Appl Biochem Biotechnol (2014) 173:378–390

DOI 10.1007/s12010-014-0846-x

Design of Clayware Separator-Electrode Assembly

for Treatment of Wastewater in Microbial Fuel Cells

Pritha Chatterjee & M. M. Ghangrekar

Received: 28 February 2014 / Accepted: 2 March 2014 /

Published online: 20 March 2014
# Springer Science+Business Media New York 2014

Abstract Performance of six different microbial fuel cells (MFCs) made from baked clay-
ware, having 450 ml effective anodic chamber volume, was evaluated, with different config-
urations of separator electrode assemblies, to study the feasibility of bioelectricity generation
and high-strength wastewater treatment in a single-chambered mediator-less air-cathode MFC.
Superior performance of an air-cathode MFC (ACMFC) with carbon coating on both sides of
the separator was observed over an aqueous cathode MFC, resulting in a maximum volumetric
power of 4.38 W m−3 and chemical oxygen demand (COD) removal efficiency of more than
90 % in a batch cycle of 4 days. Hydrophilic polymer polyvinyl alcohol (PVA) was success-
fully used as a binder. The problem of salt deposition and fouling of cathode could be
minimized by using a sock net current collector, replacing the usual stainless steel wire.
However, electrolyte loss due to evaporation is a problem that needs to be resolved for better
performance of an ACMFC.

Keywords Air cathode . Fouling . Microbial fuel cell . Separator electrode assembly . Volumetric
power . Wastewater treatment

Introduction

Microbial fuel cell (MFC) is a technology where the two major problems of human society that
is environmental pollution and energy crisis are addressed simultaneously. It treats wastewater
and simultaneously generates energy in the form of electricity for direct on-site use [1]. The
MFC converts the chemical energy stored in the chemical bonds of organic compounds in the
waste to electrical energy through catalytic action of anode respiring bacteria [2]. Normal MFC
structure is two-chambered with an anodic chamber and a cathodic chamber separated by a
proton exchange membrane (PEM). Oxidation of organic matter takes place in the anodic
chamber. Oxidation of the substrate releases electrons which, due to an absence of any
alternative external electron acceptor in the anodic chamber, reduces anode and travels through
the external circuit to the cathode. On the cathode, it is used to reduce oxygen to water in the

P. Chatterjee : M. M. Ghangrekar (*)

Department of Civil Engineering, Indian Institute of Technology, Kharagpur 721302, India
e-mail: ghangrekar@civil.iitkgp.ernet.in
Appl Biochem Biotechnol (2014) 173:378–390 379

presence of protons coming from the anodic chamber through the PEM. Thus, carbon neutral
energy liberation, in the form of direct electricity, is possible using wastewater as fuel in MFC.
Although there have been a lot of improvement in the MFC research, large-scale practical
application of MFCs is yet to be achieved because of its high cost and low-energy conversion
efficiency [3, 4]. Oxygen reduction reaction (ORR) is the major reaction that takes place at the
cathode. While the solubility of oxygen (mole fraction basis) in water is only 4.6×10−6 at
25 °C, in air, it is 0.21 [5, 6]. Hence, the ORR at aqueous air cathode is limited due to
nonavailability of oxygen. To address this problem, researchers have developed air-breathing
cathodes. The single-chambered air cathode offers several advantages over two-chambered
systems such as the following: (a) The cathode does not need to be aerated, and oxygen in the
air can directly react at the electrode; (b) recycling or chemical regeneration of the catholyte is
not required; (c) higher volumetric power density is easily achievable due to smaller cell
volume [7]; and (d) the overall volume and footprint of the MFCs will be less in air-cathode
configuration due to elimination of cathodic chamber. A volumetric power as high as
1,550 W m−3 was reported for a 2.5-ml MFC containing platinum catalyst on cathode and
using J-cloth sandwiched between carbon cloth anode and the carbon cloth/Pt/
polytetrafluoroethylene (PTFE) cathode as separator [8].
The membrane or the separator in the MFC is a very important component. It acts as a
separator for the aerobic and anaerobic compartments in the MFC as well as allows passage of
ions through it [9]. It accounts for 38 % of the total cost of a laboratory-scale MFC [10].
Behera et al. [11] used clayware membrane as separator and obtained a maximum power
density of 16.8 W m−3. This MFC with manufacturing cost less than US$1 gave a fairly good
performance compared with other MFCs prepared using expensive materials. Ajayi et al. [12]
prepared a low-cost membrane electrode assembly by coating a terra-cotta pot with graphite
paint and obtained a maximum power density of 33.13 mW m−2 using a graphite felt anode.
The present work aims to study the feasibility of bioelectricity generation in single-
chambered mediator-less air-cathode MFC using clayware membrane as a separator and
simultaneously treating high-strength wastewater employing a cheaper catalyst binder polyvi-
nyl alcohol (PVA). A comparative performance study, with respect to wastewater treatment
and electricity generation, of six different MFCs with different configuration of separator
electrode assemblies was accomplished to achieve this objective.

Materials and Methods

MFC Construction

This study was carried out with four laboratory-scale clayware pot MFCs (Fig. 1c) having an
average wall thickness of 4 mm and an anodic chamber volume of 450 ml with different
configurations of separator electrode assemblies. MFC-1 was a dual chamber MFC with
aqueous cathode, and the other three were single-chambered air-cathode MFCs. After 75 days
of operation, MFC-2 and MFC-3 were operated under aqueous cathode conditions and named
as MFC-5 and MFC-6, respectively (Table 1). Carbon cloth having a projected surface area of
100 cm2, reinforced with stainless steel (SS) mesh was used as anode in all these MFCs. Two
graphite plates having a surface area of 68 cm2 each were used as cathode for MFC-1, and it
was placed in a plastic container filled with aerated tap water working as a cathode chamber.
Other MFCs were coated with Vulcan XC-72R (Cabot Corporation) carbon powder at a
loading of 0.5 mg cm−2. PVA was used as a binder at a loading of 0.5 mg cm−2. The ink
was prepared and applied as described by Duteanu et al. [13]. These MFCs were having
380 Appl Biochem Biotechnol (2014) 173:378–390

approximate cathode surface area of 150 cm2. The inner surface of the separators on the anode
side of MFC-3, MFC-4, and MFC-6 was also coated with the carbon ink maintaining the same
loading. While SS wires were used as cathodic current collectors in all these MFCs except
MFC-4 where an SS sock net was used as cathodic current collector (Fig. 1a), to ensure proper
distribution of electrons and reduce ohmic losses. Electrodes were connected through
concealed copper wires through an external resistance of 100 Ω.

MFC Operation

Each MFC was inoculated with 60 ml of heat-treated anaerobic sludge collected from septic
tank bottom (volatile suspended solids of 19.95 g l−1 and total suspended solids of
30.22 mg l−1) and operated at room temperature (30 °C). Feed solution containing sodium
acetate as a source of carbon having chemical oxygen demand (COD) of about 3,000 mg l−1
was used. The acetate medium also contained (per gram of COD) NaHCO3, 1,500 mg; NH4Cl,
318 mg; CaCl2·2H2O, 250 mg; MgSO4·7H2O, 64 mg; K2HPO4, 27 mg; and KH2PO4, 9 mg.
Trace metals were added as FeSO4·6H2O, 10.00 mg l−1; MnSO4, 0.526 mg l−1; ZnSO4·7H2O,
0.106 mg l−1; H3BO3, 0.106 mg l−1; and CuSO4·5H2O, 4.5 μg l−1; CoCl2, 105.2 μg l−1;
(NH4)6Mo7O24·4H2O, 105.2 μg l−1 (Behera et al. 2010). Every fourth day, fresh feed was

a b

c
Load

Anode current collector

Cathode current collector
Cathode
Anode
Wires inside the MFC
Wires outside the MFC

Fig. 1 a MFC-4 provided with sock net current collector. b MFC-3 after fouling. c Schematic of the MFC
Appl Biochem Biotechnol (2014) 173:378–390 381

Table 1 Operating conditions of the different MFCs

MFC Anode chamber Anode Cathode Catholyte Cathodic current

volume (ml) collector

MFC- 450 Carbon cloth Graphite Aerated tap SS wire

1 plate water
MFC- 450 Carbon cloth Carbon Air SS wire
2 powder
MFC- 450 Carbon powder and Carbon Air SS wire
3 carbon loth powder
MFC- 450 Carbon powder and Carbon Air Sock net
4 carbon powder
cloth
MFC- 450 Carbon cloth Carbon Aerated tap SS wire
5 powder water
MFC- 450 Carbon powder and Carbon Aerated tap SS wire
6 carbon cloth powder water

MFC microbial fuel cell, SS stainless steel

given to the MFCs. All the MFCs were operated for 75 days. MFC-6 was continued to operate
as an air-cathode MFC after 75 days until 120 days to study the effect of fouling.

Analysis and Calculations

The potential and current generated by the cells were measured by a digital
multimeter with data acquisition unit having internal impedance of 10 Ω (Agilent
Technologies, Malaysia). Open circuit voltage (OCV) was measured after keeping the
circuit open for about an hour. Power was calculated from these data according to the
formula P=IV, where P=power in milliwatt, I=current in ampere, and V=voltage in
millivolt. Volumetric power was calculated by normalizing power to working volume
of anodic chamber. Polarization studies were carried out by varying the external
resistances from 10,000 to 1 Ω. Internal resistance of the MFCs was measured from
the slope of the plot of voltage versus current [14]. The anode and cathode potentials
were measured using Ag/AgCl (BaSI) reference electrode. The coulombic efficiency
(CE) of the MFC was calculated by integrating the measured current over time
relative to the theoretical current possible based on the observed COD removal. The
CE evaluated over a period of time t is calculated as Eq. 1 [15]:

.
CE ¼ MIt FbVΔCOD ð1Þ

where M is the molecular weight of oxygen (32), F is Faraday’s constant, b is the

number of electrons (4) exchanged per mole of oxygen, V is the volume of liquid in
the anodic compartment, and ΔCOD is the change in COD over time t.
The elemental composition of the cathode material was determined by energy disper-
sive X-ray (EDX) analysis in a scanning electron microscope with Oxford EDX detector
(JSM-5800, JEOL, Japan). Influent and effluent CODs and volatile and suspended solids
in the inoculum sludge were monitored according to the Standard Methods [16].
382 Appl Biochem Biotechnol (2014) 173:378–390

Results

Wastewater Purification

The COD concentration in the wastewater was used as the parameter to understand wastewater
treatment efficiency of the MFCs. The supernatant from the anodic chamber was collected, and
COD was measured to get an idea of COD removal. The average COD removal efficiencies
were 69.2±1.5, 76.4±2.2, 89.5±2.4, 90.7±2.0, 72.5±2.0, and 78.7±2.0 % in MFC-1, MFC-2,
MFC-3, MFC-4, MFC-5, and MFC-6, respectively (Fig. 2a). This demonstrates that the
effective treatment efficiency of the air-cathode MFCs was higher than the aqueous cathode
MFCs. The reason can be attributed not only to the varying cathode structure but also to the
varying anode configuration. Additional carbon coating on the separator on the anode side
favored biofilm formation, and this resulted in higher COD removal in MFC-3, MFC-4, and
MFC-6. Comparatively lower wastewater treatment efficiency was observed in the MFCs
without carbon coating on the anode side of the separator. Comparing COD removal efficien-
cies of MFC-2 (not having carbon coating on the anode side) and MFC-3 having the same
cathode configuration, a higher COD removal efficiency was observed in MFC-3 with carbon
coating on the anode side. Similar trend was found in MFC-5 (without carbon coating on the
anode side) and MFC-6 (with carbon coating on the anode side) which also had the same
cathode configuration. COD removal was measured in every operating cycle. It was observed
that removal efficiency improved with time, indicating enriched performance of the anodic
biofilm.

100
a
COD removal efficiency (%)

90
80
70
60
50
40
30
20
10
0
MFC-1 MFC-2 MFC-3 MFC-4 MFC-5 MFC-6

Cycle 1 to 5 Cycle 6 to 10 Cycle 10 to 15

Cycle 15 to 18 Cycle 20 to 30

14
b
Coulombic Efficiency (%)

12

10

0
MFC-1 MFC-2 MFC-3 MFC-4 MFC-5 MFC-6

Cycle 1 to 5 Cycle 6 to 10 Cycle 10 to 15

Cycle 15 to 18 Cycle 20 to 30

Fig. 2 a COD removal pattern and b coulombic efficiency in the six MFCs in different cycles
Appl Biochem Biotechnol (2014) 173:378–390 383

Electricity Generation

The MFCs started generating current from the first day of operation. They generated an
operating voltage (OV) of 8, 12, 7, 35, 146, and 203 mV, respectively, on the first day of
operation with 100-Ω external resistance. The corresponding OCV of 216, 192, 109, 92, 574,
and 413 mV, respectively, was observed. Higher OV in MFC-5 and MFC-6 from the beginning
of the operation was due to the presence of electrogenic bacterial biofilm developed on anode
during earlier operation as MFC-2 and MFC-3, respectively. This reduced the start-up time for
these two MFCs which otherwise was around 4 to 5 days for the other four MFCs.
The current and voltage were found to gradually increase with time. Average OV was
highest in the air-cathode MFC-4, with carbon coating on both sides of the separator and
having the SS sock net as a current collector. Throughout the stretch of observation, MFC-4
was found to give higher OV followed by MFC-3, MFC-1, MFC-6, MFC-2, and MFC-5,
respectively. This indicates that direct diffusion of oxygen from the air to the cathode surface
increases the cathodic reaction giving an overall improved performance of the air-cathode
MFC. Both OCV and OV were found to decrease as the MFCs with carbon coating as cathode
were put into aqueous mode. An average short circuit current of 8.12, 7.33, 9.15, 19.19, 8.23,
and 10.12 mA was observed in MFC-1, MFC-2, MFC-3, MFC-4, MFC-5, and MFC-6,
respectively. Short circuit current observed for MFC-4 was more than two times of the same
for MFC-3, emphasizing effectiveness of sock net current collector. Current generation got
stabilized with stable substrate degradation. The voltage generation patterns of the different
MFCs are shown in Fig. 3a for OV and in Fig. 3b for OCV.

400
350
a
Operating Voltage (mV)

300
250
200
150
100
50
0
0 20 40 60 80
Days
MFC-1 MFC-2 MFC-3 MFC-4 MFC-5 MFC-6

900
800 b
Open Circuit Voltage (mV)

700
600
500
400
300
200
100
0
0 20 40 60 80
Days
MFC-1 MFC-2 MFC-3 MFC-4 MFC-5 MFC-6

Fig. 3 Variation of a operating voltage and b open circuit voltage with time
384 Appl Biochem Biotechnol (2014) 173:378–390

Polarization and Power Density

The MFCs reached their stable performance in terms of OV and OCV within 9–10 days of
operation. Polarization studies were performed two times (cycle 8 and cycle 15) for each MFC
during the stable phase of operation. Figure 4a, b shows the power density and polarization
curves of the six MFCs, performed on the 60th day of operation (cycle 15), respectively. MFC-
4, equipped with a better current collector, produced a power density 3.2 times higher than
MFC-3 with simple SS wire as current collector and having the same anode configuration
(Table 2). The power generated by MFC-4 was also more than five times higher than the
aqueous cathode MFC-1 with graphite plates as the cathode. The aqueous cathode MFC-1
produced a higher power density than the air-cathode MFC-2 with carbon coating only on the
cathode side of the separator.
Normal carbon powder used in the cathodes of the air-cathode MFCs and graphite plate in
MFC-1 has very less electrical conductivity. Rozendal et al. [10] reported that the electrical
resistance of graphite is 1,375 μΩ cm while that of the metal titanium is 42 μΩ cm. Any metal
has lower resistance than graphite or carbon powder. So, the sock net used in MFC-4 as
cathodic current collector ensured proper distribution of electrons and also reduced the ohmic
losses of the reactor, thereby giving a higher power density and lower internal resistance. Zuo
et al. [17] pressed a SS mesh against the cathode and observed that the maximum power
produced increased by 28 % compared with the same system without the mesh. In the present
study, the sock net made of SS performed even better as a current collector giving more than
300 % higher power than the MFC without sock net. Thus, sock net can be used as a more
efficient current collector in MFCs. Its higher efficiency can be attributed to its flexibility

5000
a
Volumetric Power (mWm-3)

4500
4000
3500
3000
2500
2000
1500
1000
500
0
0 20000 40000 60000 80000
Current Density (mA m -3)
MFC-1 MFC-2 MFC-3 MFC-4 MFC-5 MFC-6

600
b
500

400
Voltage (mV)

300

200

100

0
0 20000 40000 60000 80000
Current Density (mA m-3)
MFC-1 MFC-2 MFC-3 MFC-4 MFC-5 MFC-6

Fig. 4 Pattern of variation of a power density and b voltage with current density
Appl Biochem Biotechnol (2014) 173:378–390 385

Table 2 Electricity generated in the different MFCs

MFC No. of days of Operating Open circuit Maximum Maximum Internal

operation voltage (mV) potential (mV) volumetric power density resistance (Ω)
−2
power density (mW m )
(mW m−3)

Max. Avg. Max. Avg. Cycle Cycle Cycle Cycle

8 15 8 15

MFC- 75 219 207±4 798 711±62 1,275 838.4 32 21 76

1
MFC- 75 189 161±10 619 585±23 503.1 515.7 16.81 17.24 239
2
MFC- 120 239 207±10 649 547±56 1,185 1,373 39.6 45.89 62
3
MFC- 75 347 310±12 595 491±49 4,219 4,381 141 146.42 23
4
MFC- 75 162 153±4 605 574±10 354.8 377.1 11.86 12.6 308
5
MFC- 75 210 201±5 419 412±5 598.7 640.4 20.01 21.4 109
6

MFC microbial fuel cell

which allows it to firmly adhere to the cathode surface thereby reducing any loose contact or
gaps between the cathode surface and the current collector, which in turn reduces electron loss
from the surface of cathode.
The power density obtained for MFC-3 with respect to cathode surface area
(45.89 mW m−2) in this study is slightly higher than 33.13 mW m−2, reported previously
for terra-cotta biobattery by Ajayi et al. [12], while the power density observed in this
experiment for MFC-4 (146.42 mW m−2) was much higher. The internal resistances of
MFC-1, MFC-2, MFC-3, MFC-4, MFC-5, and MFC-6 were 76, 239, 62, 23, 308, and
109Ω, respectively. As stated earlier, proper current collector reduced the ohmic losses,
and the system enjoyed a lower internal resistance. Internal resistance of MFC-2 and
MFC-5 was found higher than that of MFC-3 and MFC-6. While MFC-3 and MFC-6 had
carbon coating on both sides of the separator, MFC-2 and MFC-5 had only their outer
surface coated with carbon ink to work as cathode and having carbon cloth anodes. This
increased the distance between the electrodes, thereby increasing their internal resistance.
The binder used in the ink on the cathode might also have reduced the permeability for
the charge transfer and thus increasing the internal resistance of the cell to some extent.
Due to high porosity of the clayware pot and hot climate during the experiment, it
was difficult to maintain electrolyte level in the anode chamber due to consistent
evaporation loss. MFC-3 having both sides coated with carbon particles experienced
lesser electrolyte loss than MFC-2 due to reduced porosity of the separator, but it was
not completely eliminated. So while scaling up the air-cathode MFC for real waste-
water, we must consider the need of a hydrophobic material to prevent electrolyte
loss. However, a hydrophobic material might reduce the conductivity of the carbon
powder, and it would also cause the cathode to become too dry, thereby limiting
effective proton transfer [18]. So, a hydrophobic material having some anionic groups
in it might be a suitable choice.
386 Appl Biochem Biotechnol (2014) 173:378–390

Electrode Potential

The OV of MFC-4 was highest among all these MFCs followed by MFC-3, MFC-1, MFC-6,
MFC-2, and MFC-5. During polarization, it was observed that the anode potentials of the
MFCs remained almost in the same range (Fig. 5), which indicates that the difference in their
OVs cannot be due to the difference in microbial activities within the anode. The cathode
potential of MFC-4 was considerably higher than that of the other MFCs, which indicates that
the major limitation in the performance of the other MFCs was coming from the cathode. The
solubility of oxygen (mole fraction basis) in water is only 4.6×10−6 at 25 °C while that in air is
0.21 [5, 6]. So, the ORR in aqueous air cathode of MFC-1, MFC-5, and MFC-6 is limited due
to nonavailability of oxygen. Although MFC-2 and MFC-3 had an air-breathing cathode, its
operating potential as well as its cathode potential was found to be similar to that of MFC-1.
This can be attributed to the fact that they did not have proper arrangement for current
collection. This limitation was overcome in MFC-4 by employing a sock net, and higher
cathode potential could be achieved.

Coulombic Efficiency

The average coulombic efficiencies obtained for MFC-1, MFC-2, MFC-3, MFC-4, MFC-5,
and MFC-6 were 6.17±1.52, 4.53±1.60, 7.99±1.95, 10.61±1.74, 3.47±1.21, and 4.16±
1.23 %, respectively (Fig. 2b). Significant variation in CE was observed depending upon the
electrode configuration used. The MFC provided with sock net current collector demonstrated
the highest CE compared with others. While using mixed anaerobic sludge as inoculum and
without using catalyst on the electrodes, the CE of more than 10 % achieved in this experiment
is superior as compared with the values reported earlier [19]. However, still, it indicates that the
entire organic matter was not oxidized by electrogenic bacteria, but other groups of bacteria
like methanogenic bacteria were also utilizing the substrate. This is why coulombic efficiency
was observed to decrease slightly with each cycle. Anaerobicity might have been lost during

300
200
Potential (mV)

100
0
-100 0 5 10 15 20 25 30 35
-200
-300
-400
Current (mA)

Anode MFC-1 Cathode MFC-1 Anode MFC-2

Cathode MFC-2 Anode MFC-3 Cathode MFC-3
Anode MFC-4 Cathode MFC-4 Anode MFC-5
Cathode MFC-5 Anode MFC-6 Cathode MFC-6
Fig. 5 Anode and cathode potentials as a function of current
Appl Biochem Biotechnol (2014) 173:378–390 387

sampling and feeding processes, thus causing oxygen to act as the electron acceptor and
reducing the number of electrons transported through the external circuit.

Effect of Current Collector and Fouling

White patches were observed on cathode surface of MFC-2 and MFC-3 after 3 to 4 weeks of
operation indicating cathode fouling (Fig. 1b). OV at 100-Ω external resistance was found to
decrease gradually with time. Figure 3a shows the variation in OV of MFC-3 in the first
75 days, and Fig. 6 shows how the average OV and cathode potential dropped after reaching a
steady state in MFC-3. This drop coincided with the appearance of white coating on the
cathode surface. The deposition was not uniform over the surface but concentrated at random
locations over the surface of the separator. The deposition on the cathode surface blocked the
diffusion of oxygen and thereby limited the ORR which was reflected by lowering of OV and
cathode potentials. The deposition on the cathode surface was scraped off, and its elemental
composition was determined (Table 3). The fouling layer mainly consisted of inorganic salts
especially sodium salts which constituted 34.5 % of the total constituents by weight. Ion
chromatography analysis of the powder indicates that the major part of the powder was acetate
and chloride salts of sodium. It can be noted that sodium is the main element present in the
artificial wastewater given to the anodic chamber. This indicates that leaching of anolyte,
occurring through the porous clayware separator, has caused deposition of salts on the cathode
surface.
The fouling material was not only inorganic salts, but biological growth was also noted
under a microscope. Oxidation of the acetate deposited on the cathode surface occurred due to
the presence of this heterotrophic biological growth thereby reducing the cathode potential
even further. Also, fouling might have caused limitation in cation transfer thereby reducing
cathode potential [20]. A 12 % decrease in power density was observed due to this fouling. Xu
et al. [21] observed a 32.3 % decrease in power production due to fouling of the membrane.
But, no such deposition was found on the surface of MFC-4 (Fig. 1a). The presence of sock net
on the cathode surface of MFC-4 ensured proper distribution of electrons on the cathode
surface, and protons coming from anode chamber were utilized uniformly for the cathodic

250
Average Potential (mV)

200
150
100
50
0
-50
-100
-150
1- 11 - 21 - 31 - 41 - 51 - 61 - 71 - 81 - 91 - 101 - 110 -
10 20 30 40 50 60 70 80 90 100 110 120
Days
Operating Voltage Cathode Potential

Fig. 6 Variation of operating voltage and cathode potential of MFC-3

388 Appl Biochem Biotechnol (2014) 173:378–390

Table 3 EDX of the separator before and after fouling

Element (% by weight) Separator before fouling Separator after fouling

Carbon 68.15 12.34

Oxygen 19.24 49.22
Silicon 6.32 0.05
Sodium 1.66 34.5
Aluminum 0.14 0.21
Potassium 0.53 1.03
Calcium 0.9 1.34
Magnesium 0.53 0.17
Iron 1.35 1
Chloride 0.51 0
Sulfur 0.53 0.14
Molybdenum 0.14 0

reaction. This resulted in good wetting of the cathode surface, and uniform utilization of
protons led to a uniform pH over the cathode surface. This also helped in avoiding pH
imbalance. Nonuniform consumption of protons in MFC-3 might have led to a localized pH
gradient over the cathode surface, causing precipitation of salts. This deposition again blocked
proton transfer, thus simultaneously increasing fouling and also reducing the voltage.

Discussion

Performance of clayware pot MFC was explored for integrated wastewater treatment and
electricity generation under different configurations of separator electrode assemblies. Costly
binders like Nafion or PTFE was replaced by cost-effective PVA in this study to reduce
production cost of MFC.

Comparison of Air Cathode and Aqueous Cathode

The major reaction that takes place at the cathode is ORR. Limited availability of oxygen at the
cathode limits the rate of ORR [5, 6]. Oxygen is reduced on the active sites of the cathode in
the presence of protons and electrons to form water. Proper distribution of electrons is
important for accelerating cathodic reaction so that a constant current is maintained in the
circuit, and protons are utilized to maintain the pH at the cathode. In air-cathode MFC, direct
diffusion of oxygen to the cathode from air is possible, and the concentration of oxygen in air
is more than the saturation concentration of oxygen in water. As expected, higher voltage
could be harvested from the MFCs having air cathode than the MFCs with aqueous cathodes.
During polarization, the air-cathode MFC with carbon coating on both anode and cathode side
of the separator with SS wire current collector (MFC-3) generated a 1.64 times higher power
than the double-chambered aqueous cathode MFC-1. However, the aqueous cathode MFC-1
generated a power density 1.62 times that was generated by the air-cathode MFC-2. It seems
quite possible that the design of current collector was not sufficient in air-cathode MFCs,
involving higher resistance, which lead to decrease in overall power. Moreover, sufficiently
high power was consumed in aerating the catholyte continuously in aqueous cathode MFC.
Appl Biochem Biotechnol (2014) 173:378–390 389

However, with proper current collector and coating on both sides of the separator, the air-
cathode MFC can generate much higher power compared with the aqueous cathode MFC.

Effect of Carbon Coating on Both Sides of the Separator

The air-cathode MFCs with carbon coating on both sides of the separator consistently generated
higher voltages, power densities, COD removal rates, and coulombic efficiencies than the MFC
with only cathode coating. Coating on both anode and cathode sides reduced the distance
between the electrodes and thereby, the entire system performed as a separator electrode assembly
with reduced internal resistance [4, 6]. Also, coating on the anode side favored better biofilm
formation and led to a better system performance. Among the air-cathode MFCs, the one with
carbon coating on both anode and cathode generated a power 2.66 times higher than that with
carbon coating only on cathode. Air-cathode MFCs with coating on both sides of the separator
give more consistent and dependable results and are recommended for improved configurations.

Effect of Cathodic Current Collector

Inclusion of a metal current collector on the cathode surface can ensure proper distribution of
electron and also reduce the ohmic losses of the MFC [4, 10, 17]. Air-cathode MFCs with
coating on both sides of the separator employed with a sock net current collector improved the
performance of the MFC and produced power density 3.2 times higher than MFC-3 having
similar configuration but provided with SS wire current collector. Comparing the power
produced by aqueous cathode MFC-1 and MFC-4, the latter produced 5.2 times higher power,
emphasizing significance of the air-cathode MFC configuration with proper current collector.
The performance of this air-cathode MFC equipped with an improved current collector
surpassed other MFCs with aqueous cathode and air cathode having SS wire current collector.
Modified design of the current collector not only improved the overall performance of MFC
but also reduced the most pressing problem of fouling of membrane and cathode in an air-
cathode MFC. Better performance of such low-cost clayware ceramic separator MFC equipped
with a sock net current collector can take this technology a step ahead toward
commercialization.

Conclusions

Air-cathode ceramic separator MFC provided with proper current collector and with carbon
coating on both sides of the separator performs better than an aqueous cathode MFC in terms of
organic matter removal and power generation. Modified design of the current collector not only
improves the performance of MFC but also reduces the most pressing problem of fouling of
membrane and cathode in an air-cathode MFC. Hence, provision of high-density current collector
is recommended for minimizing cathode fouling to support long-term operation of MFC. PVA
can be used successfully as an economical replacement for costly binders. Fouling of the cathode
in the absence of proper current collector could reduce performance of air-cathode MFC. Due to
high porosity of the clayware pot and application under hot climate, it may be difficult to maintain
electrolyte level in the anodic chamber due to consistent evaporation loss. Hence, while scaling
up the air-cathode MFC, there is a need of a hydrophobic material having some polar groups in it
to prevent electrolyte loss without increasing charge transfer resistance of the separator. Further
investigations are required to produce fouling resistant air cathodes for long-term stable perfor-
mance and make this technology sustainable and efficient.
390 Appl Biochem Biotechnol (2014) 173:378–390

Acknowledgments The financial support received from the Department of Science and Technology, Govern-
ment of India (File No. DST/TSG/NTS/2010/61) is duly acknowledged.

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