Chemical Engineering Journal 334 (2018) 1621–1629

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Chemical Engineering Journal

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Simultaneous Cr(VI) reduction and bioelectricity generation in a dual T

chamber microbial fuel cell
⁎
Meng Lia, Shaoqi Zhoua,b,c,d, , Yuting Xua, Zejun Liua, Fuzhen Maa, Liangliang Zhia, Xuan Zhoua
a
School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, 510006, PR China
b
Guizhou Academy of Sciences, Shanxi Road 1, Guiyang 550001, PR China
c
State Key Laboratory of Subtropical Building Science, South China University of Technology, Guangzhou 510641, PR China
d
Key Laboratory of Environmental Protection and Eco-remediation of Guangzhou Regular Higher Education Institutions, South China University of Technology, Guangzhou
510641, PR China

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

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

Keywords: Microbial fuel cells (MFCs) technology for treating wastewater containing Cr(VI) and generating bioelectricity
Microbial fuel cell simultaneously at an abiotic cathode by utilizing the electricigens on the biotic anode, have been run. In this
Bioelectricity generation work, the Cr(VI) is bio-electrochemically reduced to nontoxic Cr(III) in the dual chamber MFCs with different
Hexavalent chromium cathodes. The 80 mg L−1 of Cr(VI) is completely removed by MFC with carbon cloth cathode, and the MFC
Linear sweep voltammetry
exhibits higher power density than that of these MFC with carbon brush cathode and carbon felt cathode.
Reduction kinetics
Besides, the linear sweep voltammetry (LSV) of carbon cloth cathode demonstrates that the electrochemical
performance increases with the increase of the initial Cr(VI) concentration. The MFC achieves the maximum
power density of 1221.94 mW m−2 in the catholyte contained 120 mg L−1 of Cr(VI), and the power density is
great higher than the MFC with the catholyte contained 50 mg L−1 or 80 mg L−1 of Cr(VI). Meanwhile, the 100%
Cr(VI) is totally removed by the electrochemical reduction of Cr2O72− to Cr(OH)3 on the surface of carbon cloth
cathode. The present study has successfully verified that a promising MFC technology can achieve high output
power in removing Cr(VI), revealing the enormous potential of scale-up MFCs for heavy metal treatment.

1. Introduction
The heavy metal hexavalent chromium (Cr(VI)) is used widely in
many industries over the past decade years such as welding, leather
tanning, mining, electroplating, and pigment manufacturing [1]. Unlike
some organic pollutions, Cr(VI) and some other heavy metals are non-
biodegradable and can be kept for a long time in ecosystem [2]. In
general, chromium is shown in the natural environment with two va-
lence states, Cr(VI) and Cr(III) [3]. In fact, non-toxic Cr(III) is highly
distributed in insoluble minerals, and it can be used as an essential

⁎
Corresponding author at: School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, PR China.
E-mail address: fesqzhou@yeah.net (S. Zhou).

https://doi.org/10.1016/j.cej.2017.11.144
Received 14 October 2017; Received in revised form 21 November 2017; Accepted 22 November 2017
Available online 23 November 2017
1385-8947/ © 2017 Elsevier B.V. All rights reserved.
M. Li et al.
microelement for organisms at low concentrations [4]. While the Cr(VI)
with high solubility, mobility and toxicity is a mutagen, carcinogen and
teratogen, and becoming a risk to human health since Cr(VI) can enter
the food chain via contaminated drinking water [5]. If a long term
exposure of human to Cr(VI) environment will cause skin and stomach
tumors, dermatitis, liver and kidney damage [6]. Consequently, was-
tewater and drinking water contained Cr(VI) pose a serious threat to
humans and ecosystems. Considering the adverse effects, the U.S. En-
vironmental Protection Agency has identified Cr(VI) as one of the se-
venteen chemicals causing the largest threat to human health, stipu-
lating the maximum Cr(VI) concentration for discharge is 50 μg L−1
[7]. Some conventional methods such as ion exchange, adsorption,
membrane filtration, chemical precipitation, chemical oxidation and
reduction are applied to converted Cr(VI) to non-toxic Cr(III) [8–10].
Nevertheless, these treatment techniques have some inherent defi-
ciencies such as expensive cost, excessive chemical consumption, high
energy requirements, generation of a great deal of toxic sludge and
secondary pollutants [11]. Consequently, it is urgent to explore a sus-
tainable and cost-effective technique to treat wastewater containing Cr
(VI) prior to discharging them to natural bodies.
Microbial fuel cell (MFC) is a promising technology that can si-
multaneously consume organic substrates by electricigens and generate
bio-electricity [12]. Electricigens grow on the anode surface oxidize
organic matter and generate proton and electron, and then these proton
and electron are transferred to cathode through the proton exchange
membrane and the external circuit, respectively. Finally, chemical ac-
tion is produced when they combine with electron acceptors in the
cathode chamber [13]. Oxygen from ambient air with high redox po-
tential has been widely used as cathode electron acceptor [14]. Nitrate,
permanganate, ferric ion and ferricyanide have been confirmed as
electron acceptor in previous reports [15]. If contaminates can be used
as electron acceptors in the MFC cathode, the operational cost of MFCs
can not only be decreased, but also the MFC technology can recover the
metal resources and increase some benefits of treatment wastewater.
Therefore, some contaminates with high redox potential such as nitrate
and trichloroethene have caused wide public concern [16,17].
Cr(VI) has an oxidation reduction potential of 1.33 V (vs standard
hydrogen electrode; SHE), much higher than hexacyanoferrate (0.36 V)
and O2 (1.23 V) in half-cell reaction [18]. Besides, the Nernst equation
suggests that the electrons produced in the anode by the oxidation of
organic substrates can promote the reduction of Cr(VI) in the cathode,
together with a bio-electricity generation. The Nernst equation displays
the half-cell reaction in the cathode chamber:
Cr2O27 − + 14H+ + 6e− → 2Cr 3 + + 7H2 O (1)
RT [Cr 3 +]2
E= E0− × ln
nF [Cr2O27 −][H+]14 (2)
where E0 is the redox potential at the standard half-cell; R is the molar gas
constant (8.31448 J mol−1 K−1); T is the temperature (K); n is the number
of electrons exchanged and F is the Faraday’s constant (96485.3 C mol−1).
This above description theoretically indicates that Cr(VI) can be con-
sidered as a terminal electron acceptor in the catholyte while harvesting
electricity from a dual MFC. It should be noted that the MFC can produce
bio-electricity and simultaneously treat wastewater containing Cr(VI)
based on the degree of the generated voltage [19]. As can be estimated
from Eq. (1) and Eq. (2), the voltage of MFC largely depends on the pH of
catholyte and initial concentration of Cr(VI).
Besides, the liquid-MFC is sample and convenient, and it has quicker
reduction rate of Cr(VI) than the Plant-MFC [20] and the biological
reduction method [21]. In our study, the MFC has achieved higher than
power density (1221.91 mW m−2) than the MFC with non-wet proof
plain carbon cloth cathode (767.01 mW m−2) [22] and the MFC with
graphite plate cathode (55.5 mW m−2) [23]. The MFC in our study for
hexavalent chromium removal and bioelectricity generation has great
potential for scale-up application as compared to the other studies
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Chemical Engineering Journal 334 (2018) 1621–1629
[20,22,23].
The optimal experimental conditions were obtained to meet the
requirements for wastewater treatments by MFC technology. The aim of
this work was to figure out the reduction mechanism and reduction
efficiency of Cr(VI) in MFCs under different configurations. In this
study, the dual chamber MFCs were used for simultaneous Cr(VI) re-
duction and bioelectricity generation from a synthetic wastewater
containing Cr(VI). The Cr(VI) concentration along with the bioelec-
tricity generation was evaluated in different pH, initial concentration of
Cr(VI) and different cathode materials. Besides, the linear sweep vol-
tammetry (LSV) was used to evaluate the electrochemical activities of
Cr(VI). To demonstrate the final product of Cr(VI) reduction, the
chromium precipitation on the carbon cloth was characterized by
scanning electron microscopy (SEM) and energy dispersive X-ray
spectroscopy (EDS). Meanwhile, the long term stability of MFC output
voltage and Cr(VI) reduction were also carried out.
2. Materials and methods
2.1. MFC construction
The dual chamber microbial fuel cells made of plexiglass were used
in our work. And each chamber had an effective volume of 340 ml
(length = 7 cm, width = 7 cm, height = 7 cm). The anode chamber and
cathode chamber were separated by proton exchange membrane (PEM,
Nafion™ 117, Dupont Co.), and the PEM was boiled in H2O2 (30% v/v),
deionized water, H2SO4 (0.5 M), and then stored in deionized water,
each for 1 h as described by Liu and Logan [24]. The carbon felt (ef-
fective area = 16 cm2) were used as anode electrode of MFC. The
carbon cloth, carbon brush, carbon felt (effective area = 16 cm2) were
used as the cathode electrode of MFC, and they were purchased from
Shanghai Hesen Electrical Co., Ltd. Prior to use, these carbon materials
were washed with acetone and then heated in the muffle furnace at
450 °C about 30 min based on the previously reported method [25]. The
distance between two electrodes was about 3 cm and they were con-
nected by titanium wires with an external resistance of 1000 Ω.
2.2. Inoculation and operation
The inoculum bacteria in anode chamber was originated from a
stable running MFC in our lab [26]. The nutrient medium (pH 7.0) in
anode chamber contained the following: 0.75 g L−1 acetate, 0.13 g L−1
KCl, 0.31 g L−1 NH4Cl, 4.97 g L−1 NaH2PO4·H2O, 2.75 g L−1
Na2HPO4·H2O, 5 ml L−1 vitamin and 12.5 ml L−1 mineral solution.
After the vaccination phase, the anode chamber was filled with 340 ml
anode medium, and the cathode chamber was filled with 0.13 g L−1
KCl, 0.31 g L−1 NH4Cl, 4.97 g L−1 NaH2PO4·H2O, 2.75 g L−1
Na2HPO4·H2O, 11.36 g L−1 NaCl and hexavalent chromium. The pH
value of the cathode chamber was adjusted with HCl (0.1 M). The two
chambers were continuously sparged with nitrogen for 30 min to re-
duce dissolved oxygen, and the magnetic stirring apparatus was used in
the MFC to reduce the solution transfer resistance. To explore the ef-
fects of different parameters on MFCs, the pH (1–7), initial Cr(VI)
concentration (50–120 ppm), different electrode materials including
carbon felt, carbon brush and carbon cloth were studied. All MFCs were
operated in room temperature.
2.3. Calculations and characterization
The voltage (U) of MFC was continuously recorded utilizing a digital
multimeter (M2700, Keithley instrument, USA) every minute. The
power (P = UI) and current (I) were determined as previously reported
[27]. The power density and polarization curves were calculated by
varying the external resistance from 10000 Ω to 20 Ω. The concentra-
tion of Cr(VI) was measured by colorimetry utilizing diphenylcarbazide
in acidic solution. One milliliter of sample was dropped into the 50 ml
M. Li et al. Chemical Engineering Journal 334 (2018) 1621–1629

colorimetric tube. Then, the deionized water was dropped to the stan-
dard scale of colorimetric tube. Subsequently, 0.5 ml of (1 + 1) sul-
phuric acid and 0.5 ml of (1 + 1) phosphoric acid were dropped into
the solution, respectively. After shaking the solution, 2 ml of color agent
was added into the mixture. Finally, the sample was measured in the
spectrophotometer (UV-2800, Unico (Shanghai) Instrument Co., Ltd.) at
the 540 nm of wavelength and the results were obtained by calculating
the data from the standard curve.
The chromium reduction activities were tested by using linear
sweep voltammetry (LSV) by an electrochemical workstation (CS310,
Wuhan CorrTest instruments Corp., LTD). The LSV was performed from
−1.0 to 1.0 V at a scan rate of 5 mV s−1 in a three electrode systems,
with Ag/AgCl as reference electrode, platinum wire as counter elec-
trode and cathodes as working electrode. Electrochemical impedance
spectroscopy (EIS) measurement was carried out over the frequency
range of 100 kHz to 10 mHz at open circuit condition in 50 mM phos-
phate buffer solution. The metal deposition on the cathode was ob-
served by scanning electron microscopy (SEM) (Carl Zeiss EVO LS10,
UK). Besides, the chemical elements on the cathode surface were de-
tected using the energy dispersive spectroscopy (EDS).

3. Results and discussion

3.1. Effects of pH

MFC performance and the reduction of Cr(VI) varied with respect to

pH. This change in cathode chamber can bring alterations in membrane
potential, reduction of Cr(VI), ionic concentrations, and proton shut-
tling [28]. To study the effect of pH, the reduction of Cr(VI) was
evaluated by using a synthetic wastewater containing 80 mg L−1 Cr(VI)
ion. Seven parallel MFCs were run at the same initial Cr(VI) con-
centration with different catholyte pH values (1–7) and one MFC was
used as control experiment. As can be seen from Fig. 1, the Cr(VI) was
rapidly reduced and achieved 100% removal efficiency in 82 h at pH 2.
The reaction time required for the complete reduction of Cr(VI)
(80 mg L−1) was 120 h and 144 h at pH 3 and pH 4, respectively.
Nevertheless, the same reaction time for the reduction of all Cr(VI) at
the other pH values would spend longer time than that of low pH.
Obviously, the reduction rate of Cr(VI) increased with the decrease of
pH. Clearly, the order of reduction rate in different pH was pH 2 > pH
3 > pH 4 > pH 5 > pH 1 > pH 6 > pH 7. However, the reduction
rate not further increased at lower pH (pH = 1). This was attributed to
that the hydrogen ion in the cathode chamber at pH 1 was diffused to
the anode chamber, resulting in a decrease of pH in the anolyte. The
low pH of anolyte would restrain the growth of microorganism on the
anode electrode and reduce the power output of MFC. The above results
were consistent with the Cr-Pourbaix diagram [29]. Under acidic con-
ditions, the reduction of Cr(VI) was thermodynamically favored due to
the increase of standard potential along with hydrogen ion concentra-
tion [30].
In order to explicitly figure out the effect of different pH in reduc-
tion Cr(VI), the pseudo first-order model and pseudo second-order
model were used to study the reduction kinetics of Cr(VI). As shown in
Fig. 1b and Table S1, the fitting degree of reduction kinetic of Cr(VI)
obtained from the pseudo second-order model was higher than the
fitting degree achieved from the pseudo first-order model, which in-
dicated the reduction process of Cr(VI) was in line with the pseudo
second-order model. Clearly, in the pseudo second order model, the
order of rate constant was: pH 2 (0.1567 h−1) > pH 3
(0.1389 h−1) > pH 4 (0.1257 h−1) > pH 5 (0.1146 h−1) > pH 1
(0.1012 h−1) > pH 6 (0.0885 h−1) > pH 7 (0.0326 h−1) > control
(0.0086 h−1). Obviously, the rate constant increased with the increase
of pH value in the catholyte. And the rate constant was exceptional in
the catholyte of pH 2, which was mainly due to the fact that more
hydrogen ion diffused to anode chamber through the PEM, restraining
the normal metabolism of electricigens.
Fig. 1. Effect of catholyte pH on the reduction of Cr(VI) (a. Time course of Cr(VI) in the
catholyte with different pH; b. Reduction kinetics of Cr(VI)).
3.2. Effects of different cathode materials
To study the effect of different cathode materials, the carbon cloth,
carbon brush and carbon felt were chosen as the cathode electrodes in
this study. The synthetic wastewater containing 80 mg L−1 Cr(VI) at
optimal pH of 2 was used to evaluate the effect of different cathode
materials on the performance of MFCs. As shown in Fig. 2a, the Cr(VI)
concentration in MFC with carbon cloth cathode rapidly declined.
99.1% of Cr(VI) in the cathode chamber was removed at 60 h and Cr
(VI) was completely removed at 72 h. However, it can be seen from
Fig. 2a that Cr(VI) complete removal in MFCs with carbon brush
cathode or carbon felt cathode needed 300 h and 444 h, respectively. In
addition, the experimental data were fitted by the pseudo first-order
model and pseudo second-order model for exploring the order of the
reaction. As exhibited in Fig. 2b, the reduction kinetic of Cr(VI) could
be well fitted by the pseudo second-order model as compared to pseudo
first-order model. Also, the results could be obtained by the rate con-
stant from the Table 1. Clearly, the MFC with carbon cloth cathode
(0.1567 h−1) had higher rate constant than that of carbon brush
cathode (0.1064 h−1) and carbon felt cathode (0.0719 h−1), indicating
the carbon cloth could be used as an efficient electrode for removal of
Cr(VI) in MFC. In addition, Fig. 2c exhibited the maximum Cr(VI) re-
moval efficiency and power density for MFCs with different cathode
materials. Obviously, the Cr(VI) could be completely removed within
72 h by MFC with carbon cloth electrode and the maximum power
density was achieved (1221.91 mW m−2). However, only 33.45% and
12.72% of Cr(VI) removal efficiency were obtained for MFCs with
carbon brush electrode and carbon felt electrode, respectively.

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Fig. 2. Effect of different cathodic materials (a. Time course of Cr(VI) concentration in the cathode chamber; b. Reduction kinetics of Cr(VI); c. Cr(VI) removal efficiency and output
power in the end of the 60 h operation period; d. Nyquist plots of EIS).

Table 1
Pseudo first-order model and pseudo second-order model rate constant, correlation coefficients and corresponding resistances for Cr(VI) reduction in MFC.

Electrode Carbon cloth Carbon brush Carbon felt Cr(VI) concentration (mg L−1)

50 80 120

−1
First order model Rate constant (h ) 0.0736 0.0388 0.0205 0.0752 0.0736 0.0348
R2 0.9924 0.9256 0.9108 0.9496 0.9924 0.9575
Second order model Rate constant (h−1) 0.1567 0.1064 0.0719 0.1768 0.1567 0.1328
R2 0.9989 0.9994 0.9991 0.9974 0.9989 0.9993
Rs (Ω) 11.89 73.90 115.12 – – –
Rct (Ω) 5.33 71.40 111.84 – – –
Rin (Ω) – – – 48.32 36.78 21.04

Moreover, the power density in MFC with carbon cloth electrode was
2.69 folds and 8.49 folds higher than that of carbon brush electrode and
carbon felt electrode, respectively. Li et al. reported the carbon cloth
with high electronic conductivity and flexibility could be used as
cathode for application in electrochemical devices [31].
In order to further evaluate the different cathode materials, the
resistance of different electrodes was also assessed by the EIS in elec-
trochemical workstation with a three electrodes system. The EIS tests
were operated for different electrodes at the open circuit state, and the
Nyquist plots and corresponding equivalent circuit model were shown
in Fig. 2d and Table 1. The intersection of the semicircle on the Z′ axis
corresponded to the ohmic resistance, and the charge transfer resistance
could be calculated by diameter of the semicircle. All electrodes dis-
played different resistance due to different materials used. It should be
noted that the ohmic resistance for carbon cloth was 5.6 Ω, which was
close to carbon brush electrode (4.8 Ω) and carbon felt electrode (4.3
Ω). And this phenomenon suggested that the carbon cloth had similar
conductivity with carbon brush electrode and carbon felt electrode. The
previous study reported that the electrode with low ohmic resistance
can offer outstanding electrical conductivity and enhance the electron
transfer number [26]. However, the charge transfer resistance of elec-
trode played more important role in cathode reaction than ohmic re-
sistance [32]. And the charge transfer resistance had something to do
the activation energy of the cathode and it was an indicative parameter
of the reaction kinetics occurring on the cathode [33]. What‘s more, the
electrode with low charge transfer resistance was easily appeared
oxygen reduction reaction [25]. Herein, the smaller charge transfer
resistance for carbon cloth (7.52 Ω) than carbon brush (73.86 Ω) and
carbon felt (113.66 Ω) was greatly favorable to the reduction of Cr(VI)
in MFC. And the low charge transfer resistance of carbon cloth

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M. Li et al. Chemical Engineering Journal 334 (2018) 1621–1629

Fig. 4. Cathodic linear sweep voltammetry (LSV) curves of different concentration of Cr

(VI).

electrode could be attributed to the low activation energy barrier for

electrochemical reaction. The EIS results was consistent with reduction
of Cr(VI), indicating the carbon cloth was a promising electrode ma-
terial for application in MFC for removing Cr(VI).

3.3. Effects of initial Cr(VI) concentration

To study the effect of initial Cr(VI) concentration on the perfor-

Fig. 3. Effect of initial concentration on the (a) reduction of Cr(VI) and (c) output power;
b. Reduction kinetics of Cr(VI).
mance of MFC, three parallel MFCs were set at different initial Cr(VI)
concentration (50–120 mg L−1) with same initial pH of 2 in MFC as-
sembled carbon cloth cathode. As shown in Fig. 3a, the shapes of re-
duction curve of Cr(VI) were similar to those in Fig. 1 and Fig. 2a. For
the initial Cr(VI) concentration of 50 mg L−1, Cr(VI) was completely
removed within 48 h. Similarly, the initial Cr(VI) concentration of
80 mg L−1 and 120 mg L−1 were completely removed within 72 h and
132 h, respectively. However, only 87.12% and 50.95% Cr(VI) were
removed for the initial Cr(VI) concentration of 80 mg L−1 and
120 mg L−1 within 48 h, respectively, which was mainly attributed to
relatively higher depletion of the organic matter by electricigens in the
anode chamber [6]. At relatively higher Cr(VI) concentration, the
electron accepted by the electron acceptor in the cathode chamber was
greater than those generated during the metabolism process in the
anode chamber. Nevertheless, the further reduction of Cr(VI) was
possible due to the replenishment of organic matter in the anode
chamber [34]. To further explore the removal of Cr(VI), the reduction
kinetics of Cr(VI) was studied by the same method as 3.2. As exhibited
in Fig. 3b and Table 1, the pseudo second-order model can be better
fitted to elaborate the reduction process of Cr(VI) in the cathode of MFC
than that of pseudo first-order model. Besides, the rate constants were
calculated to be 0.1768, 0.1567 and 0.1328 for the initial Cr(VI)

Table 2
Comparisons of the MFC studies for different metal reduction and power generation.

Metals Anode material Cathode material Electron donor (g L−1) Maximum power density (mW m−2) References

Vanadium Carbon fiber felt Carbon fiber felt Glucose:0.81 572 [39]
Sulphide:0.01
Vanadium Carbon fiber felt Carbon fiber felt Gluse:0.81 970 [38]
Silver Carbon cloth Graphite felt Sodium acetate:1.6 317 [40]
Silver Graphite plate Graphite felt Sodium acetate:1.28 109 [41]
Mercury Graphite felt Carbon paper Sodium acetate:0.82 433 [42]
Copper Graphite plate Graphite Ti plate Sodium acetate:1.64 430 or 800 [43]
Copper Graphite felt Graphite felt Sodium acetate:0.82 319 [44]
Chromium Carbon felt Carbon cloth Sodium acetate:0.75 1221.91 This work

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M. Li et al.
concentration range of 50–120 mg L−1, respectively. Obviously, the
rate constant declined by 24.88% with the increase in the initial Cr(VI)
concentration. The results that decrease of rate constant at higher
concentration Cr(VI) solution were also found in this report of Xu et al.
[35].
In order to evaluate the performance of MFC, the power density and
polarization curve were measured by variable external resistance
method. As can be seen from Fig. 3c, the maximum power density in-
creased from 857.13 mW m−2 to 1221.91 mW m−2 and the open circuit
potential increased from 0.897 V to 1.19 V with initial Cr(VI) con-
centrations of 50 mg L−1 to 120 mg L−1. The improvement in maximum
power density and open circuit potential was closely related to the in-
itial Cr(VI) concentration, and the facts were in accordance with the
phenomenon observed from analysis utilizing the Nernst equation
based on Eq. (3):
E= 1.33 + 0.01 log(Cr2O27 −)−0.138pH (3)
In addition, the increase in power density and open circuit potential
might be the decrease in internal resistance of MFC leading to the in-
crease in ionic strength [36]. Generally, the internal resistance
(Table 1) of MFC can be calculated from the polarization curve. The
internal resistance of MFC at 50 mg L−1, 80 mg L−1 and 120 mg L−1
were 48.32 Ω, 36.78 Ω and 21.04 Ω, respectively, and the results were
also demonstrated by the reduction of Cr(VI).
The application of MFC for simultaneous heavy metal reduction and
bioelectricity generation was crucial for the serious environmental
pollution and energy problem. Consequently, enhancement of output
power and total reduction of heavy metal was the key of this tech-
nology. In our work, the carbon cloth was used as cathode of MFC for
simultaneous reduction of Cr(VI) and bioelectricity generation, and the
MFC exhibited the excellent electrochemical performance. The findings
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Chemical Engineering Journal 334 (2018) 1621–1629
Fig. 5. The (a, c) SEM pictures, (b) EDS spectrum and ele-
mental mapping images for (d) C, (e) O and (f) Cr of cathode
in MFCs after operation.
shown in our study were in good line with the results observed in the
literature for other reduction of heavy metal. As shown in Table 2, an
overview of different heavy metals investigated in various configura-
tions, mainly based on vanadium, silver, mercury and copper, also in-
cluding the maximum power density of MFCs. Clearly, the heavy metal
vanadium, silver and copper were widely studied. Obviously, the power
density in our study for reduction of Cr(VI) was greatly higher than
reduction of Vanadium, Silver, Mercury and Copper in other literatures.
And 100% Cr(VI) was removed and the MFC achieved excellent power
density of 1221.91 mW m−2, suggesting that the MFC for simultaneous
Cr(VI) reduction and bioelectricity generation was an ideal technology.
3.4. Chromium reduction activities on cathode
The LSV was used to evaluate the cathode electrochemical proper-
ties due to the effects of different Cr(VI) concentration. As shown in
Fig. 4, the cathode exhibited the much steeper wave slope in the I-V
curves at higher Cr(VI) concentration, and the electrochemical reaction
rate was obtained in the 120 mg L−1 of Cr(VI), which was consistent
with the reduction kinetics of Cr(VI). In addition, the phenomenon also
indicated that the reduction reaction on cathodes could be accelerated
at higher Cr(VI) concentration, which was in accordance with the lower
internal resistance at higher Cr(VI) concentration (Table 1). Besides, the
LSV phenomenon could also be explained by the relationship between
flux of reacting species (J) and current (I) (Eq. (4)) [37]:
I ∂C (x ,t ) ⎤
−J0 (0,t ) = = D0 ⎡ 0
nAF ⎣ ∂x ⎦x = 0 (4)
Obviously, the current (I) was proportional to the flux of Cr(VI)
transferred to the cathode surface J0(0,t), and the flux was also propor-
tional to the concentration gradient of Cr(VI) at the cathode surface. The
M. Li et al. Chemical Engineering Journal 334 (2018) 1621–1629

Table 3
Cr(VI) removal reported in other literatures and that achieved in this work.

Methods Initial concentration Removal (%) Reference

(mg L−1)

Bioreduction 50 74 [45]
Adsorption 80 26.5 [9]
Adsorption 100 99 [46]
Photocatalytic reduction 40 97 [47]
Photocatalytic reduction 50 99.8 [48]
Electrocoagulation 24 92 [49]
Reduction coagulation 100 99.81 [50]
precipitation
Nanofiltration 17.09 96.6 [51]
Bactria reduction 10 80 [52]
Diaphragm glow discharge 21 98.77 [53]
Microbial fuel cell 50 100 This work
Microbial fuel cell 80 100 This work
Microbial fuel cell 120 100 This work

Obviously, it can be seen from the Eq. (3) that the reduction potential
was greatly high and the reduction reaction was very intension under
the low pH. Accordingly, the Cr(VI) could be completely reduced in the
system with a low pH of catholyte. It should be noticed from the Fig. 6c
that the MFC still could keep a stable electrochemical performance after
30-cycle operation, which also indicated that MFC was an identical
technology for Cr(VI) removal and bioelectricity generation simulta-
neous.

3.5. Surface characteristics of cathode

As can be seen from the graphical abstract, the electrons from anode
eventually were transferred to the cathode, driving reduction Cr(VI) to
Cr(III). After Cr(VI) reduction process in the batch system using carbon
cloth cathode, the electrodes were examined using SEM. As shown in
Fig. 5a, a large number of precipitation deposited in the carbon cloth,
indicating that precipitation was produced by the electrochemical re-
duction of MFC. In our work, the catholyte pH increased from 2.0 to
3.78 ± 0.15 with the constant replacement of Cr(VI). According to the
Cr-Pourbaix diagram [29], the generated Cr(III) existed in the form of
Cr(OH)3. Besides, the previous study demonstrated that under experi-
mental temperature the solubility product constant of Cr(OH)3 was very
small so that Cr(III) would precipitate on the electrode after its pro-
duction [38]. Herein, the surface elements in the precipitation were
also analyzed by EDS and elemental mapping images. Obviously,
carbon, oxygen and chromium were the main elements of electrode and
these elements were distributed homogeneously over the whole elec-
trode, further confirming the form of precipitation.

3.6. Stability of fed-batch operation

To the best of our knowledge, the stability was an important in-

Fig. 6. Stability test of MFC used carbon cloth cathode with the fresh 80 mg L−1 Cr(VI)
solution during the long-term cycle operation. (a) The cell voltage-time curves; (b) Cr(VI)
reduction vs. time curves; (c) Power density curves.
equation showed that higher concentration Cr(VI) could exhibit faster
electrochemical reaction rate (120 mg L−1 > 80 mg L−1 > 50 mg L−1).
The acetate form the anode chamber was consumed by electricigens
in the anode electrode, and the large number of electron and proton
were released into the solution. The proton through the PEM was
transferred to the cathode chamber, and the electron was transferred to
the cathode electrode through the anode electrode and external circuit.
Then the proton, electron and Cr(VI) ion had a chemical reaction so that
the Cr(VI) was reduced to Cr(III). During this reaction, the reduction
efficiency of Cr(VI) was strongly dependent on the pH of catholyte.
dicator to evaluate the performance of MFCs. The long-term stability of
MFC was evaluated by carrying out successive Cr(VI) reduction in the
cathode, and the initial Cr(VI) concentration was 80 mg L−1. Thirty
successive cycles were operated over 90 d, and the performance of MFC
was monitored in terms of cell voltage, Cr(VI) concentration and power
density. As can be observed from Fig. 6a, the cell voltage slowly de-
creased and the maximum cell voltage increased from 0.745 V to
0.829 V with the replacement of fresh substrate. Correspondingly, the
maximum power density (Fig. 6c) also increased from
1189.98 mW m−2 to 1221.91 mW m−2. Besides, the Cr(VI) was totally
removed within 72 h in each cycle (Fig. 6b). The performance of MFC
kept stable, and the cell voltage and power density slightly decreased.
The results should be attributed to the better stability of MFC.
Additionally, the removal of Cr(VI) was also compared in our stu-
dies and the other literatures. In contrast to traditional treatment

1627
M. Li et al.
method such as bioreduction, adsorption, photocatalytic reduction,
electrocoagulation, nanofiltration and bacteria reduction, the MFC
technology (Table 3) for reduction of Cr(VI) had more advantages. MFC
technology had higher Cr(VI) concentration tolerance than the biolo-
gical treatment, and a considerable of toxic waste sludge was not pro-
duced. Meanwhile, MFC technology could generate bioelectricity while
it removing Cr(VI). To sum up, MFC technology that an outstanding
bio-electrochemical technology could effectively remove Cr(VI) and
harvest bioelectricity simultaneously.
4. Conclusions
This study demonstrated that the MFC technology could be used to
remove Cr(VI) from wastewater and harvest bioelectricity simulta-
neously. The maximum removal efficiency of 100% was obtained in
72 h at pH 2, which was higher than that of the traditional treatment
method in other literatures. Besides, the EIS and power density of
electrodes indicated that the carbon cloth of low resistance displayed
excellent electrochemical performance on bioelectricity generation and
Cr(VI) removal in comparison with carbon brush and carbon felt elec-
trodes. It should be noted that the higher concentration of Cr(VI) could
enhance the power density, and the MFC produced the maximum power
density of 1221.91 mW m−2 at 120 mg L−1 of Cr(VI), which was 1.10
times and 1.43 times higher than that of MFC at 80 mg L−1 and
50 mg L−1, which was consistent with LSV results. In addition, the
stable nontoxic Cr(OH)3 was founded and verified by the EDS analysis.
Consequently, the high power density, high Cr(VI) removal confirmed
that MFC technology could be scaled up for treating wastewater con-
taining Cr(VI) and generating renewable energy simultaneously.
Acknowledgments
We gratefully acknowledged financial support from the Ministry of
Science and Technology of China for State Key Research and
Development Project (2016YFC0400708).
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.cej.2017.11.144.
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