i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

Fabrication of Ni nanoparticles-dispersed carbon

micro-nanofibers as the electrodes of a microbial
fuel cell for bio-energy production

Shiv Singh a, Nishith Verma a,b,*

a
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
b
Center for Environmental Science and Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

article info abstract

Article history: A nickel (Ni) nanoparticles- (NPs) dispersed web of carbon micro-nanofibers (ACFs/CNFs)
Received 5 May 2014 was fabricated as the electrode of a microbial fuel cell (MFC) for bio-energy production
Received in revised form using Escherichia coli as a microbial catalyst. The multiscale web of ACFs/CNFs was prepared
19 October 2014 using chemical vapor deposition, with the Ni NPs as the catalyst and benzene as the carbon
Accepted 13 November 2014 source to grow the CNFs on the ACF substrate. The Ni NPs attached at the tips of graphitic
Available online 6 December 2014 CNFs facilitated the transfer of E. coli-released electrons to the anode of MFCs. Linear sweep
voltammetry was performed to determine power density and open circuit potential (OCP)
Keywords: of the prepared MFCs. The power density and OCP were experimentally measured as
Microbial fuel cells 710 5 mV and 1145 20 mW/m2, respectively, which were approximately 9 times greater
Power density than those of the ACF substrate-based MFCs. The transition metal-CNFs-based electrodes
Escherichia coli prepared in this study may be a potentially alternative to the expensive noble metals-based
Carbon nanofiber electrodes presently used in MFCs.
Metal nanoparticles Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Considering that the municipal or domestic wastewater con-

Introduction
Presently, the enormous amount of fossil fuels is burnt to
generate electricity. This has caused significant increase in
the concentration levels of carbon dioxide in the atmosphere,
leading to global warming and also, the gradual depletion of
fossil fuels. Therefore, there is a need to explore clean source
of energy as an alternative to fossil fuels. In this context, mi-
crobial fuel cells (MFCs) have drawn considerable attention of
researchers. MFCs are novel electrochemical devices which
can convert microbial metabolic power into electricity.
tains significant amounts of biodegradable organic wastes,
such devices have potential of producing electricity from the
wastewater treatment plants [1,2]. These devices may also be
potentially used for the recovery of metals and nutrients from
industrial effluents [3,4].
One of the challenges in developing efficient MFCs is the
fabrication of high-quality electrodes. The electrodes should
be relatively inexpensive, highly conductive and should have
large surface area. Anode is responsible for the electron
transfer, whereas the preferred reaction on cathode is oxygen
reduction. Studies have shown that biocompatibility,

* Corresponding author. Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India. Tel.: 91
512 2596352; fax: 91 512 2590104.
E-mail addresses: vermanishith@gmail.com, nishith@iitk.ac.in (N. Verma).
http://dx.doi.org/10.1016/j.ijhydene.2014.11.073
0360-3199/Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
1146 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3
electronic conductivity and high electro-catalytic activity to-
wards the oxidation of metabolites are vital parameters for
the selection of anode to enhance power density [5,6]. Cathode
is also a restrictive component of MFCs [7]. In the cathode
chamber, atmospheric oxygen is usually used as the electron
acceptor. Despite oxygen being readily available and having
high oxidative potential, an efficient catalyst is required to
overcome the large over-potential of oxygen.
In the past decade, several noble metals-based carbon
electrodes have been fabricated for MFCs, because of their su-
perior activity, biocompatibility, and high electrical conduc-
tivity. Platinum (Pt) is the dominant metal used as a catalyst in
the electrode for the oxidation of metabolites and oxygen
reduction [8]. The other noble metals-based catalysts used for
MFCs are Ru/Pt loaded on carbon nanotubes (CNTs) [9,10], Au
nanoparticles (NPs) sputtered in carbon-paper [11], and
TieTiO2/Pt composite [8]. Different forms of carbon without
metals have also been developed as electrodes for MFCs, for
examples, the graphene deposited carbon cloth [12], reticulated
carbon foam [13], the electrospun polyacrylonitrile-based car-
bon nanofibers (CNFs) [14] and graphitic carbon felt [15,16].
The present study describes the development of the nickel
(Ni) NPs-dispersed and chemical vapor deposition- (CVD)
grown multiscale forming web of carbon micro-nanofibers
(ACFs/CNFs) as the electrodes (anode and cathode) of a dou-
ble chambered MFC. The development of the metal NPs-
dispersed ACFs/CNFs is relatively newer. Such materials
have been applied as efficient adsorbents for environmental
remediation [17e19]. In the most recent application the
bimetals-dispersed ACF/CNF was applied as the electrode of a
glucose biosensor [20]. Ni-based materials have been used in
other bioelectrochemical systems, in particular, microbial
electrolysis cells for hydrogen evolution [21e25]. For the first
time, Ni-ACF/CNF has been fabicated and demonstrated as an
effective electrode for MFCs in the present study. The Ni NPs
had the following multiple roles: (1) as the CVD catalyst for the
growth of the CNFs on the ACF substrate, (2) as the facilitator
of electron transfer from Escherichia coli (E. coli) to anode, and
(3) as the catalyst for oxygen reduction at cathode. The CNFs
provided biocompatibility to the growth of biofilms and
increased the electroconductivity of the electrodes.
Materials and methods
Materials
Ni(NO3)2.6H2O (purity > 97%), sodium dodecyl sulfate (SDS,
purity > 99%), C6H6, potassium hexacyanoferrate (K3Fe(CN)6,
purity > 99%), sodium acetate (CH3COONa, purity > 98%), su-
crose and other reagents, used for preparing buffers of NaCl,
KCl, Na2HPO4 and KH2PO4 were procured from Merck, Ger-
many Hydrogen (purity > 99.999%) and nitrogen (pu-
rity > 99.999%) gases were purchased from Sigma Gases, India.
The phenolic resin precursor-based ACFs were purchased
from Gun Ei Chemical Industry Co. Ltd., Japan. The E. coli (K-
12) culture was indigenously purchased. The reagents used to
prepare Luria Bertani (LB) medium, including tryptone and
yeast extract, were purchased from Thomas Baker Laboratory
Reagent, India. All aqueous solutions used in this study were
prepared in Milli-Q water. The MFC was fabricated from the
acrylic pipe procured from a local market. Proton exchange
membrane (PEM, nafion 117) was purchased from Sinsil In-
ternational, India.
Synthesis of Ni-ACF/CNF electrodes
The preparation of CNFs on the ACF substrate has been pre-
viously described [19]. Briefly, the pretreated ACF samples
were impregnated with the 0.4 M-Ni(NO3)2.6H2O salt dispersed
in water, using the wet incipient method. Approximately 0.3%
(w/w) SDS was used as an anionic surfactant in the impreg-
nating solution to prevent the agglomeration of Ni(NO3)2
crystals and facilitate their uniform dispersion in the ACF
during impregnation. After the impregnation, the ACF sam-
ples were dried for 6 h at room temperature (30 5  C) and
then for another 12 h at 120  C. Next, calcinations, reduction
and CVD were performed on the impregnated ACF sample in a
vertical reactor. The detailed configuration of the reactor and
the arrangement for holding samples are described in the
previous study [26]. The calcination and reduction of the
impregnated sample were performed in a N2 atmosphere at
400  C for 4 h and in a H2 atmosphere at 550  C for 2 h,
respectively. During the calcination and reduction, flow rates
of the gases were maintained constant at 200 standard cc per
min (sccm). Ni(NO3)2 dispersed in the ACFs were converted to
the metallic state (Ni NPs) after calcination and reduction. The
produced Ni NPs decomposed C6H6 during the CVD, forming a
multiscale web of ACFs/CNFs. The CVD was performed at
800  C for 2 h. A few samples of Ni-ACFs/CNFs were ultra-
sonicated in a 0.05 M-HNO3 solution for 5 min to dislodge the
Ni NPs from the tips of the CNFs. The prepared Ni-ACFs/CNFs
were directly used as anode and cathode in MFCs, without
requiring any further treatment. For the reference purposes,
the three types of materials used as the electrodes for MFCs in
this study are termed as (1) ACF, (2) Ni-ACF/CNF, and (3) ACF/
CNF. ACFs/CNFs were produced by sonicating Ni-ACFs/CNFs.
Fig. 1 schematically describes the steps involved in the prep-
aration of electrode materials for MFCs developed in this
study.
Construction and operation of MFCs
The supplementary figure S1 shows the schematic illustration
of an MFC. The H-shaped MFC consisted of two chambers
(effective volume 200 ml) fabricated from an acrylic pipe
(inner diameter 67.0 mm). They were connected using a
40 mm-diameter pipe. A PEM (nafion 117) sheet (exposed
area 2800 mm2) was used in the connecting pipe to separate
the chambers. The electrodes were held using a Teflon-frame-
suspended 3 mm-brass wire in the respective chambers. The
anode and cathode (working area 8 cm2) were electrically
connected via an external circuit, made of a 3 mm-thick brass
wire, to a resistor (5000 U). An electronic multimeter (Model
2000, Keithley) was used to measure voltage across the
resistor. The distance between the anode and cathode was
100 mm.
The anode chamber was filled with approximately 50 ml
volume of 10 mM-PBS (prepared using 8.0 g-NaCl, 0.2 g-KCl,
1.44 g-Na2HPO4, and 0.24 g-KH2PO4 at pH 7), 50 ml volume of
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3
Fig. 1 e Schematic illustration of the fabrication of the Ni-ACF/CNF electrodes for MFCs.
100 mM-sucrose solution made up in 10 mM-PBS, 50 ml vol-
ume of E. coli-LB broth (108e109 CFU/ml at pH 7) and 50 ml
volume of 12 mM-CH3COONa. N2 was continuously purged
through the anolyte solution for 30 min to establish an
anaerobic condition. The cathode chamber was filled with
200 ml of 100 mM-K3Fe(CN)6 solution prepared in 10 mM-PBS.
The initial pH of the catholyte solution was 7.0. The base of the
cathode chamber was fitted with a bubble disperser externally
connected to a peristaltic pump (speed 100 rpm) which
continuously dispensed the atmospheric air (~200 sccm) in the
cathode chamber during the test. Both electrodes (anode and
cathode) were fabricated from the same material: the ACF
substrate, or Ni-ACF/CNF, or ACF/CNF. The tests were per-
formed in the batch mode at room temperature.
Electrochemical measurement and analysis
Power density and open circuit potential (OCP) were obtained
at the scan rate of 1.0 mVs1 from 1 V to 0 V, using the
potentiostat (AUTOLAB-PGSTAT302N) and the linear sweep
voltammetry (LSV) method [27]. Nova software was used to
draw the polarization curves. Tests were replicated 5 times for
a single MFC set-up. The area-power densities (P mW/m2) of
the prepared MFC were calculated using P V  I/A, where V is
the measured voltage, I is the current with respect to the
applied voltage and A is the area (8 cm2) of either anode or
cathode. Before measurements, the MFCs were left idle for 5
days, connected to a 5000 U-resistor, for the stabilization of
cell voltage, because it was found to slowly increase during
the initial period of the tests. After 2 days of initialization, the
voltage nearly stabilized, although a slight fluctuation was
observed. Therefore, the electrochemical analysis was per-
formed after 5 days when the cell voltage had completely
stabilized. The electrochemical impedance spectroscopy (EIS)
measurements were performed to determine the internal re-
sistances of the MFC, using the FRA software and the poten-
tiostate. EIS measurements were performed for the cell from
100,000 to 0.01 Hz at the potential amplitude of 0.01 V. The EIS
1147
measurements of the MFC were obtained at the OCP of the
respective electrodes. The counter and reference electrodes of
the potentiostate were connected to the cathode, whereas the
working electrode was connected to the anode.
Surface characterization of electrocatalyst
ACFs, Ni-ACFs/CNFs and the ACFs/CNFs were characterized
using several techniques, including atomic absorption spec-
troscopy (AAS), scanning electron microscopy (SEM), energy
dispersive X-ray (EDX) spectroscopy, X-Ray diffraction (XRD),
Raman spectroscopy and Brunauer-Emmet-Teller (BET) sur-
face area and pore-size distribution (PSD) measurements. The
AAS (Varian AA-240, USA) analysis of the impregnating solu-
tion was performed to calculate the Ni loading in the ACFs.
The surface topographies of the ACFs, Ni-ACFs/CNFs and the
ACFs/CNFs were examined using field emission SEM (Supra
40VP, Zeiss, Germany). XRD analysis was performed to
determine the crystal size and patterns of the Ni NPs
dispersed in the ACFs/CNFs. A Cu-Ka radiation (k 1.54178 A )
was used for determining the XRD patterns in a 2q range of
10 e120 and scan rate of 3 per min. Raman analysis (Model:
Alpha, Make: Witec, Germany) was performed to determine
the relative disorder or graphitization (ID/IG) in the prepared
electrode samples. The data were collected using the Ar-ion
laser (l 532 nm) as an excitation source and a CCD as the
detector in the range of 500e4000 cm1 in air at 25  C. The SBET,
total pore volume (Vtotal) and PSD of the prepared electrodes
were determined using nitrogen at 77 K and the Autosorb-1C
Quantachrome instrument.
Result and discussion
Ni loading on prepared electrode materials
The Ni loading in the impregnated ACF samples was deter-
mined to be ~450 mg/g. The loading was ~30% higher than that
1148 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3
Fig. 2 e SEM images of (AeA) ACF, (BeB) Ni-ACF, (CeC) Ni-ACF/CNF, (DeD) ACF/CNF, and EDX spectra of (E) Ni-ACF and (E)
Ni-ACF/CNF samples. Inset shows the focus area for EDX.
in the samples impregnated without using SDS. The surfac-
tant enhanced the metal loading and dispersion in the ACFs
by preventing the agglomeration of the salt crystals in the
impregnating solution. As shown later, the uniform Ni loading
facilitated the dense and uniform growth of CNFs on ACFs.
Surface topography
The surface morphologies of the fabricated materials were
examined using SEM. Fig. 2 describes the SEM images at low
(5e15 KX) and high magnifications (100e200 KX). Fig. 2(AeA0 )
shows the SEM images of the ACF substrate. The ACF surface
was smooth. Macro-pores were visible on the external surface.
Fig. 2(BeB0 ) shows the SEM images of the Ni NPs-dispersed
ACF (Ni-ACF) samples. The Ni NPs were uniformly dispersed
on the ACF surface. The Ni NPs were also observed inside the
pores. Fig. 2(CeC0 ) shows the SEM images of Ni-ACFs/CNFs.
The growth of the CNFs on the ACF was uniform and dense.
As shown later, the CNFs were graphitic and enhanced the
conductivity of the prepared electrodes. The shiny Ni NPs
present at the tips of the CNFs confirmed the tip-growth
mechanism. Fig. 2(DeD0 ) shows the SEM images of the ACF/
CNF samples. As observed, most of the Ni NPs were dislodged
from the tips during the ultrasonication.
Fig. 2(EeE0 ) describes the EDX spectra of the Ni-ACF and Ni-
ACF/CNF samples. The area-spectrum (Fig. 2E) showed the
presence of carbon and Ni, confirming that NiO was
completely reduced to metallic (Ni) state during the H2-
reduction at 550  C. Fig. 2E0 shows the point-EDX spectra of Ni-
ACFs/CNFs. The spectra confirmed the shiny NPs as Ni. No
other foreign impurities were detected.
XRD patterns
The XRD analysis of the ACF and Ni-ACF samples was per-
formed to determine the structure of the crystalline phase,
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3 1149

using JCPDS software (No- 04-0850). Fig. 3a shows the XRD
spectra of ACFs (shown in black) and Ni-ACFs (shown in blue).
There was a common characteristic peak at 2q angle of ~26 in
both samples, attributed to the crystallographic index of (0 0 2)
in the amorphous carbon. The spectra of the Ni-ACFs exhibi-
ted five distinctive peaks at 2qs 44.5, 51.8, 76.3, 92.9 and
98.44 , corresponding to (1 1 1), (2 0 0), (2 2 0), (3 1 1) and (2 2 2)
indices, respectively. The spectra of the Ni-ACFs also revealed
that the prepared samples contained Ni in its pure metallic
FCC phase (previously confirmed using the EDX analysis). The
crystallite size of the Ni NPs, calculated using the Scherrer
formula, was found between 10 nm (corresponding to 44.5 )
and 31 nm (corresponding to 76.3 ).
Raman spectra
Raman spectroscopy was used to investigate the presence of
ordered and disordered phases in ACFs/CNFs. Fig. 3b describes
the Raman spectrum of the ACF and Ni-ACF/CNF samples. The
first vibrational peak observed at 1342.6 cm-1 was attributed to
the disordered phase (D-band), whereas the second vibra-
tional peak at 1580.4 cm-1 was attributed to the graphitic
phase (G-band) of carbon. The D-band represents the vibra-
tions of carbon atoms having dangling bond with the unsat-
urated sp3 hybridized valence in the planar terminations of
the disordered graphite structure, whereas the G-band rep-
resents the planar geometry (sp2 hybridized) of carbon atoms.
The ID/IG ratio reflects the degree of disorder, as expressed in
the sp3/sp2 carbon ratio [28]. The ID/IG ratio of ACFs was
determined to be 1.17. The ratio decreased to 1.06 in Ni-ACFs/
CNFs. Therefore, Ni-ACFs/CNFs contained higher degree of
graphitization than ACFs. In other words, ACFs had more
disordered structure than ACFs/CNFs. The graphitic phase
enhanced the conductivity of the ACF/CNF electrode, resulting
in the relatively superior performance of Ni-ACFs/CNFs,
shown later.
SBET, Vtotal and PSD analysis
The BET surface area of the prepared electrodes was deter-
mined using the linearized BET equation fitted to 20 data
points corresponding to the amounts of nitrogen adsorbed vs
relative pressures (P/P0) ranging from 0.05 to 0.35. The micro-
porosity and meso-porosity of the prepared materials were
determined using density functional theory (DFT) and the
Barrett-Joyner-Halenda (BJH) method, respectively. Before
starting the adsorption/desorption analysis, the prepared
samples were heated at 150  C for 12 h in vacuum.
Table 1 presents the data of the analysis. The SBET and Vtotal
of the ACFs were determined to be 1140 m2/g and 0.609 cc/g,
respectively. The micro-porosity contents of the ACFs were
significantly high (~86% of the total pore volume). The SBET and
Vtotal values significantly decreased in the Ni(NO3)2-impreg-
nated samples because of the blockage of the pores with the
salts. However, the calcination increased SBET and pore vol-
ume, as the pores were opened up. The SBET and Vtotal values
increased to ~805 m2/g and 0.450 cc/g, respectively, in the NiO-
ACF samples. The reduction of NiO to Ni NPs further increased
the SBET and Vtotal values to 959 m2/g and 0.558 cc/g, respec-
tively, in Ni-ACFs. Both NiO- and Ni-ACF samples were largely
microporous. Such materials are not considered to be
conducive for the adsorption or attachment of large size
molecules such as E. coli. Interestingly, although Ni-ACF/CNF
had relatively lesser SBET (~597 m2/g) and VTotal (0.376 cc/g),
the material was considerably mesoporous (~47%), and
therefore, was suitable for the growth or multiplications of E.
coli. As shown later, the performance of the electrodes fabri-
cated using the multiscale web of Ni-ACFs/CNFs was superior
to that of Ni-ACFs.

Performance of MFCs using different electrode materials

Fig. 4 describes variation in polarization and power density

with increasing current densities, for the ACF, Ni-ACF/CNF,
and ACF/CNF samples. The bioelectricity was successfully
generated from the MFCs constructed using the prepared

Table 1 e SBET, Vtotal and PSD of the prepared materials.

Sample SBET Vtotal PSD (%)
(m2/g) (cc/g)
Micro Meso Macro
ACF 1140 0.609 86.48 5.64 7.86
Fig. 3 e (a) XRD patterns and (b) Raman spectra of the ACF Ni(NO3)2-ACF 482 0.270 85.40 9.48 5.11
and Ni-ACF samples. (For interpretation of the references NiO-ACF 805 0.450 86.29 8.91 4.78
to colour in this figure legend, the reader is referred to the Ni-ACF 959 0.554 79.27 17.33 3.39
Ni-ACF/CNF 597 0.376 47.87 47.34 4.78
web version of this article.)
1150 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3

electrodes. During the initial stage of the test, OCP was rela-
tively lower, attributed to discontinuity in the formation of
biofilm on the anode, possibly because of a relatively lesser
number of E. coli produced, thereby resulting in a small elec-
tron transfer rate to the anode. As the metabolic activity
progressed, the number of colonies of E. coli grew. The biofilm
formed on the anode became stable and the electron transfer
rate or OCP increased.
E. coli is not electrochemically conductive. However, it is
mentioned that there are two ways of transferring the elec-
tron to the anode surface by E. coli in the absence of media-
tor(s). (1) E. coli present in the biofilm can self-mediate the
extracellular electron transfer through the electrochemically
activated excretion of electron shuttling redox molecules
which work as a mediator for the electron transfer [6,29,30],
Fig. 5 e EIS analysis of the ACF, Ni-ACF/CNF and ACF/CNF
and (2) the pili of E. coli also facilitate the electron transfer to
samples at the respective OCP. Inset shows the magnified
anode [31]. In addition to the redox molecules produced by E.
plots for the Ni-ACF/CNF and ACF/CNF samples.
coli and/or the pili of E. coli, the metal NPs or carbon-based
nanomaterials can also facilitate the electron transfer from
E. coli to electrodes in the mediator-less MFCs [32,33].
water was used. Therefore, CE was not measured and the
Here, it is also important to mention that Ni or ACFs/CNFs
other parameters (power density, current density, OCP, and
do not exhibit antibacterial activities and have been used as
electrochemical impedance) were considered to be sufficient
electrode materials in MFCs and also in microbial electrolysis
to study the performance of the MFCs, discussed below.
cells [22,34]. To corroborate this aspect of the material, an
The OCP and current density of the Ni-ACF/CNF-based
antibacterial test was performed on the ACFs and Ni-ACFs/
MFCs were determined to be 710.0 5 mV and
CNFs using E. coli. The tests were performed using plate
~4650 20 mA/m2, respectively, which were significantly
count method. The results are included in the supplementary
higher than those (380.0 5 mV and 1400 mA/m2, respectively)
figure S2, showing an insignificant antibacterial effect of the
of the MFCs constructed from the ACF substrate. The area-
produced materials in this study. The colony counts of E. coli in
power density of the multiscale forming web-based MFCs
the broths containing the ACFs and Ni-ACFs/CNFs were found
was ~9 times greater than that of the ACF-based MFCs. The
to be approximately the same (~108 CFU/ml) as in the control
relative superior performance of Ni-ACF/CNF-based MFCs was
even after 72 h, thus showing no sensitivity of E. coli to the
attributed to the following three characteristics of the mate-
electrode materials. Therefore, the electrochemical activity
rial. (1) It had large (~47%) mesopore-contents which were
attributed to E. coli remained unchanged during the operation
favorable for the attachment of E. coli and the growth of bio-
of the MFCs and the performance of MFCs was considered to
films. Further, E. coli may have produced adhesins on pili and
be affected by the anodic reactions only. It is also mentioned
fimbriae, facilitating the attachment of the biofilm on the
that the Coulombic efficiency (CE) may be diminished by
surface of ACFs/CNFs [31]. (2) The graphitic phase present in
alternate electron acceptors present in the anolyte, for
the CNFs facilitated the electron transfer from the c-type cy-
example, wastewater [35]. In the present study, synthetic
tochrome of E. coli to the anode [32]. Therefore, the charge
transfer resistance (shown later) was smaller in Ni-ACFs/
CNFs, which was the reason for the production of high cur-
rent density (4650 20 mA/m2), using the MFC based on the
Ni-ACF/CNF electrodes. (3) The presence of the Ni NPs at the
tips of the CNFs also facilitated the electron transfer.
To further examine the role of the Ni NPs, polarization
tests were performed on the MFCs constructed using the
ACF/CNF samples. As shown in Fig. 4, the OCP (565 5 mV)
and power density (1005 20 mW/m2) of the MFCs based on
the ACF/CNF samples were smaller than that of the Ni-ACFs/
CNFs-based MFCs. All or most of the Ni NPs were removed

Table 2 e MFC parameters of ACF and Ni-ACF/CNF

calculated using Nyquist plots.
Sample Rs (U) Rct (U) W (U)
ACF 220.4 90.8 14.28
Fig. 4 e Polarization and power density curves for different Ni-ACF/CNF 44.6 1.8 9.17
ACF/CNF 49.5 3.6 11.23
electrodes prepared in the study.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3 1151

from the Ni-ACF/CNF samples by sonication under the pre-

Current density sent sonication conditions. In our previous study, the iden-

~1000e7000
(mA/m2)

2350e7530

1150e1900
tical sonication conditions were used to dislodge or remove

200e400
350e650
the Ni NPs from the ACF/CNF [26]. A negligible amount of Ni

~4000
4650

~700
5670

1181
530

430

260
140
NPs may have been left on the surface of the ACFs after

37
e
sonication. Therefore, indeed, the graphitic structure of CNFs
was responsible for power generation using the electrodes
fabricated from the sonicated samples (ACF/CNF). Therefore,
density (mW/m2)

it may be concluded that the Ni NPs facilitated the generation

19.31e61.3
686e1487

151e2470

166e1326
of current via the electron transfer to the anode. A small
Power

300e830
38e118

36e170

10e110
crystal size (10e31 nm) of the Ni NPs in ACFs/CNF had the
1145

4250

1313

52.5
240

462

5.7
11
catalytic effect on the reduction of atmospheric oxygen in the
cathode chamber [8].
In general OCPs should be the same for different elec-
trodes. However, the OCPs have been measured to be different
OCP (mV)

434e867

329e759
481e941

300e620
400e810
700e800

390e570
in many cases including this study, if the electrodes are
~720

~700

~300
different or modified [7, 9, 10, 14, 27, and 33]. The difference in
710

480

749

700
500
e

the OCPs for the different electrode materials used in this

study is attributed to the enhanced electron transfer at the
Polyacrylonitrile based carbon nanofiber

anode prepared from the mesoporous CNFs, in comparison to

Reticulated vitreous carbon electrodes
Carbon cloth with gas diffusion layers

the microporous ACFs. The former materials favor the biofilm

Copper-phthalocyanine and Ni NPs

formation or microbial activity via the increased bacterial

RuePt/MWNT and SnePt/MWNT

adhesion, also discussed earlier in SBET, Vtotal and PSD

Pt dispersed on carbon paper
Au sputtered carbon paper

analysis.
Cathode

Pt-coated carbon cloth

EIS analysis
Porous carbon fiber

Plain carbon cloth

EIS analysis was performed to determine the different

Bare carbon felt
Graphic sheets
Ni-ACFs/CNFs

voltage losses in the MFCs, attributed to the ohmic (solution)

Carbon felt

resistance (Rs), charge transfer resistance (Rct) and the War-

CNT/Pt

burg mass transfer diffusion resistance (W). Rs depends on

the conductivity of electrolytes and electrodes, PEM, and
Pt

different electrical interconnections between electrodes,

whereas Rct depends on the conductivity of cathode. Fig. 5
Reticulated vitreous carbon electrodes
Graphite,SnePt/MWCNT anode with

shows the Nyquist plots and an electrical model of the

Fe3O4/CNT dispersed carbon paper
Graphene deposited carbon cloth

MFCs. Table 2 summarizes the resistances of different

methylene blue and natural red

PPy/GO-modified graphite felt

electrodes-based MFCs, calculated using the Nyquist plots.

Table 3 e A comparison of performance of double chambered MFCs.

Au sputtered carbon-paper

The Rs, Rct and W values obtained for the Ni-ACF/CNF-based

Anode

MFCs were lowest (44.6, 1.8 and 9.17 U, respectively) amongst

Plain carbon paper

Plain carbon paper

Plain carbon paper

Plain carbon paper

the prepared MFCs, attributed to the favorable condition

available for the growth of biofilm in the mesospores con-
Graphic sheets
Ni-ACFs/CNFs

Graphite rods
Carbon brush

taining ACFs/CNFs and high conductivity of the CNFs, which

Carbon felt
TieTiO2/Pt

facilitated electrons transfer to cathode. Further, the Rs, Rct

and W values obtained for the MFCs based on the non-
sonicated samples were lower than those (49.5, 3.6 and
11.23 U, respectively) for the sonicated samples, attributed to
Sludge from industrial effluent

the Ni NPs present in the former samples. Therefore, the Ni

NPs also facilitated the electron transfer from the electrolyte
Shewanella oneidensis MR-1

to the electrodes of the MFC. On the contrary, the Rs value

Geobacter sulfurreducens

Pseudomonas aeruginosa
Biocatalyst

Domestic wastewater

was the highest for the ACF-based MFCs, because of the

Anaerobic sludge

absence of graphitic contents and the metal (Ni) NPs. The Rct
Activated sludge

and W values obtained for the ACF substrate-based electrode

E. coli (DH5a)
Wastewater

Wastewater
E. coli (K12)

E. coli (K12)

MFCs were also significantly high. Therefore, the produced

electrons were not easily transferred to cathode, adversely
Sludge

Sludge

Sludge

E. coli

affecting the efficacy of the MFC.

The solution resistance (Rs), the x-intercept of the Nyquist
plot, should be the same for different anode materials. How-
References

ever, the different interfacial contact resistances between an

study
Present

anode and an electrolyte can produce different Rs [36e38],

[10]

[11]
[12]
[13]
[14]
[16]
[27]
[31]
[33]

keeping the other parameters unchanged, including electro-

[1]
[2]
[4]
[7]
[8]
[9]

lyte, PEM, and distance between the electrodes. Here, the

1152 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3
difference (~5 U) observed between the Rs value of the Ni-ACF/
CNF in comparison to that of the ACF/CNF is attributed to the
presence of the conductive Ni NPs at the tips of the CNFs,
which were in contact with the electrolyte solution, whereas
the difference (~ 180 U) between that of the ACF and ACF/CNF
or Ni-ACF/CNF anode is attributed to the conductive graphitic
CNFs dispersed on the ACF substrate, also in contact with the
solution.
The performance of the double chambered MFC based on
the Ni-ACF/CNF electrodes was compared to the different
types of carbon-based electrodes discussed in the literature
when possible. Table 3 describes the comparative data. The
OCP and power density values of the MFCs prepared in this
study are relatively higher in most cases and comparable in
few cases. In general, the noble metal-based electrodes per-
formed superior to the transition metals-based electrodes.
Also, the metal-dispersed carbon electrodes performed su-
perior to those without metal.
This may be mentioned that if one were to determine the
role of Ni NPs or graphitic carbon separately in anode and
cathode, the tests should be performed using the same ma-
terial for one of the electrodes and different materials for the
other electrode, and vice-versa. Based on the data, it may be,
however, inferred that Ni-ACF/CNF was the best material
because of its effects (facilitating the electron transfer at the
anode and on the catalytic oxygen reduction at the cathode),
considered together.
Conclusions
The multiscale forming web of ACFs/CNFs dispersed with Ni
NPs was fabricated and applied as the efficient anode and
cathode of a double chambered MFC. The MFC produced high
OCP (710 mV), current density (4650 mA/m2) and power den-
sity (1145 mW/m2). The prepared electrode material having
significant mesoporosity, electrical conductivity, and
dispersed Ni NPs facilitated electron transfer to the anode and
the catalytic reduction of oxygen at the cathode. The MFCs
were stable and had small internal resistances. The novel and
efficient Ni-ACF/CNF prepared as the electrodes of MFCs may
be an alternative to the expensive noble metals-based
electrodes.
Acknowledgments
The authors gratefully acknowledge the Gun Ei Chemical In-
dustry Co. Ltd., Japan for supplying ACFs. The authors are also
thankful to the Center for Environmental Science and Engi-
neering at IIT Kanpur for carrying out the research.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2014.11.073
references
[1] Mansoorian HJ, Mahvi AH, Jafari AJ, Amin MM,
Rajabizadeh A, Khanjani N. Bioelectricity generation using
two chamber microbial fuel cell treating wastewater from
food processing. Enzyme Microb Technol 2013;52:352e7.
[2] Liu Y, Harnisch F, Fricke K, Sietmann R, Schro der U.
Improvement of the anodic bioelectrocatalytic activity of
mixed culture biofilms by a simple consecutive
electrochemical selection procedure. Biosens Bioelectron
2008;24:1006e11.
[3] Ichihashi O, Hirooka K. Removal and recovery of phosphorus
as struvite from swine wastewater using microbial fuel cell.
Bioresour Technol 2012;114:303e7.
[4] Choi C, Cui Y. Recovery of silver from wastewater coupled
with power generation using a microbial fuel cell. Bioresour
Technol 2012;107:522e5.
[5] Rosenbaum M, Zhao F, Quaas M, Wulff H, Schro der U,
Scholz F. Evaluation of catalytic properties of tungsten
carbide for the anode of microbial fuel cells. Appl Catal B
Environ 2007;74:261e9.
[6] Wang Y-F, Tsujimura S, Cheng S-S, Kano K. Self-excreted
mediator from Escherichia coli K-12 for electron transfer to
carbon electrodes. Appl Microbiol Biotechnol 2007;76:1439e46.
[7] Ghasemi M, Daud WRW, Rahimnejad M, Rezayi M, Fatemi A,
Jafari Y, et al. Copper-phthalocyanine and nickel
nanoparticles as novel cathode catalysts in microbial fuel
cells. Int J Hydrogen Energy 2013;38:9533e40.
[8] Akman D, Cirik K, Ozdemir S, Ozkaya B, Cinar O.
Bioelectricity generation in continuously-fed microbial fuel
cell: effects of anode electrode material and hydraulic
retention time. Bioresour Technol 2013;149:459e64.
[9] Ghasemi M, Ismail M, Kamarudin SK, Saeedfar K,
Daud WRW, Hassan SHA, et al. Carbon nanotube as an
alternative cathode support and catalyst for microbial fuel
cells. Appl Energy 2013;102:1050e6.
[10] Sharma T, Mohana Reddy AL, Chandra TS, Ramaprabhu S.
Development of carbon nanotubes and nanofluids based
microbial fuel cell. Int J Hydrogen Energy 2008;33:6749e54.
[11] Faa Alatraktchi, Zhang Y, Angelidaki I. Nanomodification of
the electrodes in microbial fuel cell: Impact of nanoparticle
density on electricity production and microbial community.
Appl Energy 2014;116:216e22.
[12] Liu J, Qiao Y, Guo CX, Lim S, Song H, Li CM. Graphene/carbon
cloth anode for high-performance mediatorless microbial
fuel cells. Bioresour Technol 2012;114:275e80.
[13] Lepage G, Albernaz FO, Perrier G, Merlin G. Characterization
of a microbial fuel cell with reticulated carbon foam
electrodes. Bioresour Technol 2012;124:199e207.
[14] Ghasemi M, Shahgaldi S, Ismail M, Kim BH, Yaakob Z, Wan
Daud WR. Activated carbon nanofibers as an alternative
cathode catalyst to platinum in a two-chamber microbial
fuel cell. Int J Hydrogen Energy 2011;36:13746e52.
[15] Du Z, Li H, Gu T. A state of the art review on microbial fuel
cells: a promising technology for wastewater treatment and
bioenergy. Biotechnol Adv 2007;25:464e82.
[16] Ghasemi M, Wan Daud WR, Ismail M, Rahimnejad M,
Ismail AF, Leong JX, et al. Effect of pre-treatment and
biofouling of proton exchange membrane on microbial fuel
cell performance. Int J Hydrogen Energy 2013;38:5480e4.
[17] Bikshapathi M, Singh S, Bhaduri B, Mathur GN, Sharma A,
Verma N. Fe-nanoparticles dispersed carbon micro and
nanofibers: surfactant-mediated preparation and application
to the removal of gaseous VOCs. Colloid Surfaces A:
Physicochem Eng Asp 2012;399:46e55.
[18] Chakraborty A, Deva D, Sharma A, Verma N. Adsorbents
based on carbon microfibers and carbon nanofibers for the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 1 4 5 e1 1 5 3
removal of phenol and lead from water. J Colloid Interface
Sci 2011;359:228e39.
[19] Singhal RM, Sharma A, Verma N. Micro-nano hierarchal web
of activated carbon fibers for catalytic gas adsorption and
reaction. Industrial Eng Chem Res 2008;47:3700e7.
[20] Hood AR, Saurakhiya N, Deva D, Sharma A, Verma N.
Development of bimetal-grown multi-scale carbon micro-
nanofibers as an immobilizing matrix for enzymes in
biosensor applications. Mater Sci Eng C 2013;33:4313e22.
[21] Rausch S, Wendt H. Morphology and utilization of smooth
hydrogen-evolving raney nickel cathode coatings and porous
sintered-nickel cathodes. J Electrochem Soc
1996;143:2852e62.
[22] Hrapovic S, Manuel MF, Luong JHT, Guiot SR, Tartakovsky B.
Electrodeposition of nickel particles on a gas diffusion
cathode for hydrogen production in a microbial electrolysis
cell. Int J Hydrogen Energy 2010;35:7313e20.
[23] Selembo PA, Merrill MD, Logan BE. Hydrogen production
with nickel powder cathode catalysts in microbial
electrolysis cells. Int J Hydrogen Energy 2010;35:428e37.
[24] Jeremiasse AW, Hamelers HVM, Saakes M, Buisman CJN. Ni
foam cathode enables high volumetric H2 production in a
microbial electrolysis cell. Int J Hydrogen Energy
2010;35:12716e23.
[25] Selembo PA, Merrill MD, Logan BE. The use of stainless steel
and nickel alloys as low-cost cathodes in microbial
electrolysis cells. J Power Sour 2009;190:271e8.
[26] Singh S, Singh A, Bais VSS, Prakash B, Verma N. Multi-scale
carbon micro/nanofibers-based adsorbents for protein
immobilization. Mater Sci Eng C 2014;38:46e54.
[27] Lv Z, Chen Y, Wei H, Li F, Hu Y, Wei C, et al. One-step
electrosynthesis of polypyrrole/graphene oxide composites
for microbial fuel cell application. Electrochim Acta
2013;111:366e73.
[28] Battumur T, Mujawar SH, Truong QT, Ambade SB, Lee DS,
Lee W, et al. Graphene/carbon nanotubes composites as a
counter electrode for dye-sensitized solar cells. Curr Appl
Phys 2012;12(Suppl. 1):e49e53.
1153
[29] Zhang T, Cui C, Chen S, Yang H, Shen P. The direct
electrocatalysis of Escherichia coli through electroactivated
excretion in microbial fuel cell. Electrochem Commun
2008;10:293e7.
[30] Qiao Y, Bao S-J, Li CM. Electrocatalysis in microbial fuel cells-
from electrode material to direct electrochemistry. Energy &
Environ Sci 2010;3:544e53.
[31] Sugnaux M, Mermoud S, da Costa AF, Happe M, Fischer F.
Probing electron transfer with Escherichia coli: a method to
examine exoelectronics in microbial fuel cell type systems.
Bioresour Technol 2013;148:567e73.
[32] Wang Y, Li B, Cui D, Xiang X, Li W. Nano-molybdenum
carbide/carbon nanotubes composite as bifunctional anode
catalyst for high-performance Escherichia coli-based microbial
fuel cell. Biosens Bioelectron 2014;51:349e55.
[33] Park IH, Christy M, Kim P, Nahm KS. Enhanced electrical
contact of microbes using Fe3O4/CNT nanocomposite anode
in mediator-less microbial fuel cell. Biosens Bioelectron
2014;58:75e80.
[34] Singh S, Joshi HC, Srivastava A, Sharma A, Verma N. An
efficient antibacterial multi-scale web of carbon fibers
with asymmetrically dispersed AgeCu bimetal
nanoparticles. Colloid Surfaces A Physicochem Eng Asp
2014;443:311e9.
[35] Logan BE, Hamelers B, Rozendal R, Schro der U, Keller J,
Freguia S, et al. Microbial fuel cells: methodology and
technology. Environ Sci Technol 2006;40:5181e92.
[36] Lee LTL, He J, Wang BH, Ma YP, Wong KY, Li Q, et al. Few-
layer MoSe2 possessing high catalytic activity towards
iodide/tri-iodide redox shuttles. Sci Rep 2014;4:1e7.
[37] An J, Kim B, Jang JK, Lee HS, Chang IS. New architecture for
modulization of membraneless and single-chambered
microbial fuel cell using a bipolar plate-electrode assembly
(BEA). Biosens Bioelectron 2014;59C:28e34.
[38] Taek Lee K, Yoon HS, Ahn JS, Wachsman ED. Bimodally
integrated anode functional layer for lower temperature
solid oxide fuel cells. J Mater Chem 2012;22:17113e20.