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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
Bioengineering and Environmental Centre (BEEC), CSIR-Indian Institute of Chemical Technology, Hyderabad 500 607, India
Defence Research and Development Laboratory (DRDL), Kanchan Bagh, Hyderabad 500 058, India
a r t i c l e
i n f o
Article history:
Received 9 December 2011
Received in revised form 17 January 2012
Accepted 24 January 2012
Available online 14 March 2012
Keywords:
Multi walled carbon nanotube (MWCNT)
Carbon nanopowder (CNP)
Microbial fuel cell
Electrogenic activity
Wastewater treatment
Distillery wastewater
a b s t r a c t
Carbon based multiwalled nanotubes (MWCNT) and nanopowder (CNP) impregnated using conductive
epoxy resin on anodic surface were evaluated for bioelectricity generation in single chambered microbial
fuel cells in comparison with plain graphite anode (MFCP). The study demonstrated the positive function
of carbon nano structures impregnated anode with respect to power generation. MFCMWCNT exhibited
higher electrogenic activity (267.77 mW/m2) followed by MFCCNP (168.45 mW/m2) and MFCP
(107.51 mW/m2). MFCMWCNT and MFCCNP showed 148% and 57% enhancement in the power generation
respectively compared to MFCP. Microbial mediators were also found to be more effective with modied
anodes operation. Impregnation with nano material facilitates higher surface area that enables higher
charge transfer from anolyte to electrodes. Impregnated anodes showed marginal inuence on substrate
degradation. Further, feasibility of MWCNT impregnated anode was evaluated with real eld distillery
wastewater which depicted good electrogenic activity (245.34 mW/m2) and yield (3.43 W/m3).
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Microbial fuel cells (MFC) are the devices that facilitate the production of electrical energy from organic wastes using exoelectrogenic bacteria as biocatalyst [14]. Anodic oxidation and cathodic
reduction reactions are the key controlling factors for electrogenic
activity in MFC. The microorganisms oxidize the organic matter
leading to release of electrons and protons. These protons will
transfer to the cathode through membrane generating the potential difference between anode and cathode resulting in an electron
ow (current) through the external circuit. Anode plays a crucial
role in MFC operation which is hub for various bio-electrochemical
reactions and helps to mediate electron transfer to the electrode
from exoelectrogens [35].
High electrical conductivity, chemical stability, inert nature
(non-oxidative), non self-destructive and catalytic activity, sustainability of its properties with time and high surface area are
some of the important properties of the anode which can inuence
the performance of MFC. However, the susceptibility of anode to
microbial growth, afnitive mechanical contact and synergistic
interaction of the biocatalyst with anode (biocompatibility) are
also important to mediate the electron transfer [5,6]. Based on
the economics, practical applicability and efcient performance
32
microora (3.6 g VSS/l) through feed (0.5 l). Fuel cells were operated in the fed-batch (up-ow) mode at neutral pH (7.0 0.15) under anaerobic microenvironment. After inoculating, designed
synthetic wastewater [DSW, composition in g/l (glucose-3.0,
NH4Cl-0.5, KH2PO4-0.25, K2HPO4-0.25, MgCl2.6H2O-0.3, FeCl30.025, NiSO4-0.016, CoCl2-0.025, ZnCl2-0.0115, CuCl2-0.0105,
CaCl2-0.005 and MnCl2-0.015)] was fed for ve cycles at an organic
loading (OL) of 3.65 kg COD/m3 to adopt the culture to system
microenvironment. Anolyte was re-circulated at 100 ml/h using
peristaltic pump in order to reduce the substrate gradient. Before
changing the feed, inoculum was allowed to settle down for
30 min and then exhausted feed (0.4 l) was replaced with fresh
feed. The settled inoculum of 0.1 l was used for subsequent operations. Feeding, decanting, and recirculation operations were carried
with peristaltic pumps. The anode chamber was sparged with oxygen free N2 gas for 4 min after every feeding and sampling event to
maintain anaerobic microenvironment. Similarly, MFCDW was
operated with real eld distillery wastewater (COD-82.20 g/l,
TDS-21.60 g/l, VFA-1.94 g/l, SS-1.10 g/l, pH-4.21, color-120,000 Hazen units, total alkalinity-4.00 g/l, chlorides-4.10 g/l, sulfates0.10 g/l) to evaluate the practical application of the above study
under similar operating conditions. MWCNT impregnated electrode was used as the anode in this case. On 24 h of regular intervals, the samples were collected from anode chamber and
preserved at 4 C.
2.4. Bio-electrochemical analysis
Current output parameters and substrate degradation were
considered as the two key parameters to evaluate the performance
of fuel cells. Potential difference/open circuit voltage (OCV) and
current (I; measured in series at 50 X) were recorded on digital
multi-meter. Power (mW) was derived from P = IV equation. Power
density (mW/m2) and current density (mA/m2) were calculated
with the function of surface area of anode (m2). Power yield (W/
kg CODR) was obtained by relating power with the amount of
COD removed. Volumetric power production (mW/m3) was calculated based on maximum power generated in a cycle in relation to
total liquid volume of the anode. Bio-electrochemical behavior of
MFC in association to mixed consortia was studied in situ employing cyclic voltammetry (CV) using potentiostat-glavanostat system
(Autolab, PGSTAT12, Ecochemie). CV was recorded by applying a
potential ramp at a scan rate of 30 mV/s over the range from
+0.5 to 0.5 V to working electrode (anode of MFC) to gradually
change the potential. During electrochemical evaluation, cathode
of MFC was used as counter electrode, Ag/AgCl (S) as reference
electrode and wastewater as electrolyte. Current and voltage were
monitored to evaluate polarization behavior at various external
resistances (50 X to 30 K X). Cell potential and anode potential
were measured against saturated Ag/AgCl (S) electrode. Outlet
from anode chamber of all MFC were monitored for COD, pH,
and VFA as per standard methods [34] to evaluate treatment
efciency.
3. Results and discussion
3.1. Performance of fuel cells with variable anodic surface
impregnations
3.1.1. Electrogenic activity
The experimental data clearly illustrated the positive function
of anodic surface coatings/modications with MWCNT and CNP
on electrogenic activity (Fig 1; Table 1). However, the performance
of fuel cell varied with type of anode used. During rst cycle of
operation MFCp showed maximum power density (PD) of
33
MFCP
250
MFCCNP
MFCMWCNT
200
150
100
50
0
0
96
192
288
384
480
Time (h)
Fig. 1. Performance of MFC with carbon nanopowder (MFCCNP) and carbon
nanotubes (MFCMWCNT) impregnated graphite anodes in comparison with plain
graphite electrode (MFCP) with respect to power density (PD) during ve cycles of
operation with DSW.
Table 1
Experimental output pertaining to the various anodic impregnations used in MFC operation with DSW and distillery wastewaters as substrates.
a
b
Output parameters
MFCPa
MFCCNPa
MFCMWCNTa
MFCDWb
242
3.11
0.75
107.52
11.0/4.41
2200
0.56
1.49
0.344
7.007.60
352
3.35
1.18
168.45
11.0/6.08
2350
0.57
2.33
0.537
6.957.35
426
4.40
1.87
267.77
11.0/11.25
2350
0.59
3.69
0.817
6.827.30
406
4.23
1.72
245.34
10.0/11.05
1800
0.45
3.43
0.954
7.007.60
a
30
-400
20
2
Voltage (mV) Power density (mW/m )
34
10
0
300
MFC P
MFC CNP
MFC MWCNT
200
100
-300
-200
MFCP
-100
MFCCNP
MFCMWCNT
0
0
100
200
300
400
500
600
10
15
20
25
30
Resistance ()
Fig. 2. Polarization behavior of three fuel cells during fth cycle of operation with
DSW.
b 100
MFCP
95
MFCCNP
20m
90
MFCMWCNT
85
MFCCNP
10m
5m
MFCP
RDAP (%)
Current (A)
15m
80
75
-5m
70
-10m
40
-15m
-0.75
MFCMWCNT
-0.50
-0.25
0.25
0.50
0.75
Voltage (V)
Fig. 3. Cyclic voltammetric (CV) proles of three MFC during fth cycle of operation
with DSW.
20
0
0
10
15
20
25
30
Resistance ()
Fig. 4. Fuel cell characterization with respect to (a) anode potential and (b) relative
decrease in anodic potential (RDAP).
was limited by external resistance. At applied low external resistance, the electron delivery to the cathode was limited by kinetic
and/or mass transfer, and the RDAP increased linearly with
decreasing external resistance. The conditions where external
and internal resistance limitations were equal between these two
lines, a horizontal line from the intersection were drawn to estimate the external resistor that allowed to measure sustainable
power (Fig. 4b). All fuel cell operations demonstrated similar sustainable resistance of 11 KX in concurrence with different sustainable power density. The maximum sustainable power density was
registered with MFCMWCNT (11.25 mW/m2) followed by MFCCNP
(6.08 mW/m2) and MFCP (4.41 mW/m2). Maximum sustainable
power density was observed with modied anodes indicating that
nanostructure impregnations provides more surface area which
gives more stability to the system at higher resistance.
35
8.0
MFC P
MFC CNP
7.6
MFC MWCNT
pH
7.2
6.8
6.4
6.0
C1
C2
C3
C4
C5
Cycle number
b
1.5
1.0
0.5
0.0
MFCP
MFCCNP
MFCMWCNT
65
MFCP
MFCCNP
MFCMWCNT
60
55
250
50
C1
C2
C3
C4
C5
Cycle number
Fig. 5. Process evaluation of three MFC with respect to (a) pH variation (b) power
and specic power yield and (c) COD removal efciency during ve cycles of
operation with DSW.
Power (mW)
power yield (W/kg CODR)
MFCMWCNT visualized effective power output with good bioelectrochemical function. Therefore, to study its practical applicability, real eld distillery wastewater (MFCDW) was used as anolyte
and evaluated its performance under similar operating conditions.
The experimental data documented good power output using distillery wastewater (Fig. 6; Table 1). During rst cycle of operation
PD of 127.27 mW/m2 was observed which gradually improved
with every additional feeding event as observed with DSW. Consistent improvement in the power output was registered up to fourth
cycle of operation where maximum PD of 245.35 mW/m2 was registered. Later in the fth cycle almost similar performance was registered (243.00 mW/m2). Compared to DSW operated MWCNTanode, the time required for stabilization was higher for MFCDW
which might be due to the complexity of the wastewater used as
anolyte. Even though the time required for stabilization was higher, the variation in power output was negligible. Volumetric power
yield of the MFCDW was registered as 3.43 W/m3 (Table 1).
During stabilization phase of operation, polarization curve
MFCDW evidenced 400 X as cell design point which is comparable
to the cell design point registered with MFCMWCNT (DSW)
(Fig. 7a). However, maximum power density observed with DW
(28.01 mW/m2) was comparatively lower than DSW. The stabilization of voltage at various resistances was also observed to be
similar in polarization with both the wastewaters. However, relatively higher potential drop was observed at low resistances when
operated with DW. E0cathode was found to be 84 5 mV which is
200
150
100
50
0
0
96
192
288
384
480
Time (h)
Fig. 6. Power generation potential of MFCDW with distillery wastewater as
substrate during ve cycles of operation.
a
300
Voltage (V)
20
200
150
10
100
50
Voltage
Power density
0
100
200
250
Current (A)
30
25m
20m
15m
10m
5m
Cycle 3
0
-5m
-10m
-15m
-20m
-25m
-0.75
Cycle 5
Cycle 1
-0.50
400
500
0.25
0.50
600
50
7.6
Outlet pH
COD removal
80
45
60
40
7.4
20
pH
RDAP (%)
b 100
0.75
Voltage (V)
0
300
-0.25
0
400
300
40
7.2
35
200
36
100
0
7.0
0
10
15
20
Resistance (k )
25
30
Fig. 7. Fuel cell characterization of MFCDW (a) polarization study (b) anode
potential and RDAP during fth cycle of operation.
almost similar with the MFC operated with DSW. Signicant drop
in E0anode was noticed during operation of MFCDW (Fig. 7b). E0anode
suggested the possibility of effective electron discharge below
10 KX of external resistance similar to other experimental variations studied (Fig. 7b). E0 also decreased signicantly when resistance applied was less than 5 KX. The linear t drawn for RDAP
during the stabilized phase of MFCDW operation demonstrated to
possess the maximum sustainable power density of 11.05 mW/m2
and at sustainable resistance of 10.0 KX (Fig. 7b). Function of MFCDW
at higher resistance indicates the stability of the system in discharging the electrons effectively. The observation made from the cell
potentials and RDAP evidenced the application of the MWCNT
impregnated anode for improved performance of the fuel cells.
Bio-electrochemical behavior of MFCDW was evaluated during
ve cycles of operation. The catalytic current during FS
(23 0.5 mA) was almost similar throughout the ve cycles, while
the current during RS ( 15 6 mA) varied (Fig. 8). This is an evidence for strong oxidation along with reduction throughout the
ve cycles, which supports the increase in substrate utilization. Redox pairs were identied in CVs from third to fth cycles pertaining to the involvement of cytochrome c (0.25 V to 0.30 V) and
avoproteins or iron-sulfur proteins ( 0.09 V to 0.28 V) as mediators. The redox behavior of MWCNT impregnated anodes was almost similar with both DW and DSW. The catalytic currents were
less during rst cycle and found to increase with every additional
feeding event before stabilization from third cycle of operation.
Voltammograms of the third to fth cycles were very much similar
with negligible variation in the redox signals.
30
C1
C2
C3
C4
C5
Cycle number
Fig. 9. Evaluation of treatment of distillery wastewater using MFCDW with respect
to COD removal and pH variation.
The distillery wastewater showed feasibility of power generation along with wastewater treatment (Fig. 9). During ve cycles
of operation substrate degradation was found to increase consistently with the function of cycles due to the adaptation of consortia. First cycle operation showed lower substrate degradation
(45.20%) which gradually increased with number of cycles operated and registered maximum during fth cycle of operation
(49.32%, 0.45 kg CODR/m3-day). MFCDW showed SPY of 0.954 W/
kg CODR which is relatively on higher side compared to fuel cell
operation with DSW. Anolyte pH was found to vary between 7
and 7.6 during ve cycles of operation.
4. Conclusions
Nano structures impregnated anodes were employed to increase surface area of the graphite electrode using multiwalled carbon nanotubes (MWCNT) and carbon nanopowder (CNP) as surface
impregnations. Modied anodes depicted higher power output
than plain electrode which might be due to the effective colonization of microbial consortia. Modied electrodes also evidenced
improvement in wastewater treatment. Modied anodes also
found to show effective electron transfer by the involvement of
mediators such as avo proteins, iron-sulfur proteins and cytochrome c. Anode modied with MWCNT evidenced practical applicability in MFC operation with distillery wastewater. The
involvement of the mediators was also not effected with the usage
of real eld wastewater as substrate. In summary, the performance
of the MFC was found to depend on the nature and surface area of
the anode.
Acknowledgements
Authors acknowledge the Director, CSIR-IICT for his support and
encouragement in carrying out this work. GM acknowledges the
Council for Scientic and Industrial Research (CSIR), New Delhi,
for providing senior research fellowship.
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