching the composite membrane between the anode and cathode
electrodes as mentioned in our previous reports [11,21,32]. The
MEA was further assembled into a cylindrical single-chambered
MFC (28 mL) with the cathode-side of the MEA facing the air. The
anode chamber was lled with nutrient solution containing 1 g/L
glucose, 0.1 g/L yeast, 0.5 g/L NaCl, 0.28 g/L NH4Cl, 0.1 g/L, 0.68 g/L
KH2PO4, 0.87 g/L K2HPO4, having a pH of 7 which was then inoculated with wastewater that was collected from Anna University
sewage treatment plant (Chennai, India).
2.7.2. Analytical measurements and calculations
Cell voltage was recorded using a digital multimeter (Model 702,
Metravi, India). Polarization curves were obtained by varying the
applied external resistance at a time interval of 10 min. Current
density and power density were determined by Ohm's law [9,11].
. Oxygen mass transfer coefcients for each composite membrane were determined by following the protocol of O LefebVre
et al. (2009). The (dissolved oxygen) DO probe (Extech 407510A,
Taiwan) was inserted in an uninoculated MFC tted with the
desired composite membrane and lled with distilled water previously sparged with nitrogen gas to remove DO. The mass transfer
coefcient of oxygen in the membrane, KO (cm s
1) was determined
by monitoring the DO concentration over time and using Eq. (4):
KO
V/At ln [(COeC)/CO]

Internal resistance was characterized using (electrochemical

impedance spectrometer) EIS methods. The impedance measurements were taken from 500 kHz to 1 MHz by applying a sine wave
(10 mV rms) on top of the bias potentials with a potentiostat
((BioLogic VSP, France). The three-electrode mode is used to
analyze an individual electrode. To know the anode internal resistance, anode and cathode electrodes were used as working and
counter electrodes, respectively. The reference electrode was an
Ag/AgCl (KCl-sat.) electrode [33]. All tests were done in triplicates
and the average values were calculated.
3. Results and discussion
3.1. FTIR spectrum
Fig. 1 exhibits the FT-IR spectra of the SPSEBS, SPSEBS-TiO2,
SPSEBS-S-TiO22.5%, SPSEBS-S-TiO2 5%, SPSEBS-S-TiO2 7.5%, and
SPSEBS-S-TiO2 10%. It was slightly difcult to differentiate the
structural changes of the sulfonated composite membranes and
SPSEBS from Fig. 1. This was due to the presence of eSO3H groups in
the side chains of SPSEBS, that made it difcult for the identication
of the eSO3H attached to the surface of TiO2 nano-particles. The peak
at 3400 cm
1 was the characteristic signal of eOH. On increasing the
SeTiO2 concentration hydroxyl peaks were widened, due to the
eOH group of sulfonated TiO2. These results also revealed that the
hygroscopic property increased while adding sulfonated TiO2.
3.2. Morphology observation
The surface morphology was analyzed from scanning electron
microscope (Fig. 2). The inorganic particles appeared to have well
dispersed in both low and high wt % composites. The ller particles
were distributed relatively in a uniform fashion. The ller particles
were observed to be clearly embedded in the polymer matrix,
which established the connectivity in the composites. The SeTiO2
particles were dispersed homogeneously with the interspaces lled
with SPSEBS up to 7.5%, while the 10% TiO2 composite membranes
showed formation of agglomeration on the surface of the polymer
matrix. This implies that the prepared composite membranes (up to
7.5%) can be expected to perform consistently well in the MFCs.
From the images, it was observed that the concentration of llers
gradually increased from 2c to 2f in the sulfonated composite

(4)

Where, V is the liquid volume in the anode chamber, A is the

membrane cross-sectional area, CO is the saturated oxygen concentration in the cathode chamber, and C is the DO concentration in
the anode chamber at time t [9].
The Coulombic Efciency (CE) was calculated using following
Eq. 5
CE Cp/CT  100%

(5)

where, Cp is the total Coulombs calculated by integrating the current over time. CT is the theoretical amount of Coulombs that can be
produced from the amount of glucose which was degraded [9,11].

Fig. 1. FTIR spectra of various concentration of sulfonated composite membranes,

unsulfonated membrane composite and base membrane.

S. Ayyaru, S. Dharmalingam / Energy 88 (2015) 202e208

205

Fig. 2. SEM images of (a) SPSEBS, (b) SPSEBS-TiO2 (c) SPSEBS-S-TiO22.5%, (d) SPSEBS-S-TiO25%, (e) SPSEBS-S-TiO27.5% TiO2 and (f) SPSEBS-S-TiO210% composite membranes.

membranes. The unsulfonated composite membrane with 7.5% of

TiO2 represented by 2b also showed the presence of higher concentration of ller (see Fig. 2).
3.3. X-ray diffraction (XRD)
X-ray diffraction (XRD) analysis is an effective technique to study
the morphological information, especially the crystallinity of the
composite membranes. Fig. 3 shows the XRD patterns of SPSEBS,
SPSEBS-TiO2 and SPSEBS-S-TiO2 composite membranes. From the
XRD proles, it can be seen that on increasing the concentration of
sulfonated e TiO2 from 2.5% to 7.5 % the crystallinity of the composite
membranes decreased. This indicated that the presence of amorphous
domain in the sulfonated nanocomposite membranes which was
greatly decreased the crystallinity. The addition of TiO2 llers could
not decrease the peak intensity of SPSEBS-TiO2 membrane when
compared with Sulfonated composites. SPSEBS-TiO2 membrane

clearly showed the reection due to crystalline TiO2 on the surface but
in the case of sulfonated composite membranes no clear reections
were found. This behaviour suggested that TiO2 particles present in
sulfonated composite membranes were amorphous nature.
The addition of SeTiO2 llers resulted in changes in crystalline
properties, the intensity of which depended on the amount of
added SeTiO2. The crystallinity of the sulfonated membrane
decreased with the increase in the percentage of SeTiO2till 7.5%. As
the SeTiO2concentration further ascended beyond 7.5%, due to
higher loading of SeTiO2, (10%) inhomogeneous composite membrane was formed.
3.4. Water uptake and ion exchange capacity
Water uptake and ion exchange capacity of the membrane play an
important role in conductivity. With the increase in water uptake and
IEC, proton conductivity increased due to increase in the mobility of

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S. Ayyaru, S. Dharmalingam / Energy 88 (2015) 202e208

Fig. 3. XRD patterns of SPSEBS, unsulfonated SPSEBS-TiO2 composite membrane and

different concentration of sulfonated SPSEBS-S-TiO2 composite membranes.

ions in the water phase. To conrm the hygroscopic property of

membranes by incorporating SeTiO2 and TiO2 particles, the water
uptakes were measured. Table 1 lists the IEC and water uptake values
of the membranes at room temperature. The SPSEBS membranes
with sulfonic acid functionalized TiO2 showed higher water uptakes
when compared to the SPSEBS membranes with non-functionalized
TiO2. The increased water uptake content of composite membrane
was attributed to the incorporated SeTiO2particles in the composite
membrane that can supply more acid sites to absorb water compared
with the SPSEBS-TiO2 and pristine SPSEBS membranes. This
conrmed the hydrophilic nature of the SeTiO2. However, increasing
the loading of SeTiO2 from 7.5 % to 10 % did not signicantly change
the measured liquid water uptake.
The SPSEBS-S-TiO2 7.5% membrane showed the highest IEC
value of 3.35 meq g
1 compared with the pristine SPSEBS of
1.89 meq g
1and the SPSEBS-TiO2 7.5% of 1.62 meq g
1. Nanocomposite membranes containing 2.5e7.5% SeTiO2 showed higher
IEC values than pristine as well as un-sulfonated TiO2 composite
membrane. The increased IEC values illustrated that more acid sites
were resulted from acidic SeTiO2 particles existed in SPSEBS-STiO2composite membranes. The improved acidic property was
expected to enhance the membrane proton conductivity [18]. On
the other hand, the SPSEBS-TiO2 membrane showed the lowest IEC
value due to the presence of non-proton-conductive TiO2 particles.

Fig. 4. Nyquist plot for proton conductivity of different SPSEBS-S-TiO2 composite

membranes, non sulfonated SPSEBS-TiO2 composite membrane and SPSEBS.

5%, SPSEBS-S-TiO2 7.5%, and SPSEBS-S-TiO2 10% were 1.52  10
2,

1.08  10
2, 1.75  10
2, 2.51  10
2, 3.57  10
2 and
2.72  10
2 S cm
1 respectively. The proton conductivity of all the
sulfonated membranes increased distinctively with the increasing
SeTiO2 concentration upto 7.5% and then decreased above 7.5%. The
conductivity of the composite membranes with sulfonated SeTiO2
was superior to that of SPSEBS and SPSEBS-TiO2 membranes. Thus,
the addition of SeTiO2effectively increased the proton conductivity
of the membranes compared with SPSEBS-TiO2 membranes. Ke
et al. obtained similar results with sulfonated SiO2 in Naon at wet
condition in the chemical fuel cell [27]. The lower proton conductivity of SPSEBS-TiO2 membrane compared with SPSEBS under wet
condition was due to the non-proton conductive property of TiO2.
The reasons for proton conductivity of sulfonated composite
membranes were: (1) water uptake of the composite membrane
increased with the SeTiO2addition as shown in Table 1; (2) an
additional proton conduction pathway was created due to molecular water absorption by SeTiO2, part of the proton can be conducted by hopping mechanism between TiO2eSO2eOH and water
molecules [34e36]. However, higher SeTiO2 loading (10%) did not
contribute to any additional increase in proton conductivity. The
increased H diffusion of the SeTiO2 based SPSEBS membranes
when compared to the pure SPSEBS membrane is the combined
results of the enhanced water uptake as well as the acidity.

3.5. Proton conductivity

3.6. MFC performances

The results of impedance measurement for the determination of

proton conductivity are plotted in Fig. 4. The proton conductivities
for SPSEBS, SPSEBS-TiO2 7.5%, SPSEBS-S-TiO2 2.5%, SPSEBS-S-TiO2

The enrichment and adaptation of the electrochemically active

bacteria in the SCMFCs were performed in batch mode under a
xed external load of 500 U and was carried out for a period of
approximately 3weeks. All the MFCs inoculated with volume 10%
V/V initially was slower and the power density output rose after
each batch feed, then after reaching a peak a decline was observed
due to consumption of the fuel. All MFCs attained the peak power
around 3rd or 4th batch (300 or 400 h), beyond which no further
increase in the power density was observed which suggested that
the anode biolm was enriched with electrochemically-active
bacteria thus rendering it stable. Subsequently the polarization
curves were obtained from all SCMFCs using various resistances
(1 MUe50 U) at 20 min interval period which was required for
stabilization of the voltage.

Table 1
Comparison of IEC values and water uptake of the SPSEBS-S-TiO2 composites,
SPSEBS-TiO2 and SPSEBS membranes.
Membrane type

IEC (mmol g
1)

Water uptake (%)

SPSEBS
SPSEBS-TiO2 7.5%
SPSEBS-TiO2-SO3H
SPSEBS-TiO2-SO3H
SPSEBS-TiO2-SO3H
SPSEBS-TiO2-SO3H

1.89
1.62
2.25
3.02
3.35.
3.02

163
170
185
200
220
218

2.5%
5%
7.5
10%

3
5
8
9
11
10

S. Ayyaru, S. Dharmalingam / Energy 88 (2015) 202e208

207

Table 2
Comparison of oxygen mass transport, columbic efciency and internal resistance of
SPSEBS-S-TiO2 composites, SPSEBS-TiO2 and SPSEBS membranes.
Membrane type
SPSEBS
SPSEBS-TiO2 7.5%
SPSEBS-TiO2-SO3H
SPSEBS-TiO2-SO3H
SPSEBS-TiO2-SO3H
SPSEBS-TiO2-SO3H

Oxygen mass transport Columbic

Internal
(KO) (cm/s)
efciency (%) resistance (U)
3.5  10
5 cm/s
0.8  10
5 cm/s
2.5% 0.88  10
5 cm/s
5%
0.7  10
5 cm/s
7.5% 0.64  10
5 cm/s
10% 0.60  10
5 cm/s

75
72
80
83
87
85

3
2
4
3
4
5

66
60
55
45
35
37

4
3
2
1
0.8
0.5

Table 3
Comparison of sulfonated composite membranes with commercial Naon 117
membrane.
Membrane specications

Fig. 5. Performance of SPSEBS-S-TiO2 composite membranes, SPSEB-TiO2 composite

membrane and SPSEBS membrane in single chamber MFC.

Fig. 5 shows the SCMFC (single chambered microbial fuel cell)

performance of various membranes. The power density measured
with the composite membranes with sulfonated inorganic llers,
SPSEBS-S-TiO2 2.5%, SPSEBS-S-TiO2 5%, SPSEBS-S-TiO2 7.5%, and
SPSEBS-S-TiO2 10% were 975 11, 1200 15, 1345 17 and
1105 13 mW m
2 respectively. The power density of SPSEBS-TiO2
7.5% and SPSEBS were 835 8 and 695 7 mW m
2 respectively. It
was noticed that the performance of SPSEBS-S-TiO2 membranes
was superior to SPSEBS-TiO2 and SPSEBS membranes, because of
the increased number of acid sites (eSO3H) in the polymer matrix
that effectively increased the proton conductivity and improved the
performance in MFC in wet condition. The performance was
observed to increase with increasing SeTiO2 content up to 7.5%
(where the highest performance was observed) and beyond which,
the performance of composite membranes decreased. This declined
performance was caused by aggregation of SeTiO2 conductors in
membranes. Aggregates of such inorganic materials reduce the
mobility of H ion and thus presumably have a negative effect on
the performance of composite systems. This result was well
consistent with previous proton conductivity measurements.
Cheng Bi et al. and L. Wang et al. reported better performances
with the sulfonated metal oxide based membranes than the pristine and non-sulfonated membrane at wet condition in PEM fuel
cell [18,29]. Alessandra D'Epifanio et al. have prepared composite
membrane with Naon and sulfonated ZrO2 and its performance
was evaluated in 30% (relative humidity) RH at 70  C. The composite membrane produced 200% higher performance than a
pristine Naon membrane [37].
Different types of composite membranes have been investigated
in MFC and their results were compared with commercial Naon
[38,39]. In comparison to our previously reported work with Naon
(300 10 mW/m2) in MFCs under the same condition [10], the
composite membrane (SPSEBS-S-TiO2 7.5%) delivered 4-fold higher
power density. This was mainly due the sulfonation of TiO2 which
increased the IEC, proton conductivity and MFC performance. This
may make this approach useful for constructing large scale MFC. In
contrast, SPSEBS-TiO2 composite membrane showed better performance than SPSEBS, due to the low oxygen permeability of
composites, which maintained the anaerobic condition and
reduced the aerobic metabolism in anode compartment.
Table 2 lists the internal resistance, CE and oxygen mass transport of the different sulfonated composite membranes, non-

Proton conductivity (S cm
IEC (meq g
1)
Water uptake (%)
Thickness (mm)
Ko (cm s
1)
Power density (mW m
2)
Cost (m
2)

SPSEBS-TiO2-SO3H (7.5%)

1

2

3.574  10
3.35
220
180
0.64  10
5
1345 17
200

Naon 117
2  10
2
0.982
22
175
1.6  10
4
300 7
1500

sulfonated composite membrane and pristine SPSEBS. The low internal resistance of all the composite membranes under operating
conditions were attributed to the incorporation of hygroscopic
SeTiO2 and TiO2 particles. Compared to TiO2 additive, the SeTiO2
particles contributed more to decrease the internal resistance due
to its higher proton-conductive behaviour. The oxygen mass
transfer coefcient of SPSEBS (3.5  10
5 cm s
1) was found to be
much higher than other membranes. The SPSEBS-S-TiO2 composite
and SPSEBS-TiO2 membranes had lower oxygen mass transfer coefcients due to incorporation of inorganic metal oxides. The oxygen mass transfer coefcient rates decreased with an increase in
the amount of SeTiO2 added into the SPSEBS matrix.
Table 3 shows the comparison of sulfonated composite membranes with commercial Naon membrane. In comparison to
Naon 117 based MFC under the same condition [11], the SPSEBS-STiO2 7.5% membrane based MFC delivered more than 4-folder
higher power density. In addition, 600 7 mW m
2 obtained with
SPSEBS in our previous work [9] was also dramatically increased to
1345 17 mW m
2 by incorporation of sulfonated TiO2 (7.5%)
which means a 124% higher power density with sulfonated composite membrane. It is noted that the present work remarkably
improved the power generation. The organic compound removal
was found to be around 75 10% for all the composite membranes
studied in the microbial fuel cell during the performance.
The demonstrated composite membrane is an environmentally
safe, efcient and a cheaper alternate for the Naon. The testing of
the prepared composite membranes showed excellent results and
it would be a promising candidate for application in MFCs for the
treatment of waste water and simultaneous electricity generation.
Lower oxygen crossover, increased CE and low sludge formation are
additional supports for wastewater treatment applications. Additionally, the membranes are also non-uorinated in nature and
hence would prove to be cost efcient also.
4. Conclusion
In this paper, unique composite SPSEBS-S-TiO2 membranes with
high water uptake and good proton conductivity that will be a
potential candidate as PEM for MFC applications were prepared.
The composite membranes were characterized by XRD, FT-IR, SEM
techniques and the physical and chemical properties were studied.

208

S. Ayyaru, S. Dharmalingam / Energy 88 (2015) 202e208

Among the studied membranes, SPSEBS-S-TiO2 membrane (7.5%)

exhibited the highest IEC value, proton conductivity capacity,
lowest internal resistance and cell performance. The improved
performance was due to the sulfonation effect of SeTiO2 particles
which combined the proton conductivity with water absorbing
properties. The oxygen mass transfer coefcient (KO) of composite
membranes was also found to be lower than SPSEBS. This work
demonstrated that these sulfonated inorganic llers in polyelectrolyte nanocomposite membranes are an effective approach to
improve the MFC performances. In comparison to our previous
work with SPSEBS, the sulfonated composite membrane produced
124% higher power output in an SCMFC that may be attributed to (i)
the higher proton conductivity (ii) lower oxygen permeability (iii)
lower internal resistance of the sulfonated composite membranes.
Thus such membranes have great potential to be used as a PEM for a
high-power MFC. This work may also provide a new universal
approach for improving other MFCs. Our future studies will be
focused on the antifouling properties of sulfonated membranes and
the use of different types of sulfonated metal oxides like ZrO2 and
SiO2.
Acknowledgement
The authors thank, the Department of Science and Technology
(DST) India (letter no. DST/TSG/AF/2010/09, dt.01-10-2010) and
UGC-Meritorial Student Fellowship (2010e2013) Department of
Chemistry, Anna University Chennai, India for their nancial support to carry out this work.
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