Applied Energy 211 (2018) 1089–1094

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

A high-performance rotating graphite fiber brush air-cathode for microbial T

fuel cells
⁎ ⁎
Shuiliang Chena,b, , Sunil A. Patilb,1, Uwe Schröderb,
a
Department of Chemistry and Chemical Engineering, Jiangxi Normal University, 330022 Nanchang, China
b
Institute of Environmental and Sustainable Chemistry, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany

H I G H L I G H T S G RA P H I C A L AB S T R A C T

• Apresented
binder-free rotating air-cathode is
for enhancing ORR electro-
catalysis in MFCs.
• Itreduction
provided more three-phase oxygen
interface and enhanced
mass transfer.
• Itcatalysis
showed enhanced ORR electro-
under a slow speed rotation
conditions.
• Itpractically
could be arranged horizontally in
relevant systems to avoid
water leaking.
• Bioenergy harvested by the MFCs or
the flow of wastewater would be used
to rotate such air-cathodes.

A R T I C L E I N F O A B S T R A C T

Keywords: Microbial fuel cells (MFC) represent an emerging technology to harvest electric energy from waste streams like waste-
Bioenergy waters. To further increase MFC performance, the individual fuel cell processes, such as the cathodic oxygen reduction
Microbial fuel cell (ORR) need to be further improved. The commonly used, two-dimensional air-cathodes usually show limited performance
Rotating air-cathode due to a low three-phase ORR interface and a low oxygen mass transfer rate. To address these issues, a binder-free rotating
Co-doped carbon
three-dimensional air-cathode that provides a larger three-phase ORR interface and an enhanced oxygen mass transfer
Oxygen reduction reaction
rate is reported in this paper. The cathode is prepared by coating a self-supporting N and P co-doped carbon ORR catalyst
Power output
layer onto a graphite fiber brush current collector (GB/NPC). No binder and diffusion layer are used to avoid the
limitations associated with these components. The electrochemical tests demonstrate enhanced ORR electrocatalysis
under rotation conditions. In MFCs, a high performance was achieved by operating the GB/NPC air-cathode at a slow
rotation speed. For example, at 20 rpm, it delivered three times higher cathodic current (1.02 ± 0.05 mA cm−2) and two
times higher power output (879 ± 16 mW m−2, normalized to the projected surface area of air-cathode) than its
counterpart non-rotating, static air-cathode (0.35 ± 0.03 mA cm−2 and 486 ± 11 mW m−2, respectively). The rotating
conditions increased the availability of catalytic sites for the ORR, and improved oxygen diffusion and OH− transport at
or within the air-cathode. This study thus presents a promising approach for enhancing the performance of air-cathodes,
which is often the major performance-limiting component of the MFCs.

⁎
Corresponding authors at: Department of Chemistry and Chemical Engineering, Jiangxi Normal University, 330022 Nanchang, China (S. Chen).
E-mail addresses: slchenjxnu@jxnu.edu.cn (S. Chen), uwe.schroeder@tu-braunschweig.de (U. Schröder).
1
Present address: Department of Earth and Environmental Sciences, Indian Institute of Science Education and Research (IISER), Mohali, Sector 81, S A S Nagar, Punjab 140306, India.

https://doi.org/10.1016/j.apenergy.2017.12.013
Received 9 November 2017; Received in revised form 23 November 2017; Accepted 1 December 2017
Available online 18 December 2017
0306-2619/ © 2017 Elsevier Ltd. All rights reserved.
S. Chen et al.
1. Introduction
As an emerging wastewater treatment and bioenergy recovery ap-
proach, research domains and application range of microbial fuel cells
(MFCs) are expanding rapidly [1–3]. This microbial electrochemical
technology takes advantage of mixed cultures containing electroactive
bacteria to mineralize the organic waste present in wastewaters and to
generate electric power simultaneously. It has the potential to reduce
the energy consumption of wastewater treatment process and to recover
the bioenergy contained in different types of wastewaters [4,5]. The
realization of practical applications of the MFC technology is still
hampered by (i) comparatively low current or power outputs, which
limits its efficiency of pollutant removal, (ii) its high capital cost and
(iii) poor long-term operational stability of the cathode. Thus, in-
creasing power generation and long-term stability at decreased cost
level, is the key to achieve its real-world applications [6–9].
The cathode is widely regarded as the major performance-limiting
component of the MFCs [8,10,11]. Over the past decade, several studies
have focused on the development of noble-metal free ORR cathode
catalysts to replace high-cost, precious metal catalysts. A series of such
ORR catalysts, including heteroatom-doped carbon [12–14], metal
oxides and activated carbon [15] and Fe, Co, Ni and Mn catalysts has
been explored [8,10,11,16–18]. Beside the catalytic activity of ORR
catalysts, the quantity of active catalytic sites, mass transport of OH−,
the rates of electron transfer and oxygen diffusion also greatly affect the
cathode performance. The most feasible cathode configuration for
large-scale application of MFCs, e.g., for wastewater treatment, is the
air-cathode because its use solves the issue of limited oxygen solubility
in water, and makes purging obsolete thus greatly reduces the energy
consumption for wastewater treatment [19,20]. The non-limiting
availability of oxygen at the air-cathodes, ultimately, makes it possible
to achieve higher current densities.
The commonly used air-cathode is based on an ORR catalytic layer
and a waterproof, air-breathing diffusion layer, which are bonded onto
the both sides of a current collector using polymer binders [19–21].
However, it shows limited performance despite the use of highly active
ORR catalysts. The possible reasons are: (i) its two-dimensional (2D)
three-phase ORR interface, which provides a limited surface area and
catalytic sites for ORR, (ii) its operation under static conditions, which
lead to a low oxygen mass transfer rate, and (iii) the use of polymer
binder, which covers a large number of active sites of ORR catalyst and
obstructs the oxygen diffusion through such cathode. The use of binder
and additional diffusion layer adds to the cost and importantly, leads to
a high electrode resistance, which decreases the electron transfer rate.
Moreover, the biofouling and salt deposition also greatly decrease the
long-term stability of the 2D air-cathodes [22–27].
It was reported recently that increasing the exposed area of the air-
cathode could enhance the power density of MFCs [28]. Inspired by the
rotating biological contactor, developed to improve oxygen diffusion to
the attached biofilms for aerobic bacterial metabolism of organic waste
[29], a rotating cathode loaded with Pt catalyst was firstly attempted by
He et al. in 2007 to improve the availability of oxygen to the cathode in
a sediment MFC [30]. About 70% power output improvement by the
rotating cathode compared to a non-rotating cathode was reported. The
contribution of rotation to the real ORR catalytic performance of the
rotating cathode was, however, not studied in this case. Notably, no
research has been conducted on the use of such approach for typical
MFCs proposed for harvesting bioenergy from different wastewaters so
far. Therefore, in order to address the limitations as mentioned earlier
for routinely used 2D air-cathodes; the approach of using rotating air-
cathodes was thoroughly investigated in this study. Fig. 1 shows a
proposed schematic of the MFC equipped with the rotating air-cathode
for harvesting bioenergy from the practical wastewater treatment pro-
cess.
The air-cathode was prepared by binder-free coating of N, P co-
doped carbon ORR catalyst onto a graphite fiber brush current collector
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Applied Energy 211 (2018) 1089–1094
Fig. 1. Schematic of the MFC equipped with a rotating air-cathode for harvesting energy
from the practical wastewater treatment process. The rotating air-cathode can be ar-
ranged horizontally and driven by the flow of wastewater or by the power that is gen-
erated by the wastewater treating MFCs when it is used for practical wastewater treat-
ment.
(denoted as GB/NPC). It was first characterized electrochemically for
ORR reaction and then tested in practically relevant two-chambered
MFCs under static and rotating conditions. The effect of rotating speed
on the performance of the GB/NPC air-cathode was studied system-
atically. The MFC equipped with the rotating air-cathode was able to
harvest two times more electric power than its counterpart, non-ro-
tating, static air-cathode. The slow rotation of the air-cathode may be
driven by the wastewater flow without any external energy consump-
tion. This approach is easier to scale up because of the possibility to
arrange such cathodes horizontally at the surface of the wastewater
stream and thereby avoid the concern of water leaking that usually
occurs with the vertically arranged 2D air-cathodes. With this study, we
thus present a novel design and operational approach for enhancing the
performance of the air-cathode, which is the major performance-lim-
iting component of the MFCs.
2. Experimental
2.1. Materials
Graphite fiber brushes (GBs) with the size of 26 mm in diameter and
42 mm in length were made by fixing graphite fibers (TORAY) on a
twisted titanium wire and had a projected area of approximate 10.9 cm2
(calculated by multiplying the diameter and the length) and surface
area of 34.2 cm2. The twisted titanium wire had a diameter of about
2 mm. All chemicals including ammonium persulfate, aniline and
phytic acid (PA) (50 w/w in water) were purchased from Sigma
Aldrich.
2.2. Preparation and characterization of the GB/NPC cathode
GBs were first immersed into a 50% (w/w) concentrated sulfuric
acid for five minutes to improve their hydrophilicity and then washed
with distilled water for three times before further use. Polyaniline
(PANi) was grown onto the GB by a chemical oxidative polymerization
process. The polymerization was carried out at a temperature range of 0
to 5 °C, based on the protocol published elsewhere [31]. Briefly, sepa-
rate solutions of 0.06 M aniline and 0.015 M ammonium persulfate
were prepared by dissolving 0.559 g and 0.342 g, respectively in
100 mL 2 M HCl solution. Both solutions were then mixed vigorously,
and the GB electrode was immersed into this mixture immediately.
After oxidative polymerization for about 12 h, the composite GB/PANi
S. Chen et al.
electrode was obtained. After washing with distilled water for three
times, the GB/PANi was de-doped by using 0.5 M ammonia solution
and re-doped using 0.1 M PA solution to form GB/PANi-PA composite.
Finally, the GB/PANi-PA was placed in a high-temperature oven pre-
heated to 900 °C using a temperature ramp of 5 °C min−1 under the
nitrogen atmosphere. After annealing for 1 h at the final temperature
and cooling down to below 200 °C, nitrogen and phosphorus co-doped
carbon modified GB (GB/NPC) composite electrode was obtained. For
comparison, nitrogen single doped carbon modified GB (GB/NC) and
uncoated GB (control) electrodes were also prepared by pyrolyzing GB/
PANi and GB, respectively at the same conditions.
Scanning electron microscope (SEM; JSM-6335F, JEOL) and X-ray
photoelectron spectroscopy (XPS; ESCaLAB 250, Thermo Scientific)
techniques were used to characterize and analyze surface properties of
these electrodes.
2.3. Electrochemical tests
A three-electrode setup, as shown in Fig. S1A, was used to test the
ORR electrocatalytic activity of the GB/NPC under static and rotating
conditions. The GB/NPC connected to a rotating motor (Sol Expert
G298-2, 5–75 U/min) served as a working electrode. Graphite rod with
a surface area of 30 cm2 was used as the counter electrode, and the
reference was an Ag/AgCl (sat. KCl, +0.198 V vs. standard hydrogen
electrode) electrode. A 50 mM phosphate buffer solution with pH 7.0
was used as an electrolyte solution. All electrochemical tests were
conducted at room temperature (23 ± 2 °C). The cyclic voltammetry
(CV) tests were conducted within the potential window of +0.4 to
−0.8 V at the scan rate of 10 mV s−1 under N2 and O2 atmospheres.
Initially, CV experiments were conducted at the static conditions for
comparing only ORR catalytic activities of different air-cathodes. These
tests were conducted by immersing entire brushes electrode in the
electrolyte solution.
The rotation condition was applied only to the GB/NPC air-cathode
in further electrochemical tests. The chronoamperometry tests were
conducted at a constant potential of −0.3 V for about 1 h at each ro-
tating speed under the air atmosphere. CV tests were also conducted to
study the impact of rotating speed on ORR electrocatalytic activity. The
influence of different cathode submerging conditions on the ORR cur-
rent generation was investigated by chronoamperometry. If not men-
tioned otherwise all potential values are reported versus Ag/AgCl (sat.
KCl) reference electrode. Three independent measurements were con-
ducted for each sample.
2.4. Microbial fuel cell tests
The two-chambered setup used for testing the performance of GB/
NPC as a rotating air-cathode in MFCs is shown in Fig. S1B and Fig. 4A.
To eliminate the negative effect of dissolved oxygen on the bioanode,
an anion exchange membrane (fumasep®) was used to separate the
anode and cathode chambers. Both chambers had the same working
volume of 150 mL. GB treated at 450 °C in the air was used as the anode
in all MFC tests. The rotating GB/NPC air-cathode was operated at a
speed of 20 rpm. The distance between the two titanium wires of the
brush anode and the brush cathode was 5 cm. The catholyte was 50 mM
phosphate buffer with pH 7.0. The anolyte was modified M9 medium,
which contained 50 mM phosphate buffer, 20 mM acetate, and
12.5 mL L−1 each of vitamin and trace metal solutions. All MFC tests
were conducted at the room temperature (23 ± 2 °C). The cell voltages
of MFC across a resistor of 100 Ω were recorded every 5 min by using a
multimeter (Keithley 2700). The currents were calculated according to
the Ohm’s law. The polarization curves were obtained by scanning the
voltage from open circuit voltage to 0 V at a scan rate of 0.2 mV s−1
using the linear scanning voltammetry (LSV) method. The performance
of the uncoated GB air-cathode in MFCs was also tested at static and
rotating conditions under a similar set of experimental conditions for
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Applied Energy 211 (2018) 1089–1094
comparison purpose. The current and power densities were normalized
to the projected area of the brush air-cathode.
3. Results and discussion
3.1. Physicochemical characterization of the air-cathodes
After oxidative polymerization of aniline, a layer of nanostructured
PANi was successfully grown or deposited on the surface of graphite
fibers (Fig. S2). The original nanostructure of PANi was preserved even
after doping the material with phytic acid and pyrolysis process. XPS
spectra in Fig. S3A show that both GB/NPC and GB/NC materials
contained C, O and N elements. The GB/NCP contained extra P element.
Three types of N species, namely, pyridinic-N (398.2 eV), pyrrolic-N
(400.3 eV) and graphitic-N (401.3 eV) were identified from the high-
resolution N1s spectra (Fig. S3B and D). The P2p spectra of the GB/NPC
(Fig. S3C) were deconvoluted into two different bands at ∼131.8 eV
and 133.4 eV, corresponding to the core levels of P atoms in the form of
P-C and P-O, respectively [32]. The XPS results confirmed the suc-
cessful doping of N and P heteroatoms onto the GB/NPC electrode.
3.2. Electrochemical characterization of the air-cathodes under static
conditions
The N and P mono- or co-doped carbons have been demonstrated to
possess a high electrocatalytic activity towards ORR in alkaline fuel
cells [32–34], as well as in MFCs [13,14]. The efficient ORR catalytic
activity has been attributed to the activation of the electrons of carbon
through the conjugation with the lone-pair electrons from heteroatom
dopants and increased electronic conductivity of the materials [9]. The
O2 molecules get reduced on the positively charged C atoms that are
adjacent to the doping atoms [33,34]. CV technique was used to eval-
uate the ORR catalytic activity of the GB/NPC and other cathodes under
static conditions with either N2 or O2 purging (Fig. 2). No ORR catalytic
activity was observed under N2 purging conditions but was observed
under O2 conditions in the case of all cathodes. As can be seen in Fig. 2,
the onset potential of the GB/NPC for ORR in neutral PBS is around
0.15 V, it is much more positive compared to that of GB/NC (0.008 V)
and GB (−0.043 V) cathodes. This suggests that the presence of N and P
decreased the activation over-potentials of ORR. These results are also
in accordance with the results of one of our previous study [14],
wherein such cathodes showed higher ORR catalytic activity than that
of cathodes made with single N-doping.
3.3. Electrochemical performance of the rotating GB/NPC air-cathode at
different conditions
The effect of rotating speed on the ORR catalytic activity was stu-
died with the GB/NPC air cathodes. The CV data reveals that the
cathodic current of the GB/NPC increases rapidly with an increase in
the rotating speed from 8 to 20 rpm (Fig. 3A). Beyond 20 rpm, the rate
of increase in cathodic current becomes slower. A similar trend was
observed in the chronoamperometric measurements (Fig. 3B). The re-
lationship between the rotating speed and the current demonstrates
that the cathodic current increases rapidly at low rotating speeds (until
20 rpm) but slowly at high rotating speed (Fig. 3C). The cathodic cur-
rent jumped from 0.35 ± 0.03 mA cm−2 at the static condition to
0.83 ± 0.04 mA cm−2 at a low rotating speed of 8 rpm, then to
1.02 ± 0.05 mA cm−2 at a 20 rpm speed. As expected, negligible cur-
rent and no ORR catalytic activity were observed under N2 conditions,
and higher current and ORR catalytic activity were observed under pure
O2 conditions (Fig. 3A and B). It should be noted that the pure O2
condition is used only for comparison purpose. This is an unsustainable
approach for the real-world MFC applications. Due to the slow rotation
of the air-cathode could lead to a high cathodic current increase, thus it
could be droved by the wastewater flow without further energy
S. Chen et al. Applied Energy 211 (2018) 1089–1094

Fig. 2. Cyclic voltammograms of (A) GB/NPC, (B) GB/NC, (C) GB electrodes recorded
under N2 or O2 atmosphere at static conditions. The scan rate is 10 mV s−1.

consume when it is used for practical wastewater treatment.

At static conditions, the mass transfer rate of the reactant, O2, and
the product OH−, which mainly depend on the diffusion, is low. By
rotating the air-cathode, the O2 and OH− transfer rate are increased
due to convection induced by rotation, which is much more efficient
than that of simple diffusion at static state. Moreover, the catalyst sites
on the whole GB/NPC cathode come in contact with the electrolyte, and
the oxygen diffused to the 3-D electrode is made available for ORR,
thereby resulting in a much higher cathodic current generation.
The effect of submerging different factions of the rotating GB/NPC
air-cathode in electrolyte on the cathodic current generation and sta-
bility of supported ORR catalyst was also studied. Fig. 4A shows that
about 1/3rd to 2/5th submerged cathode produces the highest current.
This might be due to an optimized three-phase interface with maximum
availability of catalytic sites for ORR. (Note: the data obtained in Fig. 3
is based on the experiments conducted with the half-submerged
cathode). The GB/NPC air-cathode shows a good functional stability as
it retains 97% of its initial current even at a higher rotating speed of
40 rpm (Fig. 4B). This result demonstrates that the NPC catalyst is
firmly attached to the GB current collector.
3.4. Performance of the rotating air-cathode in MFCs
The performance of the rotating GB/NPC air-cathode in MFCs was
Fig. 3. (A) Cyclic voltammograms of the GB/NPC air-cathode under natural air-diffusion
conditions recorded at different rotation speeds and at a scan rate of 10 mV s−1. Control
CV tests with pure N2 and O2 purging under static conditions are presented for com-
parison purpose. The GB/NPC was half-submerged in the electrolyte solution. (Note: The
wave-shape of the CV curves was caused by the rotation. The higher the rotating speed,
the smaller is the length of wave in the curve.) (B) Representative chronoamperometric
current generation curve of the GB/NPC air-cathode recorded in the air under rotating
conditions at different speeds, and in pure N2 and O2 atmospheres recorded at static
condition. The applied potential was −0.3 V vs. Ag/AgCl. The numbers 0–80 represent
the rotating speeds in rpm. (C) Relationship between the ORR current of the GB/NPC air-
cathodes and rotating speeds. The data are presented as averages and standard deviations
based on three independent replicates.
studied by using a two-chamber MFC setup, as shown in Fig. 5A. A low
rotation speed of 20 rpm was chosen for testing its performance because
a low rotating speed not only means low energy consumption but also it
avoids the risk of mechanical catalyst losses. The MFC with the rotating
GB/NPC could generate a voltage of around 270 mV across a 100 Ω
external resistor at a rotating speed of 20 rpm, while the one operated
under static conditions generated below 170 mV voltage (Fig. 5B). Po-
larization curves show that the air-cathodes under rotating condition
led to a considerable reduction of internal resistance (Rint) of MFCs
comparing to their counterparts operated under static condition

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S. Chen et al.
Fig. 5. (A) Schematic diagram of the MFC set-up equipped with a rotating air-cathode. (B) Voltage generation by the MFC with GB/NPC air-cathode operated at rotating (20 rpm) and at
static conditions across an external resistor of 100 Ω, (C) Polarization and (D) power density curves of the MFCs with R-GB/NPC, S-GB/NPC, R-GB, and S-GB. (Scan rate: 0.2 mV s−1)
(Note: the R and S stand for rotating and static conditions, respectively; and AC stands for air-cathode).
(Fig. 5C). MFC equipped with the rotating GB/NPC had a low Rint of
approximately 53 Ω, which is two times lower than that of the static
GB/NPC (about 128 Ω). The lower Rint in the MFC with the rotating air-
cathode is most likely due to the enhancement of O2 diffusion and OH−
transport under the rotating condition. The low Rint and the high cat-
alytic cathodic current together resulted in a great improvement of the
power output of the MFC with the rotating cathode. As shown in
Fig. 5D, MFC with the rotating GB/NPC could produce a maximum
power density of 879 ± 16 mW m−2, nearly two times as that of the
MFC with static GB/NPC (486 ± 11 mW m−2). The MFC with un-
coated GB electrode operated at static and rotating conditions gener-
ated much lower power density of just around 95 ± 6 mW m−2 and
114 ± 8 mW m−2, respectively. All these results demonstrate that the
N and P co-doped carbon catalyst-based and rotating air-cathodes
outperform their counterpart just N doped carbon catalyst-based and
static air-cathodes.
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Applied Energy 211 (2018) 1089–1094
Fig. 4. (A) Chronoamperometric curves obtained
with the GB/NPC air-cathode submerged at var-
ious levels in the electrolyte solution and under
natural air-diffusion conditions. Applied potential
is −0.3 V vs. Ag/AgCl. (B) Performance stability
of the GB/NPC air-cathode in an air atmosphere
operated under the static condition and at a ro-
tating speed of 40 rpm. It is presented in terms of
% activity.
4. Conclusions
The binder-free air-cathodes made of self-supported, N, P co-doped
carbon catalysts at a graphite brush current collector (GB/NPC) showed
a considerable decrease in the ORR overpotential. The GB/NPC air-
cathodes operated under the conditions of rotation and direct air-dif-
fusion outperformed those operated under static conditions. The
cathodic current obtained with rotating air-cathodes increased sig-
nificantly at low rotation speeds, leveling off at high rotation rates.
MFCs with the GB/NPC cathodes operated at 20 rpm possessed a much
lower Rint and could generate nearly two times higher power than the
MFCs operated with static air cathodes. This performance improvement
is attributed to the increased availability of ORR catalytic active sites,
enhanced rate of electron transfer, OH− transport and O2 diffusion
under the rotation conditions. Compared to the popularly used 2D air-
cathodes, the rotating 3D air-cathode offers more ORR catalytic sites
due to the 3D architecture and binder-free characteristics.
S. Chen et al.
This study demonstrated that MFC equipped with the slowly ro-
tating air-cathode could harvest two times higher power from waste-
water than that with a static air-cathode. The low rotation of the 3D air-
cathode could be driven by the wastewater flow or by the power that is
generated by the wastewater treating MFCs without any external en-
ergy consumption when it is used for practical wastewater treatment.
However, the use of MFCs or external energy source for rotating the air
cathodes would not just diminish the net energy production but will
also increase the capital costs. Thus, considering the real-world appli-
cations, the passive rotation of the air-cathode, i.e., rotation purely by
water movement, would be the easiest and practically-relevant ap-
proach. Additionally, this approach is easier to scale up because of the
possibility to arrange such cathodes horizontally at the surface of the
wastewater stream. The concept of having a rotating cathode at the
wastewater-air interface not just gives increased performance, but also
simplifies reactor design and may enable to very simply integrate the
MFC into existing wastewater treatment facilities or wastewater chan-
nels. Further studies on the effects of biofouling on the performance of
the rotating air-cathodes and its applicability in wastewater treating
MFCs are warranted.
Acknowledgements
S. Chen acknowledges the financial support from the China
Scholarship Council, the National Natural Science Foundation of China
(grant 51678281), the Science and Technology Project of Jiangxi
Province (grants 20162BCB23024, 20161BCB24005), and the project of
Education Department of Jiangxi Province (grants, GJJ150296). S. Patil
acknowledges the Alexander von Humboldt Foundation for the fi-
nancial support.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.apenergy.2017.12.013.
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