Bioresource Technology 191 (2015) 110–116

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Enhancing the power generation in microbial fuel cells with effective

utilization of goethite recovered from mining mud as anodic catalyst
Dipak A. Jadhav a, Anil N. Ghadge b, Makarand M. Ghangrekar b,⇑
a
School of Water Resources, Indian Institute of Technology, Kharagpur 721302, India
b
Department of Civil Engineering, Indian Institute of Technology, Kharagpur 721302, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Recovery of goethite from mine mud

was confirmed from material
characterization. e- e-
 Recovered goethite from iron ore
CO2 + H+ Fe3+
mine shows catalytic behavior for A C O2
H+ a
anodic reactions. n
 MFC with treated goethite coated o t
e-
anode gave fivefold power compared d H+ h
to control MFC. e- e o
Organic H+ d
 Improved capacitance observed in Fe2+ H2 O
matter Fe e
MFC with treated goethite (hematite)
Bacteria
coated anode. PEM
 Goethite catalyst accelerates the
electron transfer between anode and
microbes.

a r t i c l e i n f o a b s t r a c t

Article history: Catalytic effect of goethite recovered from iron-ore mining mud was studied in microbial fuel cells
Received 16 March 2015 (MFCs). Characterization of material recovered from mining mud confirms the recovery of iron oxide
Received in revised form 27 April 2015 as goethite. Heat treated goethite (550 °C) and untreated raw goethite were coated on stainless-steel
Accepted 28 April 2015
anode of MFC-1 and MFC-2, respectively; whereas, unmodified stainless-steel anode was used in
Available online 4 May 2015
MFC-3 (control). Fivefold increment in power was obtained in MFC-1 (17.1 W/m3 at 20 X) than MFC-3
(3.5 W/m3). MFC with raw goethite coated anode also showed enhanced power (11 W/m3). Higher
Keywords:
Coulombic efficiency (34%) was achieved in MFC-1 than control MFC-3 (13%). Decrease in
Anode catalyst
Electro-chemical analysis
mass-transport losses and higher redox current during electrochemical analyses support improved elec-
Goethite tron transfer with the use of goethite on anode. Cheaper goethite coating kinetically accelerates the elec-
Hematite tron transfer between bacteria and anode, proving to be a novel approach for enhancing the electricity
Microbial fuel cells generation along with organic matter removal in MFC.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction material properties of electrode, microbial interaction with anode,

Microbial fuel cell (MFC) is a bioelectrochemical system (BES)
which can be used to treat wastewater along with simultaneous
electricity generation using microbes as a biocatalyst (Logan,
2008). Anodic factors such as anodic electron transfer mechanism,
⇑ Corresponding author. Tel.: +91 3222 283440; fax: +91 3222 283254.
E-mail address: ghangrekar@civil.iitkgp.ernet.in (M.M. Ghangrekar).
anolyte conditions, operating conditions, etc. govern the perfor-
mance of MFC. Thus, enhancing the performance of anode is a crucial
aspect for scale-up of MFC technology. The main drawback associ-
ated with MFC is lower power output, primarily due to the limited
electron transfer from bacteria to the anode. To enhance the power,
there is a need to expend the chemical catalysts (or mediators) for
anodic reactions, which are generally expensive and non-friendly
to environment. Due to higher cost and chances of causing further

http://dx.doi.org/10.1016/j.biortech.2015.04.109
0960-8524/Ó 2015 Elsevier Ltd. All rights reserved.
 D.A. Jadhav et al. / Bioresource Technology 191 (2015) 110–116
pollution, use of chemically synthesized catalyst for field scale appli-
cation of MFC is not a feasible solution. To solve this issue, there is a
need to look for effective, economical and efficient alternative cata-
lyst to enhance the anodic electron transfer rate.
Mining mud generated from iron ore mines can be considered
as a resource; since, it contains about 60–70% of iron oxide, 10–
30% of alumina; 2–20% silica; 2–10% sodium superoxide; 2–8% cal-
cium oxide; and trace – 0.2–0.8% titanium dioxide (Paramguru
et al., 2005). Higher amount of ferrous compounds present in the
mud can be useful for catalytic reactions in fuel cell applications.
Higher content of iron oxide compounds present in red mud can
be used as inexpensive and effective anode catalysts in bioelectro-
chemical systems (BES). The presence of ferrous compounds could
support the electron transfer in fuel cell via iron redox pathway
(Kato et al., 2012). Bioelectrochemical system such as MFC can uti-
lize this iron oxide as a catalyst to enhance extracellular electron
transfer (EET) activities in the anodic chamber (Peng et al.,
2013a,b, 2015).
Different forms of iron oxide (i.e. goethite, hematite, and mag-
netite) can serve as medium for transfer of electrons between bacte-
ria and anode (Zhou et al., 2014). In sediment MFC, Lowy et al. (2006)
found that the modification of anode with nano-crystalline mag-
netite (Fe3O4) enhanced the kinetic activity by 120% as compared
to that of unmodified anode. Utilization of 5% goethite (a-FeOOH)
resulted into 36% increment in power density as compared to MFC
with activated carbon (AC) anode (Peng et al., 2013b). In dual cham-
bered MFC, anode modified with indium tin oxide (ITO) and hema-
tite (a-Fe2O3) nano-rods improved the power by 320% than bare
anode (Ji et al., 2011). Recently, Peng et al. (2015) reported boost
in exchange current density by 20% with Fe2O3 coated AC anode as
compared to control AC anode, which was mainly due to increase
in the EET in anodic chamber of MFC. The electrochemical activity
and attached bacterial density of Fe-modified graphite felt anode
were significantly higher than unmodified anode (Wang et al.,
2013). Carbon paper anode modified with goethite nano-whiskers
facilitated EET with Shewanella loihica PV-4 strain and resulted into
60% increment in current density as compared to bare carbon paper
anode (Wang et al., 2015). Zhou et al. (2014) studied effect of iron
oxide amendment into freshwater sediments on performance of
sediment MFC and noted that higher Fe(II) concentration in fresh-
water led to higher power production.
Previously, few researchers (Wang et al., 2015; Peng et al.,
2013a,b) worked on ferrous oxide to enhance kinetic activity of
anode in MFCs using chemically synthesized goethite catalyst,
which is expensive and it may cause further pollution. However,
these researchers have indicated that presence of iron oxide on
anode is certainly effective for enhancing the performance of
MFC. Hence, the main aim of this study was to recover goethite
as a waste product from iron ore mines and utilize it as an anodic
catalyst in MFC. Effect of coating of heat treated goethite on anode
of MFC on the power production was evaluated and performance
was compared with MFC using raw goethite coated anode and
without any goethite coating on stainless steel anode. Different
electrochemical techniques were adopted to facilitate the
comparison.
2. Methods
2.1. Goethite recovery
Mining exploration mud was collected from iron ore mine of
Noamundi, Jharkhand, India. Goethite was recovered from mining
mud as per the procedure described by de Silva et al. (2011). The
Fe-ions present in red mud were separated from other ions by
addition of NaOH, which formed precipitate of iron hydroxide.
111
After successive wash, iron hydroxide precipitate was dissolved
in nitric acid. Precipitation of ferric nitrate solution was carried
out with addition of KOH to produce ferrihydrite. The precipitate
was dissolved in water to obtain ferric ion species (Fe(OH) 4 ) and
heated to 70 °C (for 60 h), which forms crystalline goethite powder.
The goethite powder was dried and sample powder was used for
material characterization. For conversion of goethite to hematite,
goethite powder was heated to 550 °C for 2 h in muffle furnace
(Cornell and Schwertmann, 2003). To determine the specific sur-
face area, total pore volume of goethite and treated goethite sam-
ples, nitrogen-adsorption–desorption was carried out for each
sample using Brunauer, Emmett and Teller (BET) surface analyzer
(SMART SORB 93, Smart Instruments Ltd., Thane, India). Before
BET analysis, both raw and treated goethite samples were degassed
at regeneration temperature of 120 °C for 1 h with high relative
pressure (P/P0 of N2 = 94.93%).
2.2. Material characterization
Thermo-gravimetric analysis (TGA) and differential thermal
analysis (DTA) were used to measure the quantity and rate of
change in weight of the material with variation in the temperature
in a controlled atmosphere, respectively. TGA measurements were
conducted with a heating rate of 10 °C/min under nitrogen atmo-
sphere at temperature ranging from 50 to 800 °C. TGA and DTG
curves were recorded with a Thermo-Gravimetric and
Differential Thermal Analyzer (Perkin Elmer Inc., Massachusett,
USA). Energy-dispersive X-ray spectroscopy (EDX) analysis was
carried out for dried goethite samples using ZEISS EVO 60
Scanning Electron Microscope (Carl ZEISS SMT, Germany) to deter-
mine the amount of different elements present in goethite
samples.
During Fourier Transform Infrared Spectrometer (FTIR) analysis,
the infrared (IR) spectra were recorded for goethite powder sam-
ples at room temperature in KBr pellets, using a NEXUS-870 FTIR
spectrometer (Thermo Nicolet Corporation, USA), under atmo-
spheric conditions to study interaction between nano-sized parti-
cles (Liu et al., 2013). FTIR spectrum was measured without any
special thermal treatment in the transmittance mode. X-ray
diffraction (XRD) is a technique that is used to identify the crys-
talline and amorphous materials. The phase structures of both
the powdered samples were determined from X-ray diffraction
(XRD) patterns, with Philips 1710 diffractometer (PW-1710,
Almelo, Netherlands) using monochromatic CuKa1 radiation at
the angles 2h = 10–100° with a scanning rate of 2° per minute. In
order to measure the XRD pattern, the raw and heated goethite
samples were ground at room temperature and passed through
200 mesh sieve.
2.3. Fabrication of MFC anodes
Recovered raw goethite was heated in muffle furnace at 550 °C
for 2 h. The homogenous mixture of poly-vinyl alcohol (PVA) bin-
der (at loading of 0.5 mg/cm2) and powder form of heated goethite
(at loading of 1 mg/cm2) was coated on stainless steel (SS) wire
mesh anode of MFC-1. Untreated raw goethite powder along with
PVA binder was coated, in same proportions as mentioned earlier,
on SS anode surface of MFC-2; whereas, goethite was not coated on
SS anode of MFC-3 operated as a control to facilitate the compari-
son. The stainless steel wire mesh having projected surface area of
107 cm2 was used as an anode in these MFCs.
2.4. MFC construction and operation
Three dual chambered MFCs were fabricated with a baked clay-
ware ceramic cylinder having effective working volume of 350 mL
112 D.A. Jadhav et al. / Bioresource Technology 191 (2015) 110–116
for anodic chamber. Wall material (about 5 mm thick) of the cylin-
der itself acted as separator (cation exchange membrane) between
anodic chamber and cathodic chamber. Three MFCs were made up
of modified/unmodified anode with surface area of 107 cm2 as sta-
ted above, and carbon felt (PanexÒ 35, Zoltek Corporation, MO,
USA) was used as cathode with projected surface area of
576 cm2. Carbon felt was wrapped over the clayware cylinder;
whereas, modified/unmodified SS anode was kept on the inner
periphery of clayware cylinder. Connections between anode and
cathode were made with titanium wire through an external resis-
tance of 100 O (unless stated otherwise). To check biodegradability
of PVA binder and its effect on power generation, a similar MFC
was fabricated with anode coated with only PVA binder and carbon
support (without goethite) and its performance was compared
with MFC-3 (control MFC).
Anaerobic mixed sludge, used as inoculum, was collected from a
septic tank, IIT Kharagpur, India. The inoculum sludge was sieved
through 1-mm sieve and heat treatment (100 °C for 15 min) was
given to suppress the growth of methanogenic consortia. This pre-
treated sludge of volume 60 mL was added in the anodic chamber
as a source of inoculum. Synthetic wastewater was prepared using
sodium acetate as a source of carbon having chemical oxygen
demand (COD) of about 3000 mg/L. Artificial wastewater was
made by adding (per L) sodium acetate, 3840 mg; NaHCO3,
4500 mg; NH4Cl, 954 mg; CaCl22H2O, 750 mg; MgSO47H2O,
192 mg; K2HPO4, 81 mg; and KH2PO4, 27 mg; FeSO46H2O,
60.00 mg, and trace metals (Jadhav and Ghangrekar, 2008). Tap
water, used as catholyte, was aerated continuously with an aquar-
ium pump (SOBO Aquarium air pump, China) to supply air at a con-
stant rate of 3.5 mL/min. Each MFC was operated for 15 batch
cycles spread over 75 days with feeding interval of 5 days, and
operated at room temperature of 27 ± 5 °C.
2.5. Analysis and measurement
The COD concentrations of influent and effluent samples were
measured by closed reflux colorimetric method (APHA, 1998).
Influent and effluent pH was measured using a water quality bench
meter (Cyber Scan, pH 620, Eutech Instruments, Singapore).
The open circuit voltage (OCV) under no current flow condition
and operating cell voltage at given resistance for each MFC were
measured using data acquisition/switch unit (Agilent
Technologies, Penang, Malaysia) connected with computer system.
Power was calculated according to the formula P = iV, where
‘P’ = power, ‘i’ = current, and ‘V’ = voltage. Volumetric current den-
sity (VCD) was calculated by dividing the current produced by
MFC with a working volume of anodic chamber. Individual elec-
trode potential was measured using Ag/AgCl reference electrode
(+197 mV vs. SHE, Bioanalytical Systems Inc., West Lafayette,
Indiana, USA). The Coulombic efficiency (CE) was estimated by
integrating the measured current relative to the theoretical current
using Eq. (1);
Rt
M 0 Idt
CE ¼
Fbv DCOD
where, I is current produced; M is molecular weight of oxygen; v is
the working volume of the anodic chamber of MFC; b is the number
of electrons exchanged per mole of oxygen = 4; F is Faraday’s
constant = 96,485 C/mol; DCOD is the difference in the influent
and effluent COD concentration (Logan, 2008).
2.6. Electrochemical analyses
Polarization studies were carried out after reaching a stable cell
potential by changing the external resistances from 40,000 to 1 X
using resistance box (GEC05R Decade Resistance Box, Renown
Systems, Kolkota, India). The internal resistance (IR) was calculated
using maximum power point method from power density curve
(Logan, 2008). To determine electrode kinetics, Tafel analysis was
carried out from polarization data as suggested by Vaszilcsin and
Nemes (2009) and Bard and Faulkner (2000).
The other electrochemical analyses such as cyclic voltammetry
(CV) and electrochemical impedance spectroscopy (EIS) were per-
formed using electrochemical workstation (Autolab PGSTAT 302N
potentiostat, Metrohm, Utrecht, The Netherland). EIS was per-
formed in a frequency range of 100 kHz–1 mHz with an AC signal
of 10 mV amplitude to determine different components of inter-
nal resistance of different MFCs (Zhao et al., 2009). Frequency
response analyzer (FRA, Metrohm, Utrecht, The Netherland) was
connected through the potentiostat to the MFCs for measure-
ment. The frequency response data were simulated using NOVA
1.9 software and corresponding equivalent circuit was fitted. CV
analysis was performed from 1 to +1 V at slow scan rate of
10 mV/s with modified stainless steel anode as a working elec-
trode, Ag/AgCl as a reference electrode (+197 mV vs. SHE) and
cathode as a counter electrode (Jadhav et al., 2014). The current
response against different applied voltages was recorded with
NOVA 1.9 software. Bio-capacitance (C) was calculated from CV
data as per Eq. (2).
,  
dV
C¼I A ð2Þ
dt
where, A is the projected surface area of electrode, I is the maximum
redox current, and (dV/dt) is scan rate.
3. Results and discussion
3.1. Material characterization
3.1.1. Thermo-gravimetric analysis
The hydroxyl (OH) ions and water contents of both raw and
treated goethite samples were determined from the TGA and
DTA. About 9.5 to 12% mass loss on ignition occurred during
thermal dehydration and corresponding degradation profile of
raw goethite powder was observed. The thermal loss noted in
raw goethite was higher than that of heated goethite (3–4%) indi-
cating that the surplus of hydroxyl units were present in raw
mud collected from iron ore mine. The results indicated that
most of the weight loss was noticed in two steps. The first weight
loss occurred at around 300 °C (Fig. S1). This phenomenon is
principally associated with loss of water content and an
endothermic peak was observed at around 300 °C. Second weight
loss was observed at 520 °C, which is associated with structural
hydroxyl content (% OH) and the possibility of goethite to hema-
tite phase transformation (Lefebvre et al., 2012), which typically
occurs at temperature more than 300 °C (Cornell and
Schwertmann, 2003; El-Sharkawy et al., 2000). The peak was
found to arise as a result of formation of an intermediate goethite
ð1Þ of higher crystalline structure followed by the expulsion of H2O
molecules from the reacting goethite, which transforms to
a-Fe2O3 above 300 °C temperature (Flores et al., 2012). DTA
results were associated with the loss of adsorbed water (Fig. 1)
and structural OH with phase transformation (Liu et al., 2013)
between temperature of 250 and 600 °C; and these phenomena
are endothermic (Cornell and Schwertmann, 2003). After heat
treatment, thermal stability of the treated goethite enhanced,
which might have occurred due to phase transformation (Eq.
(3)) from goethite to hematite (thermal dehydration).
2FeOðOHÞ ! Fe2 O3 þ H2 O ð3Þ
 D.A. Jadhav et al. / Bioresource Technology 191 (2015) 110–116
0.1
0.0
-0.1
DTG (%/min)
-0.2
-0.3
-0.4
-0.5
-0.6
0 100 200 300 400 500 600
0
Temperature ( C)
Fig. 1. DTG profile comparison of goethite powder (raw and treated).
3.1.2. Energy-dispersive X-ray spectroscopy (EDX) analysis
EDX analysis of raw and treated goethite shows that higher con-
tent of Fe-ions (about 64–73%) was present in raw and treated
goethite. Higher ferrous iron was present in raw goethite powder
along with Al, Si, Ca and minor content of other ions. EDX analysis
of the raw mine drainage mud used in present study showed high
content of Fe (73%) and O (34.3%) (Fig. S2), which confirms the
presence of Fe-oxy(hydroxi)des in the form of goethite.
3.1.3. Fourier Transform Infrared Spectroscopy (FTIR) Analysis
FTIR analysis was carried out for both goethite samples to
determine the bonding of iron species. Both raw and treated
goethite spectrum showed a minor difference in transmittance.
Appearance of peaks at 1000 and 550 cm1 was referred to Fe–O
bending and stretching modes of vibration (Fig. S3). The peaks
observed beyond 3700 cm1 were mainly due to moisture absor-
bance in raw goethite; whereas, this peaks disappeared when
goethite was heated at 550 °C, which could be attributed to bulk
hydroxyl stretching during FTIR spectra. The absorption peaks
obtained in the range of 3600–3800 cm1 indicate the characteris-
tics of OH1 ions and the bands at 550 cm1 and 1000 cm1 repre-
sent the Fe–O vibration mode. Two absorption bands observed at
890 and 780 cm1 are important characteristic bands of goethite
that has been recovered from mining mud. In treated goethite sam-
ple, the distinguishing bands of goethite gradually vanished. At the
same time, the distinctive vibrations band of treated goethite were
noted at about 550 and 450 cm1, representing phase change from
goethite to hematite due to thermal dehydration (Cornell and
Schwertmann, 1996).
3.1.4. X-ray diffraction (XRD) analysis
XRD results show that the diffraction peaks of goethite became
wider and weaker after heat treatment of goethite. The sharp peaks
noted for treated goethite indicate recovered goethite was highly
crystalline in nature. The first broad peak located at 2h value of
35–40° was noted for both raw and treated goethite samples.
However, treated goethite exhibited a semi crystalline structure
(Cheng et al., 2011) with a giant peak at a 2h angle of 35–40°
(Fig. S4). The peak intensity shows slight decrease with heat trea-
ted goethite, and then disappear and some peaks were replaced by
several new reflections. The new reflections with low intensity
appeared after heating at 550 °C, due to the transformation of
goethite to hematite (Castaldi et al., 2008). FTIR spectrums and
113
other material characteristics confirm the recovered iron oxide
from mining mud was present in the form of goethite.
3.1.5. BET analysis for surface area determination
BET analysis revealed that surface area of goethite samples
decreased from 35.7 m2/g (raw) to 32.66 m2/g (treated)
(Table S5). The decrease in surface area after heat treatment shows
that dehydroxylation of goethite results into sintering of internal
and inter-particles (Liu et al., 2013). The micro-pores were inte-
grated to meso-pores with thermal treatment, which resulted into
increase in pore size (from 7.09 to 7.63 nm) and decreased the sur-
Raw face area of treated goethite (550 °C) as compared to raw goethite
Treated (Liu et al., 2013). However, slight variation was noted in total pore
volume of treated goethite sample (0.0623 cm3/g) as compared to
raw goethite sample (0.0633 cm3/g).
700 800 3.2. Wastewater treatment
Performance of MFCs was evaluated in terms of COD removal,
which is also useful to calculate CE and energy efficiency (Logan,
2008). In present study, COD removal of 74 ± 5.3%, 78 ± 3.8% and
83 ± 6.9% was achieved in MFC-1, MFC-2 and MFC-3, respectively
(Table 1). Higher COD removal efficiency in the case of control
MFC indicates more amount of organic matter utilized by microbes
during oxidation process in anodic chamber for different reactions.
The CE represents the effective consumption of substrate for cur-
rent production over particular time period. At 100 X external
resistance, CE of 34 ± 1.9% and 33 ± 1.34% was achieved in MFC-1
and MFC-2 with COD removal of about 74 ± 5.3 and 78 ± 3.8%,
respectively (Table 1). The CE observed in MFC-3 (13 ± 0.97%)
was lower than other two MFCs; although in MFC-3 the organic
matter removal was higher than other. Higher organic matter
removal and lower CE in control MFC-3 indicates less fraction of
electrons has been effectively utilized for harvesting the charges
and they are lost for other non-electrogenic reactions due to slow
electron transfer and higher overpotential. However, increased CE
in MFC-1 and MFC-2 represents that higher amount of organic
matter has been utilized for current production. Also, application
of the goethite on anode enables the microbes to dispose of elec-
trons at sufficiently higher rates; and thus effectively facilitates
the electron transfer between bacteria and anode, which results
into increase in the charge harvesting efficiency i.e. CE.
3.3. Electricity generation
A sustainable power density of 8.6 ± 0.98, 8.26 ± 0.77 and
3.1 ± 0.46 W/m3 was achieved for MFC-1, MFC-2 and MFC-3,
respectively, at an external resistance of 100 X. Maximum OCV
of 828 ± 47, 791 ± 33, and 783 ± 37 mV was obtained for MFC-1,
MFC-2 and MFC-3, respectively. The anode potential was also less
in MFC-1 (522 ± 31 mV) as compared to 437 ± 23 mV in MFC-3,
due to improvement in electron accepting capabilities of anode
and microbial activities in anodic chamber of MFC-1. This
Table 1
Comparison of overall performance of MFCs.
MFC Parameters MFC-1 MFC-2 MFC-3
Max. power density (W/m3) 17.1 11 3.5
Max. current density (A/m3) 29 23.33 15.33
Internal resistance (X) 20 60 250
COD removal efficiency (%) 74 ± 5.3 78 ± 3.8 83 ± 6.9
CE (%) 34 ± 1.9 33 ± 1.34 13 ± 0.97
Solution resistance (X) 27.89 28.32 21.1
Polarization resistance (X) 2.4 8.32 97
Bio-capacitance (mF/cm2) 33 30 7.5
114 D.A. Jadhav et al. / Bioresource Technology 191 (2015) 110–116
improvement in potential of the goethite coated anode was much
higher as compared to that obtained for MFC with 5% a-FeOOH
modified anode (Peng et al., 2013b). Improvement in OCV and
operating current of MFC with goethite coated anode indicates
the use of goethite enhanced the electron transfer (Peng et al.,
2013b). Thus, utilization of waste product (goethite) recovered
from iron ore mine as catalyst on anode shows enhancement in
the anodic activities.
While coating goethite on anode, PVA was used as binder. The
PVA degrading capacity of most microorganisms is extremely
restricted. In the present study, the power density obtained in con-
trol MFC-3 having SS anode without any binder was 3.1 W/m3 at
an external resistance of 100 O, which was increased to
3.31 W/m3 in MFC where only PVA coated SS anode was used.
Hence, there was slight increment in power produced, by only 5–
6%, when only PVA coated anode was used in MFC as compared
to SS anode without PVA binder. Also, COD removal of 85 ± 3.8%
was attained in this MFC, which was similar to COD removal
obtained in MFC-3. Over the short period of operation, there was
no significant effect of PVA degradation on power output of MFC.
However, during long term of operation, biodegradability of PVA
might affect the power production and treatment efficiency of
MFC.
3.4. Electrochemical analyses
3.4.1. Polarization behavior
During forward polarization, maximum power density of
17.1 W/m3 was achieved in MFC-1 at an internal resistance of
20 X (Table 1). Also, power output of 11 W/m3 was achieved at
an internal resistance of 50 X in case of MFC-2 (Fig. 2). The power
output in MFC-1 was fivefold higher as compared to that of control
MFC-3 (3.5 W/m3 at 250 X). Volumetric power density of MFC-1
was comparatively higher than MFCs with ferrous oxide coated
anode used in previous studies (Peng et al., 2012; Peng et al.,
2013a,b, 2015). Enhanced power in MFC-1 was attributed mainly
due to the improved anodic reactions by faster EET and catalytic
nature of Fe-ion of treated goethite as compared to other MFCs.
In case of MFC with goethite coated anode, the conductive ferrous
ions were used by electrogenic active bacteria present in the inocu-
lum as a mediator for transfer of electrons with effective inter-
species electron transfer (Kato et al., 2012). Relatively higher CE
and sustainable power was observed when MFC-1 and MFC-2 were
operated with external resistance of 100 O. However, maximum
900
800
OV- untreated goethite
Operating Voltage (m V)
700 OV- control MFC
OV- treated goethite
600 PD- untreated goethite
PD- control MFC
PD- treated goethite
500
400
300
200
100
0 20000 40000 60000
3
Current Density (mA/m )
Fig. 2. Polarization behavior of MFCs.
power density was higher in MFC-1 than MFC-2, mainly due to
higher electron transfer rate and phase conversion of goethite to
hematite. Due to higher conductivity of hematite over goethite, it
promotes rapid movement of electrons and results into increase
in the charge density (Cornell and Schwertmann, 1996). Also, rate
of reducibility of hematite is comparatively higher than goethite.
Thus, the improvement in power production of MFC-1 was attrib-
uted to reduction in internal resistance (from 60 to 20 O) and lower
standard redox potential of hematite (Fe2O3/Fe2+ = 0.287 V vs.
SHE) as compared to goethite (FeOOH/Fe2+ = 0.274 V vs. SHE).
During polarization, negative anodic potential in MFC-1 sus-
tained even at higher current density than that of other MFCs,
showing its higher charge storing capacity at lower resistances.
Also, lower relative drop in anodic potential with increasing cur-
rent density was observed in MFC-1 as compared to other MFCs.
Lower relative drop in anode potential of MFC-1 during polariza-
tion shows reduction in the activation overpotential as compared
to MFC-3. Also, reduction in overpotential was attributed to signif-
icant growth of electrogenic bacteria on anode surface, which fur-
ther reduces the bacterial metabolism loss as well as ohmic
resistance of the cell. Thus, goethite is proved to be a suitable can-
didate as anodic catalyst to harvest the charge stored even at lower
external resistances.
3.4.2. Electrochemical impedance spectroscopy (EIS) analysis
EIS can be effectively used to analyze the response of catalyst
(or mediators) to a low amplitude AC signals over mid-frequency
range. At high frequency region, the solution resistance of all
MFCs varied from 21 to 29 O due to similar electrolyte conditions
as noted in fitted equivalent circuit (Table 1). During EIS analysis,
the polarization resistance of 2.4, 8.31 and 97 O was obtained for
MFC-1, MFC-2 and MFC-3, respectively (Fig. 3). The polarization
resistance decreased in MFC-1 and MFC-2, due to the decrease in
over-potential losses in these MFCs. As observed from Nyquist plot,
constant phase element (CPE) at low frequency region was
enhanced with catalytic activity of goethite as compared to control
MFC (Fig. 3). Warburg diffusion resistance of control MFC-3 was on
higher side than other MFCs indicating higher mass transport
losses during anodic reactions (Rabaey et al., 2010). The decrease
in mass transport losses and increase in CPE during impedance
analysis (Fig. 3) support enhanced capacitance and diffusion condi-
tion on the anode surface with the use of goethite. Thus, modified
anode of MFC with coating of treated goethite resulted into
50
16000
MFC-Treated goethite
MFC- Untreated goethite
MFC- Control
40
Power Density (m W /m 3 )
12000
30
–Z'' (Ohm)
8000
20
4000
10
0
0
25 50 75 100 125
Z' (Ohm)
Fig. 3. Nyquist plots for MFCs during EIS analysis.
 D.A. Jadhav et al. / Bioresource Technology 191 (2015) 110–116
improvement in the power output, due to decrease in overall inter-
nal resistance of the cell.
3.4.3. Tafel analysis
Tafel analysis is a technique for evaluating the kinetic activity of
electrodes that mainly correlates the exchange current density (io),
charge transfer resistance (Rct), charge transfer coefficient (b) and
Tafel slope (b) with reference to over-potential (g) of individual
electrodes (Vaszilcsin and Nemes, 2009). The exchange current
densities of 0.69, 0.37 and 0.24 mA/m2 were observed for MFC-1,
MFC-2 and MFC-3, respectively (Table 2). Three fold increment in
io was observed in MFC-1 with heat treated goethite coated anode,
which indicates faster reaction rate with lower activation energy
barrier. Also, decreased charge transfer resistance from 102 to
37 O.m2 in MFC-1 represents the capability of heat treated goethite
coated anode to support the transfer of charge at electrode–elec-
trolyte interface. Lower Rct in case of MFC-2 (69 O.m2) revealed
that addition of goethite enhances the rate of electron transfer by
reducing activation barrier that occurred for electron flow from
substrate to anode (Table 2). Increase in Rct reduces the current
density by increasing internal resistance as observed in case of
MFC-3. Also, lower values of b for MFC-1 and MFC-2 show lower
energy is lost to overcome the activation barrier due to improved
electron transfer rate in the anodic chamber (Ghadge et al.,
2014). Lower power output due to the lower exchange current
density and the higher charge transfer resistance associated with
control MFC-3 has been conquered due to the use of goethite coat-
ing on the anode in MFC-1 and MFC-2.
3.4.4. Cyclic voltammetry (CV) analysis
The catalytic behavior of goethite was examined by performing
cyclic voltammetry analysis under substrate available conditions
(turnover). No significant peaks were observed during scanning
potential from 1 to +1 V. The maximum oxidation currents of
35, 32 and 8 mA were obtained for MFC-1, MFC-2 and MFC-3,
respectively (Fig. 4). Higher redox current was noticed in case of
MFC-1 with goethite coating on anode as compared to control
MFC mainly due to faster EET and increase in electrochemical
active surface area. Significant increase in maximum current pro-
duced by MFC-1 and MFC-2 reflects that more number of electrons
were available when goethite coated anode was used, due to accel-
erated EET. For stainless steel anode, the bio-capacitance of 33, 30
and 7.5 mF/cm2 was obtained for MFC-1, MFC-2 and MFC-3,
respectively (Table 1). The capacitance value of anode is directly
related to charge storage capacity of anode. The charge storage
capacity of anode improved with coating of goethite on anode sur-
face as compared to that of unmodified SS anode. Higher redox cur-
rent during cyclic voltammetry supports enhanced bio-capacitance
of the anode surface (Deeke et al., 2012) with use of goethite.
3.5. Catalytic behavior of goethite during electron transfer
During oxidation of substrate in anodic chamber, electrons
generated reduced Fe(III) ions present in goethite. Fe(III) gets
Table 2
Tafel analysis for determination of electrode kinetics of different MFCs.
MFC Electrode io (mA/m2) Rct (X.m2) b (mV/dec)
MFC-1 Anode 0.69 37.63 26.58
Cathode 2.41 10.7 29.3
MFC-2 Anode 0.37 68.9 13.82
Cathode 0.35 75.08 33.36
MFC-3 Anode 0.24 102.28 11.77
Cathode 0.26 99.3 36.33
115
0.040
MFC-1 (treated goethite)
MFC-2 (untreated goethite)
0.032 MFC-3 (control)
0.024
Current (A)
0.016
0.008
0.000
-0.008
-1.0 -0.5 0.0 0.5 1.0
Potential (V)
Fig. 4. Turnover cyclic voltammograms for MFCs.
reduced to Fe(II) after accepting the electron which results in
phase change. During extracellular electron transfer, a part of
goethite serves as redox couple between Fe(II) and Fe(III) at the
interface of biofilm and anode. The phase change between Fe(II)
and Fe(III) might have been contributing to transitory storage
of electrons (Eq. (4)) via microbial or electrical reduction/oxida-
tion (Sun et al., 2013), which could result in the increase of
cumulative charge stored in goethite coated anode of MFC-1
and MFC-2.
Fe3þ þ e ! Fe2þ ð4Þ
The Fe ions present in goethite serve as electron conduit
between bacterial cells and electron acceptor (i.e. anode) in
MFCs (Peng et al., 2013b). The electrogenic active bacteria
(EAB) in the mixed culture have cytochrome-C present in the
inner and outer membranes, which plays important role in elec-
tron transfer mechanism (Kato et al., 2012). The shuttling of
electrons through cytochromes of bacterial cells to anode surface
has been facilitated by electron carrier capacity of Fe(III) along
with multiple redox reactions (Peng et al., 2012; Watanabe
et al., 2009). Electrogenic bacteria have ability to recognize the
surface of iron oxides (Nakamura et al., 2009) and initiate long
distance EET (Lovley, 2006) to the attached iron oxides as a ter-
minal process in its metabolism. Goethite promotes the electron
transfer of redox-active proteins due to its good biocompatibility
characteristics (Li and Gao, 2008) and enhances the electron
transfer efficiency. Therefore, application of goethite as a catalyst
kinetically enhances the electron transfer between bacteria and
anode. This mechanism of enhancement in EET helps in the
improvement of transient charge storage on anodes (Peng
et al., 2012).
Significant boost in current produced by MFC-1 represents
that more number of electrons reduced anode due to presence
of goethite, which is also evident from electrochemical analyses.
Increase in bio-capacitance, decrease in diffusion resistance as
b
well as internal resistance, and significant increment in power
produced by MFC-1, as compared to control MFC, represent
0.0009
0.0009
enhanced electron transfer and catalytic behavior of goethite as
0.0018 anode catalyst for MFC. Thus, application of cheaper and efficient
0.0007 goethite catalyst, recovered from iron ore mining mud, proved to
0.0021 be a novel approach for enhancing the electron transfer rate and
0.0007
energy generation in dual chamber clayware MFC.
116 D.A. Jadhav et al. / Bioresource Technology 191 (2015) 110–116
4. Conclusion
Utilizing goethite, recovered from iron mining mud, to enhance
CE and power from MFC was first time explored. Material charac-
terization confirms the goethite recovery from mining mud.
Fivefold increment in power was observed in MFC with
heat-treated goethite coated anode than unmodified anode, indi-
cating catalytic behavior of low-cost goethite for EET.
Improvement in bio-capacitance and charge-storage capacity of
modified anode represents enhancement in electron transfer effi-
ciency. Electrochemical analyses support that goethite coating
accelerates EET between bacteria and anode. Thus, low-cost recov-
ered goethite can serve as effective anodic catalyst for faster elec-
tron transfer, resulting into enhancement in power production of
MFC.
Acknowledgements
Grants received from Department of Science and Technology,
Government of India (File No. DST/TSG/NTS/2010/61) to undertake
this work is duly acknowledged. The authors would like to
acknowledge O. Shinde for making the red mud samples available
from iron ore mining area.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.biortech.2015.04.
109.
References
APHA, AWWA, WPCF, 1998. American Water Works Association, Water Pollution
Control Federation (Eds.). Standard Methods for the Examination of Water and
Wastewater, 20th ed. American Public Health Association, Washington, DC,
USA.
Bard, A.J., Faulkner, L.R., 2000. Electrochemical Methods: Fundamentals and
Applications, 2nd ed. John Wiley and Sons, New York.
Castaldi, P., Silvetti, M., Santona, L., Enzo, S., Melis, P., 2008. XRD, FTIR, and thermal
analysis of bauxite ore-processing waste (red mud) exchanged with heavy
metals. Clay Clay Miner. 56 (4), 461–469.
Cheng, S., Jang, J.H., Dempsey, B.A., Logan, B.E., 2011. Efficient recovery of nano-
sized iron oxide particles from synthetic acid-mine drainage (AMD) water using
fuel cell technologies. Water Res. 45, 303–307.
Cornell, R.M., Schwertmann, U., 1996. The Iron Oxides: Structure, Properties,
Reactions, Occurrences and Uses, 1st ed. VCH Publishers, Weinheim, Germany.
Cornell, R.M., Schwertmann, U., 2003. The Iron Oxides: Structure, Properties,
Reactions, Occurrences and Uses, 2nd ed. Wiley-VCH, Weinheim.
De Silva, A.R., Castro, C.D., Petter, C. O., Schneider, I.A.H., 2011. Production of iron
pigments (goethite and haematite) from acid mine drainage. In: Rüde, Freund,
Wolkersdorfer (eds.). Mine Water – Managing the Challenges. International
Mine Water Association (IMWA), Aachen, Germany, <https://www.imwa.
info/docs/imwa_2011/IMWA2011_Silva_377.pdf> (accessed 24.01.14).
Deeke, A., Sleutels, T.H., Hamelers, H.V., Buisman, C.J., 2012. Capacitive bioanodes
enable renewable energy storage in microbial fuel cells. Environ. Sci. Technol.
46 (6), 3554–3560.
El-Sharkawy, E.A., El-Hakam, S.A., Samra, S.E., 2000. Effect of thermal treatment on
the various properties of iron(III), aluminum(III) co-precipitated hydroxide
system. Mater. Lett. 42, 331–338.
Flores, R.G., Andersen, S.L., Maia, L.K., José, H.J., de Moreira, R.F., 2012. Recovery of
iron oxides from acid mine drainage and their application as adsorbent or
catalyst. J. Environ. Manage. 111, 53–60.
Ghadge, A.N., Sreemannarayana, M., Duteanu, N., Ghangrekar, M.M., 2014. Influence
of ceramic separator’s characteristics on microbial fuel cell performance. J.
Electrochem. Sci. Eng. 4 (4), 315–326.
Jadhav, G.S., Ghangrekar, M.M., 2008. Improving performance of MFC by design
alteration and adding cathodic electrolytes. Appl. Biochem. Biotechnol. 151,
319–332.
Jadhav, D.A., Ghadge, A.N., Ghangrekar, M.M., 2014. Simultaneous organic matter
removal and disinfection of wastewater with enhanced power generation in
microbial fuel cell. Bioresour. Technol. 163, 328–334.
Ji, J.Y., Jia, Y.J., Wu, W.G., Bai, L.L., Ge, L.Q., Gu, Z.Z., 2011. A layer-by-layer self
assembled Fe2O3 nanorod-based composite multilayer film on ITO anode in
microbial fuel cell. Colloid Surf. A 390, 56–61.
Kato, S., Hashimoto, K., Watanabe, K., 2012. Microbial interspecies electron transfer
via electric currents through conductive minerals. Proc. Natl. Acad. Sci. 109 (25),
10042–10046.
Lefebvre, O., Neculita, C.M., Yue, X., Ng, H.Y., 2012. Bioelectrochemical treatment of
acid mine drainage dominated with iron. J. Hazard. Mater. 241–242, 411–417.
Li, J., Gao, H., 2008. A renewable potentiometric immunosensor based on Fe3O4
nanoparticles immobilized anti-IgG. Electroanalysis 20 (8), 881–887.
Liu, H., Chen, T., Zou, X., Qing, C., Frost, R.L., 2013. Thermal treatment of natural
goethite: thermal transformation and physical properties. Thermochim. Acta
568, 115–121.
Logan, B.E., 2008. Microbial Fuel Cells. Wiley & Sons Inc., Hoboken, New Jersey, USA.
Lovley, D.R., 2006. Bug juice harvesting electricity with microorganisms. Nat. Rev.
Microbiol. 4, 497–508.
Lowy, D.A., Tender, L.M., Zeikus, J.G., Park, D.H., Lovley, D.R., 2006. Harvesting
energy from the marine sediment–water interface II: kinetic activity of anode
materials. Biosens. Bioelectron. 21 (11), 2058–2063.
Nakamura, R., Kai, F., Okamoto, A., Newton, G.J., Hashimoto, K., 2009. Self-
constructed electrically conductive bacterial networks. Angew. Chem. Int. Ed.
48 (3), 508–511.
Paramguru, R.K., Rath, P.C., Misra, V.N., 2005. Trends in red mud utilization – a
review. Min. Proc. Ext. Met. Rev. 26, 1–29.
Peng, X., Yu, H., Wang, X., Zhou, Q., Zhang, S., Geng, L., Sun, J., Cai, Z., 2012. Enhanced
performance and capacitance behavior of anode by rolling Fe3O4 into activated
carbon in microbial fuel cells. Bioresour. Technol. 121, 450–453.
Peng, X., Yu, H., Ai, L., Li, N., Wang, X., 2013a. Time behavior and capacitance
analysis of nano-Fe3O4 added microbial fuel cells. Bioresour. Technol. 144, 689–
692.
Peng, X., Yu, H., Wang, X., Gao, N., Geng, L., Ai, L., 2013b. Enhanced anode
performance of microbial fuel cells by adding nano-semiconductor goethite. J.
Power Sources 223, 94–99.
Peng, X.H., Chu, X.Z., Huang, P.F., Shan, K., 2015. Improved power performance of
activated carbon anode by Fe2O3 addition in microbial fuel cells. Appl. Mech.
Mater. 700, 170–174.
Rabaey, K., Angenent, L., Schroder, U., Keller, J., 2010. Bioelectrochemical systems:
from extracellular electron transfer to biotechnological application. In: LaBelle,
E., Bond, D.R. (Eds.), Electrochemical Techniques for the Analysis of
Bioelectrochemical Systems. IWA Publishing, London, UK, pp. 135–148.
Sun, M., Song, W., Zhai, L.F., Ru, X.R., Cui, Y.Z., 2013. Elucidating electro-oxidation
kinetics of Fe(II) in the anode of air-cathode fuel cells from an Fe(II) speciation
perspective. Chem. Eng. J. 228, 781–789.
Vaszilcsin, N., Nemes, M., 2009. Introduction to Electrochemistry by Problems.
Politehnica Publishing House, Timisßoara, Romania, pp. 132–164.
Wang, P., Li, H., Du, Z., 2013. Deposition of iron on graphite felts by thermal
decomposition of Fe(CO)5 for anodic modification of microbial fuel cells. Int. J.
Electr. Sci. 8, 4712–4722.
Wang, L., Su, L., Chen, H., Yin, T., Lin, Z., Lin, X., Fu, D., 2015. Carbon paper electrode
modified by goethite nanowhiskers promotes bacterial extracellular electron
transfer. Mater. Lett. 141, 311–314.
Watanabe, K., Manefield, M., Lee, M., Kouzuma, A., 2009. Electron shuttles in
biotechnology. Curr. Opin. Biotechnol. 20 (6), 633–641.
Zhao, F., Slade, R.C., Varcoe, J.R., 2009. Techniques for the study and development of
microbial fuel cells: an electrochemical perspective. Chem. Soc. Rev. 38 (7),
1926–1939.
Zhou, Y.L., Yang, Y., Chen, M., Zhao, Z.W., Jiang, H.L., 2014. To improve the
performance of sediment microbial fuel cell through amending colloidal iron
oxyhydroxide into freshwater sediments. Bioresour. Technol. 159, 232–239.