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Energy 88 (2015) 202e208

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A study of influence 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 mWm2 for SPSEBS-S-TiO2 7.5%, when compared
to 695 ± 7 mWm2 and 835 ± 8 mWm2 obtained for SPSEBS and SPSEBS-TiO2 membranes respectively
in a (single chambered microbial fuel cell) SCMFC. In comparison to previously reported work with
Nafion (300 ± 10 mWm2) in MFCs, the composite membrane delivered more than 4-fold higher power
density. The oxygen mass transfer coefficient (KO) of nanocomposite membranes decreased with
incorporation of the sulfonated TiO2 which in turn increased the (columbic efficiency) CE.
© 2015 Elsevier Ltd. All rights reserved.

Microbial fuel cell
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 efficient 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 efficiency; CE), and reducing material costs [7] in a way
that allows for scalable designs.

* Corresponding author. Tel.: þ91 44 2235 7763; fax: þ91 44 22357744.
E-mail address: (S. Dharmalingam).
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). Nafion 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
Nafion matrix [16e20]. However, the excessive incorporation of
these nonconductive inorganic compounds in PEM normally results

0 g of the sample was soaked in 20 ml of 0. then stirred mechanically and then degassed by ultrasonication. around 0. But in case of high temperature the water molecules get evaporated from the membrane. The sulfonated TiO2 was prepared using sulphuric acid according to the method reported by Wang L et al.3.21e25].5. However. 2. Phenolphthalein was used as the indicator. The membranes which were thus obtained were designated as SPSEBS. Materials and methodology 2. being more stable than other solid super acids. SPSEBS-S-TiO2 7. As far as MFC is considered. It was overcome by the addition of metal oxides. The composite membrane was immersed in saturated potassium chloride solution overnight. it was found that SPSEBS procured 106% higher performance than commercial Nafion due its higher proton conductivity and lower oxygen permeability [11]. [31]. having the dual function of improving water retention as well as providing additional acidic sites [28]. Then the Hþ-formed sample was washed with distilled water till the pH value was 7. Preparation of nanocomposites Sulfonated TiO2 with different content (0. FT-IR spectrum analysis FT-IR spectrum of the nanocomposite membranes was recorded from 500 to 4000 cm1 using an Alpha Bruker FTIR spectrometer for confirming the increase in eSO3H functionality with respect to increase in filler (SeTiO2) concentration. [30] Chiu-Hsun Lin et al.4. This hygroscopic property could not always lead to a desired performance improvement under fully humidified condition.5%. Water uptake Water uptake properties of the nanocomposite membranes were measured at room temperature. [29] Chang-Chun Ke et al.3. 2. the incorporation of inorganic solid acids in conventional Nafion-type membranes is of primary interest.5 wt% of pure TiO2 with SPSEBS/THF matrix was prepared for comparison purpose. which improved the water retention and the thermomechanical stability of the membranes [22]. SPSEBS-S-TiO2 5%. . the sulfated metal oxides have become subjects of intensive studies. To retain the hydrated form of the membrane at high temperature the metal oxides have been used. 2. Nafion has its own drawbacks. 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. 1.S. X-ray diffraction (XRD) The XRD spectrum of membrane samples were recorded using “X” Pert Pro diffracto meter. In general.5. In case of MFC. The glass dish was then allowed to evaporate the solvent slowly. Their conductivity is of the same order of magnitude as that of mineral acids.2. Sulfonated groups of TiO2 not only create a path for proton transport but also act as vehicle due to its negative charge. hence we have selected SPSEBS as the base polymer due its low cost and excellent properties [11. 2. Preparation of sulfonated TiO2 TiO2 nanoparticles (25 nm) were purchased from Adrich. Here we need to increase the proton conductivity at room temperature and wet condition. 7. Similar to HPAs. Sulfonation of TiO2 was confirmed by FTIR and SEM-EDX in our previous work [32]. The crystal structures of the composite membranes were characterized by (X-ray powder diffraction) XRD. In our previous work with SPSEBS in MFC. but the high affinity for polar media makes them easily soluble [27]. almost all of these composite membranes reported in literatures were prepared with Nafion for HT-PEMFC only. In this paper. to be effectively used as membrane additives.1.5. Protons released from the membrane were neutralized by 0.01 N sodium carbonate solutions. 2. The (water uptake) Wut was calculated from the (wet weight) Wwet and the (dry weight) Wdry of the membranes using the following equation: Wut ¼ (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. But at low temperature the PEM with fully humidified metal oxide could not improve the proton conductivity than the pristine membrane. because the water molecules create a path for transport of protons. One gram of TiO2 nanoparticles was added to 15 ml of 0. consists of solid electrolytes such as (heteropolyacids) HPAs [26]. in the form of nano or submicrometric particles. 2. it operates at ambient temperature (30  C) under fully wet condition. In most cases the metal oxide composite membrane showed better performance at high temperatures only. Most researchers thought that the proton conductivity of the composite membranes under fully humidified condition was remarkably reduced due to incorporating with these non-proton-conductive hygroscopic metal oxides [18.and 10 wt%) was added into the SPSEBS/THF (tetrahydrofuran) solution.02e0. The scanning angle was 1e80 with scanned at a rate of 1 min1. Dharmalingam / Energy 88 (2015) 202e208 in a decrease of proton conductivity.1. So the objective of increased PEM conductivity can be achieved by adding proton conductive acidic additives like sulfonated groups grafted metal oxide (SeTiO2particles). SPSEBS-S-TiO2nanocomposite membranes were prepared for low temperature MFC. 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. The IEC was calculated using the following formula.3. 2. 7. 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.12].5%. Ayyaru.3.1 S cm1 at room temperature. and SPSEBS-S-TiO2 10% according to the weight percentage of the filler added.5 M H2SO4 overnight to ensure that all the eSO3H groups were exchanged with Hþ ions. Always the hydrated membrane form gives better performance.5 M sulphuric acid under ultrasonication for 1 h.3. USA. 2. Morphology observation The membrane surface of the various composite membranes was observed by means of JEM-5600LV (scanning electron microscope) SEM. The ion exchange capacity The (ion exchange capacity) IEC of nanocomposite was determined by the back-titration method. Proton conductivity was obtained from the electrochemical impedance spectroscopy and single chamber-microbial fuel cell performance of composite membranes was evaluated. to allow replacement of protons with Kþ ions. Other types of very interesting compounds. SPSEBS-S-TiO2 2. S. The final SeTiO2white powder was obtained by drying the solution at 203 100  C for 24 h.2. All specimens were dried and coated with a thin layer of gold before observation. Instrumental characterization 2. 5.

Results and discussion 3. SPSEBS-S-TiO2 7. On increasing the SeTiO2 concentration hydroxyl peaks were widened. An applied voltage of 10 mV and a frequency range of 1 MHze100 Hz were employed using a potentiostat (BioLogic VSP. The SeTiO2 particles were dispersed homogeneously with the interspaces filled with SPSEBS up to 7. L is the membrane thickness (cm). (4): KO ¼ V/At ln [(COeC)/CO] Internal resistance was characterized using (electrochemical impedance spectrometer) EIS methods. Current density and power density were determined by Ohm's law [9.1 g/L yeast.7. The inorganic particles appeared to have well dispersed in both low and high wt % composites. This was due to the presence of eSO3H groups in the side chains of SPSEBS. The cathode was prepared using a carbon cloth having 0.11]. while the 10% TiO2 composite membranes showed formation of agglomeration on the surface of the polymer matrix. The MEA was prepared by sandwiching the composite membrane between the anode and cathode electrodes as mentioned in our previous reports [11. and C is the DO concentration in the anode chamber at time t [9].32]. Cp is the total Coulombs calculated by integrating the current over time. 2. 0. This implies that the prepared composite membranes (up to 7.1. The mass transfer coefficient of oxygen in the membrane. The peak at 3400 cm1 was the characteristic signal of eOH. unsulfonated membrane composite and base membrane.28 g/L NH4Cl. KO (cm s1) was determined by monitoring the DO concentration over time and using Eq. and SPSEBS-S-TiO2 10%. Metravi.1 g/L. Fig. 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. due to the eOH group of sulfonated TiO2. To know the anode internal resistance. The Coulombic Efficiency (CE) was calculated using following Eq. respectively. S. 3. SPSEBS-S-TiO22. 0. 5 CE ¼ Cp/CT  100% (5) where. 0.11].68 g/L KH2PO4. 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. CT is the theoretical amount of Coulombs that can be produced from the amount of glucose which was degraded [9. having a pH of 7 which was then inoculated with wastewater that was collected from Anna University sewage treatment plant (Chennai.5%. 2). France). 0. MFC construction and operation The anode electrode used was 30 wt.2.5 g/L NaCl. All tests were done in triplicates and the average values were calculated.5%) can be expected to perform consistently well in the MFCs.5 mg cm2 platinum coating as a catalyst. 3.21. V is the liquid volume in the anode chamber. .2. The three-electrode mode is used to analyze an individual electrode. . The impedance measurement was then carried out.6. Morphology observation The surface morphology was analyzed from scanning electron microscope (Fig.1. India). 1. It was slightly difficult to differentiate the structural changes of the sulfonated composite membranes and SPSEBS from Fig. The conductivity values were calculated using Eq.62 cm2. Dharmalingam / Energy 88 (2015) 202e208 Titre value ðin mlÞ  Normality of Na2 CO3 meq=g weight of dry polymer membraneðin gÞ (2) 2. which established the connectivity in the composites. (3) s ¼ L/RA (3) Where s is the proton conductivity of the membrane (S/cm). CO is the saturated oxygen concentration in the cathode chamber. Membrane conductivity measurement The conductivity of each composite membrane was measured using ac impedance spectroscopy. Polarization curves were obtained by varying the applied external resistance at a time interval of 10 min. 1.31]. The anode chamber was filled with nutrient solution containing 1 g/L glucose. The reference electrode was an Ag/AgCl (KCl-sat. SPSEBS-TiO2. The (dissolved oxygen) DO probe (Extech 407510A.7.% wet proofed carbon cloth.5%. Taiwan) was inserted in an uninoculated MFC fitted with the desired composite membrane and filled with distilled water previously sparged with nitrogen gas to remove DO. France) electrochemical system. Oxygen mass transfer coefficients for each composite membrane were determined by following the protocol of O LefebVre et al.) electrode [33]. The filler particles were distributed relatively in a uniform fashion. Ayyaru. The MEA was further assembled into a cylindrical single-chambered MFC (28 mL) with the cathode-side of the MEA facing the air. MFC studies 2. FTIR spectra of various concentration of sulfonated composite membranes. These results also revealed that the hygroscopic property increased while adding sulfonated TiO2. The filler particles were observed to be clearly embedded in the polymer matrix.204 IEC ¼ S. R is the membrane resistance (U) and A is the area of the electrode (cm2) [29. India). A is the membrane cross-sectional area. that made it difficult for the identification of the eSO3H attached to the surface of TiO2 nano-particles.5%. 0.7. SPSEBS-S-TiO2 5%. Analytical measurements and calculations Cell voltage was recorded using a digital multimeter (Model 702. it was observed that the concentration of fillers gradually increased from 2c to 2f in the sulfonated composite (4) Where. FTIR spectrum Fig. 1 exhibits the FT-IR spectra of the SPSEBS. (2009). 0. 2.87 g/L K2HPO4. From the images. anode and cathode electrodes were used as working and counter electrodes.

4. The unsulfonated composite membrane with 7.S.5%. SPSEBS-TiO2 and SPSEBS-S-TiO2 composite membranes. Fig. (e) SPSEBS-S-TiO27. the intensity of which depended on the amount of added SeTiO2.5% TiO2 and (f) SPSEBS-S-TiO210% composite membranes. As the SeTiO2concentration further ascended beyond 7. 2. The addition of TiO2 fillers could not decrease the peak intensity of SPSEBS-TiO2 membrane when compared with Sulfonated composites. The addition of SeTiO2 fillers resulted in changes in crystalline properties.5% of TiO2 represented by 2b also showed the presence of higher concentration of filler (see Fig. (d) SPSEBS-S-TiO25%. 3 shows the XRD patterns of SPSEBS. The crystallinity of the sulfonated membrane decreased with the increase in the percentage of SeTiO2till 7. (b) SPSEBS-TiO2 (c) SPSEBS-S-TiO22. (10%) inhomogeneous composite membrane was formed. X-ray diffraction (XRD) X-ray diffraction (XRD) analysis is an effective technique to study the morphological information.5 % the crystallinity of the composite membranes decreased. From the XRD profiles. SEM images of (a) SPSEBS.5% to 7. it can be seen that on increasing the concentration of sulfonated e TiO2 from 2. This behaviour suggested that TiO2 particles present in sulfonated composite membranes were amorphous nature. 2). membranes. Dharmalingam / Energy 88 (2015) 202e208 205 Fig. 3. proton conductivity increased due to increase in the mobility of . This indicated that the presence of amorphous domain in the sulfonated nanocomposite membranes which was greatly decreased the crystallinity.5%.3. Water uptake and ion exchange capacity Water uptake and ion exchange capacity of the membrane play an important role in conductivity. 3. With the increase in water uptake and IEC. SPSEBS-TiO2 membrane clearly showed the reflection due to crystalline TiO2 on the surface but in the case of sulfonated composite membranes no clear reflections were found. due to higher loading of SeTiO2. S. Ayyaru. especially the crystallinity of the composite membranes.5%.

XRD patterns of SPSEBS.5% SPSEBS-TiO2-SO3H SPSEBS-TiO2-SO3H SPSEBS-TiO2-SO3H SPSEBS-TiO2-SO3H 1. 1. the water uptakes were measured.5%.89 meq g1and the SPSEBS-TiO2 7. All the MFCs inoculated with volume 10% V/V initially was slower and the power density output rose after each batch feed. 4. The increased Hþ 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. Ayyaru. (2) an additional proton conduction pathway was created due to molecular water absorption by SeTiO2.52  102.5 10% ± ± ± ± ± ± 3 5 8 9 11 10 .5% and then decreased above 7.02 3. SPSEBS-S-TiO2 2. 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. The proton conductivities for SPSEBS. Table 1 Comparison of IEC values and water uptake of the SPSEBS-S-TiO2 composites. On the other hand. Nyquist plot for proton conductivity of different SPSEBS-S-TiO2 composite membranes. However. This confirmed the hydrophilic nature of the SeTiO2. SPSEBS-TiO2 and SPSEBS membranes. Table 1 lists the IEC and water uptake values of the membranes at room temperature. The proton conductivity of all the sulfonated membranes increased distinctively with the increasing SeTiO2 concentration upto 7. and SPSEBS-S-TiO2 10% were 1. Proton conductivity 3.72  102 S cm1 respectively.5 % to 10 % did not significantly change the measured liquid water uptake.02 163 170 185 200 220 218 2. Dharmalingam / Energy 88 (2015) 202e208 Fig. SPSEBS-S-TiO2 7. The increased IEC values illustrated that more acid sites were resulted from acidic SeTiO2 particles existed in SPSEBS-STiO2composite membranes.08  102.75  102.62 meq g1. Ke et al. obtained similar results with sulfonated SiO2 in Nafion at wet condition in the chemical fuel cell [27]. All MFCs attained the peak power around 3rd or 4th batch (300 or 400 h). S. The improved acidic property was expected to enhance the membrane proton conductivity [18]. MFC performances The results of impedance measurement for the determination of proton conductivity are plotted in Fig.5%.5e7.6.89 1. 3. ions in the water phase. 3. 2. 5%.25 3. To confirm the hygroscopic property of membranes by incorporating SeTiO2 and TiO2 particles. non sulfonated SPSEBS-TiO2 composite membrane and SPSEBS. Fig.5% 5% 7. 4. The conductivity of the composite membranes with sulfonated SeTiO2 was superior to that of SPSEBS and SPSEBS-TiO2 membranes. The SPSEBS-S-TiO2 7. then after reaching a peak a decline was observed due to consumption of the fuel. 3.62 2. 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. Membrane type IEC (mmol g1) Water uptake (%) SPSEBS SPSEBS-TiO2 7.206 S.5.57  102 and 2. part of the proton can be conducted by hopping mechanism between TiO2eSO2eOH and water molecules [34e36]. The SPSEBS membranes with sulfonic acid functionalized TiO2 showed higher water uptakes when compared to the SPSEBS membranes with non-functionalized TiO2.35. Thus.5%. SPSEBS-TiO2 7. 1. the addition of SeTiO2effectively increased the proton conductivity of the membranes compared with SPSEBS-TiO2 membranes. The lower proton conductivity of SPSEBS-TiO2 membrane compared with SPSEBS under wet condition was due to the non-proton conductive property of TiO2.51  102. SPSEBS-S-TiO2 The enrichment and adaptation of the electrochemically active bacteria in the SCMFCs were performed in batch mode under a fixed external load of 500 U and was carried out for a period of approximately 3weeks.5%.5% SeTiO2 showed higher IEC values than pristine as well as un-sulfonated TiO2 composite membrane. 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 1.35 meq g1 compared with the pristine SPSEBS of 1. beyond which no further increase in the power density was observed which suggested that the anode biofilm was enriched with electrochemically-active bacteria thus rendering it stable. increasing the loading of SeTiO2 from 7. Nanocomposite membranes containing 2. unsulfonated SPSEBS-TiO2 composite membrane and different concentration of sulfonated SPSEBS-S-TiO2 composite membranes. higher SeTiO2 loading (10%) did not contribute to any additional increase in proton conductivity.5% of 1. 3. the SPSEBS-TiO2 membrane showed the lowest IEC value due to the presence of non-proton-conductive TiO2 particles.5% membrane showed the highest IEC value of 3. However.

Aggregates of such inorganic materials reduce the mobility of Hþ ion and thus presumably have a negative effect on the performance of composite systems. SPSEBS-TiO2 composite membrane showed better performance than SPSEBS. Table 3 shows the comparison of sulfonated composite membranes with commercial Nafion membrane. the SeTiO2 particles contributed more to decrease the internal resistance due to its higher proton-conductive behaviour.29].6  104 300 ± 7 1500 sulfonated composite membrane and pristine SPSEBS. Alessandra D'Epifanio et al. Lower oxygen crossover. In contrast. and L. Different types of composite membranes have been investigated in MFC and their results were compared with commercial Nafion [38. Wang et al. 1345 ± 17 and 1105 ± 13 mW m2 respectively. SPSEBS-S-TiO2 5%. 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 organic compound removal was found to be around 75 ± 10% for all the composite membranes studied in the microbial fuel cell during the performance. Dharmalingam / Energy 88 (2015) 202e208 207 Table 2 Comparison of oxygen mass transport.8 0. Table 2 lists the internal resistance. 5 shows the SCMFC (single chambered microbial fuel cell) performance of various membranes. have prepared composite membrane with Nafion and sulfonated ZrO2 and its performance was evaluated in 30% (relative humidity) RH at 70  C.5% and SPSEBS were 835 ± 8 and 695 ± 7 mW m2 respectively. The power density measured with the composite membranes with sulfonated inorganic fillers. Membrane type SPSEBS SPSEBS-TiO2 7.5% 0.574  10 3.64  105 cm/s 10% 0. due to the low oxygen permeability of composites. It is noted that the present work remarkably improved the power generation. Performance of SPSEBS-S-TiO2 composite membranes. the membranes are also non-fluorinated in nature and hence would prove to be cost efficient also. The low internal resistance of all the composite membranes under operating conditions were attributed to the incorporation of hygroscopic SeTiO2 and TiO2 particles.5% SPSEBS-TiO2-SO3H SPSEBS-TiO2-SO3H SPSEBS-TiO2-SO3H SPSEBS-TiO2-SO3H Oxygen mass transport Columbic Internal (KO) (cm/s) efficiency (%) resistance (U) 3. The composite membranes were characterized by XRD. the composite membrane (SPSEBS-S-TiO2 7. In comparison to our previously reported work with Nafion (300 ± 10 mW/m2) in MFCs under the same condition [10].5%. which maintained the anaerobic condition and reduced the aerobic metabolism in anode compartment. In addition. FT-IR. the SPSEBS-STiO2 7. Compared to TiO2 additive. SPSEBS-S-TiO2 7. SPSEBS-TiO2 and SPSEBS membranes. The oxygen mass transfer coefficient of SPSEBS (3. efficient and a cheaper alternate for the Nafion. proton conductivity and MFC performance. Conclusion In this paper.5  105 cm s1) was found to be much higher than other membranes. reported better performances with the sulfonated metal oxide based membranes than the pristine and non-sulfonated membrane at wet condition in PEM fuel cell [18.5%) delivered 4-fold higher power density.35 220 180 0. 4.5  105 cm/s 0.5%) which means a 124% higher power density with sulfonated composite membrane. 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. 600 ± 7 mW m2 obtained with SPSEBS in our previous work [9] was also dramatically increased to 1345 ± 17 mW m2 by incorporation of sulfonated TiO2 (7. Ayyaru. This was mainly due the sulfonation of TiO2 which increased the IEC. The SPSEBS-S-TiO2 composite and SPSEBS-TiO2 membranes had lower oxygen mass transfer coefficients due to incorporation of inorganic metal oxides.7  105 cm/s 7. the performance of composite membranes decreased. The composite membrane produced 200% higher performance than a pristine Nafion membrane [37].60  105 cm/s 75 72 80 83 87 85 ± ± ± ± ± ± 3 2 4 3 4 5 66 60 55 45 35 37 ± ± ± ± ± ± 4 3 2 1 0.5% (where the highest performance was observed) and beyond which. Additionally. The performance was observed to increase with increasing SeTiO2 content up to 7.88  105 cm/s 5% 0.5% 0. S. columbic efficiency and internal resistance of SPSEBS-S-TiO2 composites. In comparison to Nafion 117 based MFC under the same condition [11]. CE and oxygen mass transport of the different sulfonated composite membranes. SPSEB-TiO2 composite membrane and SPSEBS membrane in single chamber MFC.8  105 cm/s 2.5%. The oxygen mass transfer coefficient rates decreased with an increase in the amount of SeTiO2 added into the SPSEBS matrix.64  105 1345 ± 17 200 Nafion® 117 2  102 0. 1200 ± 15.5%) 1 ) 2 3. The power density of SPSEBS-TiO2 7. .982 22 175 1. This declined performance was caused by aggregation of SeTiO2 conductors in membranes. Membrane specifications Fig. increased CE and low sludge formation are additional supports for wastewater treatment applications.5 Table 3 Comparison of sulfonated composite membranes with commercial Nafion 117 membrane.5% membrane based MFC delivered more than 4-folder higher power density. and SPSEBS-S-TiO2 10% were 975 ± 11. The demonstrated composite membrane is an environmentally safe.39]. This may make this approach useful for constructing large scale MFC.S. 5. Fig. SEM techniques and the physical and chemical properties were studied. Cheng Bi et al. non- Proton conductivity (S cm IEC (meq g1) Water uptake (%) Thickness (mm) Ko (cm s1) Power density (mW m2) Cost (m2) SPSEBS-TiO2-SO3H (7. This result was well consistent with previous proton conductivity measurements. SPSEBS-S-TiO2 2. 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. It was noticed that the performance of SPSEBS-S-TiO2 membranes was superior to SPSEBS-TiO2 and SPSEBS membranes.

Zhang Y. Ng HY.140:34e40. Environ Sci Technol 2006. proton conductivity capacity. Vetter S.11:201e4. Landau MV. Zhou Z. J Power Sources 2004. characterization and application studies of self-made Fe3O4/PES nanocomposite membranes in microbial fuel cell. Granular activated carbon single-chamber microbial fuel (GASCMFCs): a design suitable for large-scale wastewater treatment processes. Shen Q. Bioresour Technol 2011.01-10-2010) and UGC-Meritorial Student Fellowship (2010e2013) Department of Chemistry. Qu SG. dt.232:210e25. Rozendal R. [37] D'Epifanio A. Performance of sulfonated polystyrene-ethylene-butylene-polystyrene membrane in microbial fuel cell for bioelectricity production. Li B. Acknowledgement The authors thank. Ghoreyshi AA. Antonucci PL. Yu HM. Development of MFC using sulphonated polyether ether ketone (SPEEK) membrane for electricity generation from waste water. 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