Accepted Manuscript

Improved decolorization of dye wastewater in an electrochemical

system powered by microbial fuel cells and intensified by micro-
electrolysis

Shuai Liang, Baogang Zhang, Jiaxin Shi, Ting Wang, Lifeng

Zhang, Zhijun Wang, Cuibai Chen

PII: S1567-5394(18)30153-1
DOI: doi:10.1016/j.bioelechem.2018.07.008
Reference: BIOJEC 7186
To appear in: Bioelectrochemistry
Received date: 6 April 2018
Revised date: 6 July 2018
Accepted date: 9 July 2018

Please cite this article as: Shuai Liang, Baogang Zhang, Jiaxin Shi, Ting Wang, Lifeng
Zhang, Zhijun Wang, Cuibai Chen , Improved decolorization of dye wastewater in an
electrochemical system powered by microbial fuel cells and intensified by micro-
electrolysis. Biojec (2018), doi:10.1016/j.bioelechem.2018.07.008

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 ACCEPTED MANUSCRIPT

Improved Decolorization of Dye Wastewater in an Electrochemical

System Powered by Microbial Fuel Cells and Intensified by

Micro-electrolysis

Shuai Lianga, Baogang Zhanga,*, Jiaxin Shia, Ting Wangb, Lifeng Zhanga, Zhijun

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Wanga, Cuibai Chena

a
School of Water Resources and Environment, MOE Key Laboratory of Groundwater

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Circulation and Environmental Evolution, China University of Geosciences (Beijing),

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Beijing 100083, China
b
The Key Laboratory of Water and Sediment Sciences, Ministry of Education,
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Department of Environmental Engineering, Peking University, Beijing 100871, China
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*
Corresponding author. Tel.: +86 10 8232 2281; Fax: +86 10 8232 1081.

E-mail: zbgcugb@gmail.com, baogangzhang@cugb.edu.cn (B. Zhang).

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Abstract

Electrochemical decolorization is of particular importance for the efficient

treatment of dye wastewater. A promising electrochemical system powered by

microbial fuel cells (MFCs) and intensified by Fe-C micro-electrolysis is proposed

and enhanced decolorization of methyl orange (MO) is realized in this study. The

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decolorization efficiency reached as high as 97.1 ± 1.8% after 180 min of operation

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with initial MO concentration of 50 mg/L and applied voltage of 700 mV.

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Decolorization efficiency initially increased and then decreased with rising Fe-to-C

ratio. In addition, efficiency was enhanced with the increase of aeration rate up to 6.0
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L/min. Lower initial MO concentration and pH were also shown to facilitate MO
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decolorization. A study of mechanisms, with results from control tests and scavenger

experiments indicated that MO decolorization was contributed by the indirect

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oxidation by various oxidizing substances, especially ·O2−, that were generated during

the process. MO molecule was decomposed and low molecular weight compounds
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such as indolizine, hydrazide and thione were generated. This study advances the
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performance of MFC in dye wastewater treatment by combining with a standard

technique.
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Keywords: Microbial fuel cell; Decolorization; Methyl orange; Micro-electrolysis

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1. Introduction

Paper and pulp, leather and textile industries generate large amounts of

dye-containing wastewater daily [1-3], which can lead to environmental and public

health issues if not properly treated [4]. Synthetic dyes are typical recalcitrant

pollutants due to the presence of complex molecules such as chemically stable azo

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bond and aromatic rings [5]. Dye wastewater is high in chromaticity, toxicity and

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potential mutagenicity, and may pose detrimental effects on aquatic organisms [6,7].

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Therefore, dye wastewater should be properly disposed before discharge, especially
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for color removals.

Traditional physical decolorization of dye wastewater like adsorption and ion

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exchange can only transfer contaminants from water to another medium, and may

lead to secondary pollution [8,9]. Due to the low biodegradability of dye molecules,
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biological approaches to color removal are often restricted by microbial activity [10].
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Although chemical methods such as electrocoagulation and advanced oxidation

technologies can effectively achieve dye decolorization, they require significant time
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and energy that may restrict their practical applications [11,12]. By comparison,
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electrochemical oxidation technology is regarded as a more efficient and

easy-to-control process for dye decolorization [13]. Significant efforts have been

made to improve the performance and reduce the cost of electrochemical oxidation,

for example, different substances and methods have been used to modify the

electrodes [14-16]. Typically, microbial fuel cells (MFCs) are devices of

bioelectrochemical systems that use microorganisms as catalysts to convert chemical

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energy in organic or inorganic materials directly into electricity [17,18]. MFCs have

been employed independently for electrochemical decolorization of dye wastewater

with bioelectricity generation in both the anode and cathode chambers [19-21].

Although the voltage and current outputs are relatively low, MFCs can be used as

renewable power sources under specific circumstances, for example, bipolar

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membrane electrodialysis powered by MFCs has been successfully demonstrated for

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alkali production and the resulting alkali solution is suitable for biogas upgrading [22].

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Previous studies have also reported that methyl orange (MO), a typical azo dye, is

successfully decolorized in an aeration electrochemical system with single-chamber

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MFCs as renewable power sources [23,24], while the decolorization efficiency of this
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novel system needs to be further improved. Iron-carbon (Fe-C) micro-electrolysis is

an economical and environmentally friendly treatment method. When iron powder is

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in contact with activated carbon in acidic solution, numerous microscopic galvanic

cells are formed due to the high potential difference (0.44 V) between Fe and C [25].
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High-activity products such as active hydrogen, hydroxyl radical and ferric

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flocculants generated during this process can bring about redox reaction and
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electrocoagulation with pollutants. This reaction is especially prominent for

non-readily degradable organics at high concentration, which can, in turn, improve the

biodegradability of organic wastewater [26]. Fe-C micro-electrolysis has been utilized

in the treatment of coking wastewater [27], ionic liquid [28], dye wastewater [29], as

it is less expensive and does not require an external power supply. However, its

synergistic interactions with electrochemical oxidation to enhance pollutant removals

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have rarely been explored.

In this study, an electrochemical reactor powered by single-chamber MFCs and

intensified by micro-electrolysis was constructed and its performance of color

removal was evaluated, with MO as the target pollutant. Experiments were performed

under different conditions to investigate the effects of various operating factors.

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Possible decolorization mechanisms were investigated by specifying the functions of

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active substances and monitoring the degradation products. Results of this study

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provide insights into a cost-effective alternative to enhance electrochemical

decolorization of dye wastewater intensified by micro-electrolysis.

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2. Material and methods
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2.1. System construction and reagents

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The proposed coupling electrochemical system was composed of a single

chamber MFC and an aerated electrochemical reactor (AER). The configuration was
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shown in Schematic 1. A cubic single-chamber, air-cathode, membrane-less MFC

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with effective volume of 125 mL (5 cm × 5 cm × 5 cm) was employed as reported in

our previous studies [30,31]. Anode was made of carbon fiber felt (4 cm × 4 cm × 1
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cm, Evergrow Resources Co. Ltd, Beijing, China) and plain carbon paper (0.5 mg/cm2

of Pt attached one side, Hesen Co. Ltd, Shanghai, China) with projected surface of 16

cm2 was used as cathode. External circuit included a 1000 Ω external resistance

during the start-up period. In addition, 25 mL of anaerobic sludge obtained from an

up-flow anaerobic sludge blanket reactor was inoculated into the MFC [32]. The

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anolyte contained 50 mM phosphate buffer solution, 0.75 g/L glucose, 0.13 g/L KCl,

0.31 g/L NH4Cl, 12.5 mL/L trace mineral element solution and 1.25 mL/L vitamin

solution [30,33].

A glass beaker with effective working volume of 200 mL was employed as the

AER. Both the anode and cathode were made of carbon felt (2.5 cm × 4 cm × 1 cm)

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with a distance of 1 cm between them [23]. During the process of decolorization, they

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were connected to the electrodes of the MFCs by copper wire. Simultaneously, a

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variable resistor was connected to the circuit for adjusting the desired voltage across

the AER. An inflator with air diffuser was placed near the cathode to provide
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dissolved oxygen. To exclude the effect of adsorption, both electrodes of the AER and
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activated carbon were immersed in the target solution for 360 minutes to achieve

saturation prior to formal experiments. Dye wastewater with 0.01 M supporting

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electrolyte (Na2SO4) at initial pH (H2SO4 adjustment) and desired concentration of

MO (C14H14N3O3SNa) was synthesized for electrochemical tests. Activated carbon

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and reduced iron powder purchased from Sinopharm Chemical Reagent Co., Ltd.
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(Beijing, China) were also added at the settled ratio. All chemical reagents used were
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of analytical grade without further purification.

2.2. Experimental procedures

Successful start-up of MFC with repeatable power outputs was realized by

replenishing electrolyte every 3 days. Then, the MFC was connected to the AER,

which was intensified by Fe-C micro-electrolysis, for electrochemical decolorization

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of MO in a typical cycle of 180 min, with an initial MO concentration of 50 mg/L,

aqueous pH of 3.0, aeration rate of 6.0 L/min, applied voltage of 700 mV, mass ratio

for reduced iron powder and activated carbon (Fe-to-C ratio) of 1:1 with an exact

respective mass weight of 0.5 g [26]. Experiments were also conducted on a series of

control sets, including AER powered by MFC, Fe-C micro-electrolysis only, aeration

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only and electrolysis only, respectively. Several factors that could potentially affect

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the performance of the proposed system were investigated, including Fe-to-C ratio

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(0.5, 0.8, 1.0, 1.5), aeration rate (1.0, 3.0, 6.0, 9.0 L/min), MO concentration (20, 50,

100, 150 mg/L) and initial pH (1.0, 3.0, 5.0, 7.0), respectively. Orthogonal array, test
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with L16 (44) orthogonal table was performed to determine the degrees of importance
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of these four parameters (Table S1, Supporting Information). In addition,

concentrations of total oxidizing species (TOS) were measured and different

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scavengers were added individually or simultaneously in the solution to confirm

functions of the corresponding active substances [34]. Degradation products were also
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monitored. All experiments were carried out at room temperature (22 ± 2 ℃). Each
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test was performed in triplicate and the averaged results were reported.
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2.3. Analytical methods

To monitor the MO concentration, absorbance at of maximum absorption

wavelength of MO was recorded by a UV-visible spectrophotometer (DR 5000,

HACH, USA) [35]. A multi-functional testing instrument (SevenExcellence, Mettler

Toledo, Switzerland) was used to measure pH. Concentrations of Fe3+ and Fe2+ were

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also measured by a UV-visible spectrophotometer. Wavelength scanning experiment

for revealing the structural transformation of MO was conducted by the UV-visible

spectrophotometer at a range from 200 to 800 nm. The concentration of TOS was

determined by the N, N-diethyl-p-phenylenediamine (DPD) colorimetric method [36].

The generation of hydrogen peroxide was determined by spectrophotometry at 350

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nm [37]. Scavengers like isopropanol, Fe (II)-EDTA and

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4-hydroxy-2,2,6,6-tetramethylpiperidin 1-oxyl (TEMPOL) were added to remove

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diffusing ·OH, H2O2, and ·O2− in the solution, respectively [38]. The decolorization

products were measured by Gas Chromatography-Mass Spectrometric (GC-MS, Trace

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GC-DSQ, Thermo Fisher, USA) according to Zhang et al [24], with ultrapure helium
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as the carrier gas at a constant flow rate of 1.0 mL/min. The polarization curve was

obtained by measuring voltages at various external resistances (ranging from 10 to

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5000 Ω) to evaluate the relationship between voltage and current [39]. Voltage and

current readings of the MFC were taken by a multimeter during the decolorization
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process.
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3. Results and discussion

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3.1 Power outputs of the MFC

After successful start-up, polarization curve and power outputs of the single

chamber MFC were obtained (Fig. 1), with a maximum power density of 502.5 ± 17.1

mW/m2 at a current density of 1250.6 ± 23.4 mA/m2. This level of bioelectricity

generation was comparable to those reported in studies. For example, a maximum

power density output of 477 mW/m2 was obtained from similar cubic single-chamber
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MFC of the same volume [40].

Voltage outputs of the MFC were continuous monitored with fresh anolyte

during the 3 d operation with the AER directly connected to the MFC and the output

values were in the range of 100-720 mV. This result demonstrated that the MFC

worked properly as renewable power sources for subsequent electrolysis experiments.

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Although the capital cost of full scale MFCs might be higher than that of common DC

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power supplies, there were various application benefits for using MFCs such as the

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simultaneous treatment of domestic sewage [41]. These confirmed the promising

employment of MFCs in electrochemical processes as renewable power sources.

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3.2 Decolorization performance
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Apparent decolorization of MO was observed in AER powered by the MFC and

intensified by Fe-C micro-electrolysis (Fig. 2). The decolorization efficiency reached

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as high as 97.1 ± 1.8% after a 180 min operation at Fe-to-C ratio of 1:1, aeration rate
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of 6.0 L/min, initial MO concentration of 50 mg/L and pH of 3.0. The voltage of MFC
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was fixed at 700 mV by adjusting the variable resistor in the circuit. The range of

corresponding current during the 180 min operation was 0.4-1.2 mA. The obtained
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decolorization efficacy showed advantage to that achieved in previous studies. For

instance, decolorization efficiency only reached a maximum of 76.03% at initial MO

concentration of 200 mg/L after 150 min operation in the Fe-C micro-electrolysis

treatment [42]. Similarly, photocatalysis achieved a decolorization efficiency of

82.6% at MO concentration of 20 mg/L after a 30 min operation with Pt modified

TiO2 photocatalyst [43]. Moreover, azo dye decolorization was also accomplished

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independently in the MFCs and our results were superior to those reported in other

related studies [44,45]. Thereby, we concluded that MO could be electrochemically

decolorized effectively with MFCs as renewable power sources and intensification by

Fe-C micro-electrolysis.

Results from the control experiments also confirmed the effectiveness of the

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proposed system. Without intensification by Fe-C micro-electrolysis, decolorization

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efficiency of MO decreased to 82.4 ± 2.4%, while only 67.36% of MO was removed

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with Fe-C micro-electrolysis alone. These findings were comparable with reported

results of similar systems [24,42]. Slight MO decolorization was observed after

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electrolysis performed at 700 mV generated from the MFC. This could be attributed
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to the lower applied voltage compared to traditional electrochemical decolorization

[46]. Color removal was rarely observed with aeration only or adsorption only
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resulted from saturated activated carbon and carbon felt.

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3.3 Effects of operating factors

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When iron powder and activated carbon were combined in wastewater, numerous

microscopic galvanic cells were formed between them in the solution [26], therefore,
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Fe-to-C ratio exhibited an important effect on the decolorization efficiency of dye

solution. As shown in Fig. 3a, decolorization efficiencies of MO initially increased,

then decreased, with increasing Fe-to-C ratios that peaked at 1:1. Optimal increase in

Fe helped to promote the microscopic galvanic cell reaction in the system, and also

expedited the electromigration and redox reactions [42]. However, larger amount of

Fe could have an adverse effect on the decolorization process as Fe consumes more

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oxidizing substances to form of Fe2+ and Fe3+, instead of facilitating decolorization. In

addition, excessive carbon could also impact the contact between iron and carbon

contact by reducing mass transfer efficiency, which could also suppress the

decolorization performance. Therefore, a Fe-to-C ratio of 1:1 as the optimum was

selected in the subsequent experiments.

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Oxygen affects the generation of active substances in both the electrochemical

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and Fe-C micro-electrolysis processes. MO decolorization was enhanced with an

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increase in aeration rate from 1.0 to 6.0 L/min (Fig. 3b). Sufficient aeration not only

provided oxygen for generating active substances via cathode reaction, but also served
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as the driving force that prevented Fe-C bonding in favor of surface activation of iron
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[26]. The enhancement of decolorization efficiency in our system was mainly

attributed to these oxidation substances. Therefore, adequate aeration rate was

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conducive to improving the efficiency of decolorization. However, no further

improvement in the decolorization efficiency was observed when the aeration rate
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exceeded 6.0 L/min (Fig. 3b), at which the dissolved oxygen levels approached
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saturation in the solution. Maintaining a dissolved oxygen level below that of

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saturation with an optimal aeration rate could avoid unnecessary loss. Hence, an

aeration rate of 6.0 L/min was chosen for the subsequent experiment.

Decolorization efficiencies of MO initially increased, then decreased, with an

increase in initial MO concentration from 20 to 150 mg/L (Fig. 3c). Similar

observations were also reported in studies on MO decolorization by photocatalysis

with VS4/carbon powder nanoparticles [47]. When the initial MO concentration

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increased from 20 to 50 mg/L, the decolorization efficiency increased from 70.1 ±

1.4% to 96.8 ± 0.9% during a period of 180 min. Active substances generally have

very short lifespan and only a small amount of them had a chance to react with the

MO molecules. The probability of reaction between active substances and MO

molecules increased with increasing MO concentration [42]. However, decolorization

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efficiencies decreased at high MO concentrations (over 50 mg/L), at which the

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amount of active substances generated under the experimental conditions reached a

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maximum [42]. Additionally, during the course of the experiment, intermediates that

were produced from the decomposition of the dye could compete with the original
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dye molecules for active substances. Therefore, an initial MO concentration of 50
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mg/L was selected as optimum for subsequent experiments.

As shown in Fig. 3d, the decolorization efficiency of MO decreased slightly

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when pH increased from 1.0 to 3.0, followed by a sharp decrease when pH was over

3.0. Decolorization efficiency was only at 70.5 ± 1.3% under pH of 7.0. Acidic
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condition was conducive to the microscopic galvanic cell reaction in the Fe-C
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micro-electrolysis system and could accelerate redox reaction and coagulation [26].
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Meanwhile, acidic condition was also conducive to the production of H2O2, which

promoted decolorization of dye solution in the AER powered by MFC [23]. The

concentration of H2O2 reached 36.9 ± 2.7 mg/L after a 180 min operation at pH 1.0,

however, the yield of H2O2 decreased to 1.9 ± 0.6 mg/L when pH increased to 7.0 (Fig.

S1, Supporting Information). In addition, the Fe2+ and H2O2 generated could easily

interact to form Fenton reagent under acidic conditions, which was beneficial to the

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production of hydroxyl radicals [48]. These explained the decline in decolorization

efficiency at higher pH. Previous studies had shown that iron was inactivated by large

amounts of hydrogen generated under acidic condition, which could, in turn, inhibit

the microscopic galvanic cell reaction [26]. At low pH (less than 3.0), the carbon

cathode could compete with the hydrogen separator to prevent cell reactions [42].

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However, excellent decolorization performance was achieved even when pH was as

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low as 1.0 in the present study. This might be due to the superior aeration rate, as

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hydrogen could be discharged from the reactor just in time before causing any adverse

effects. Nevertheless, numerous Fe2+ were produced at low pH, which negatively
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affected color removal of dye wastewater due to the color-rendering property of Fe2+
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[26]. Therefore, proper pH condition should be considered in the practical

applications of the proposed system.

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MO decolorization efficiency varied during the 180 min operation in the

proposed system under designed orthogonal condition (Table S2, Supporting

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Information). Variance analysis was performed and the degree of importance of four
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factors was determined in the following order: pH > MO concentration > Fe-to-C
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ratio > aeration rate (Table S2, Supporting Information). The significance of pH on

MO decolorization efficiency in the Fenton process had also been reported previously

[49]. Besides performance efficiency, other factors such as cost should also be

considered to determine the optimal condition for actual application.

3.4 Investigation of decolorization mechanisms

In this study, MO decolorization was realized via two routes: electrochemical

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oxidation driven by MFC and Fe-C micro electrolysis. For the former, results from

control sets suggested that indirect electrochemical effects were mainly responsible

for the decolorization of MO solution. Active substances played dominant roles in this

process, as TOS increased progressively in the experiment (Fig. 4). In fact, in an

acidic solution, H2O2 was continuously generated by two-electron oxygen reductions,

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as described in the following reaction, in the AER with MFC as renewable power

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sources [50].

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O2 + 2H+ + 2e- → H2O2 (1)

Therefore, H2O2 could potentially be involved in the MO decolorization observed in

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the present study.
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Functions of Fe-C micro-electrolysis in MO decolorization were particularly

emphasized. Firstly, in terms of a single Fe-C micro-electrolysis system, H + in the

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solution was reduced to active [H] and H2 at the cathode as Eq. (2), and anodic iron

was only oxidized to form Fe2+ as Eq. (3). Those active [H] and fresh Fe2+ are highly
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chemically active and could react easily with contaminants [51]. Fe2+ was detected in
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the dye solution accordingly (Fig. 4).

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Cathode: 2H+ + 2e- → 2[H] → H2 (2)

Anode: Fe - 2e- → Fe2+ (3)

Furthermore, in our coupling electrochemical system, with generated H2O2 and Fe2+ in

acidic solution, free hydroxyl radicals (·OH) was also produced via the Fenton

process,

Fe2+ + H2O2 → Fe3+ + ·OH + OH- (4)

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As proposed, gradual increase in Fe3+ concentration with decrease in Fe2+ was

observed (Fig. 4). Additionally, ·O2− was also generated simultaneously as Eq. (5) and

(6) in the Fenton system as part of the classical Fenton chain reaction [52]. ·O2− could

also exhibit considerable effect on the removal of pollutant [53].

Fe3+ + H2O2 → Fe2+ + ·HO2 + H+ (5)

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·HO2 → H+ + ·O2− (6)

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In addition, scavenger experiments were also performed to elucidate the roles of

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active substances. All of these scavengers were target specific, with elimination of

H2O2 by Fe(II)-EDTA [54], ·OH by isopropanol [55] and ·O2− by TEMPOL [56],
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respectively. When H2O2 was eliminated in the dye solution, the decolorization
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efficiency of MO reduced by about 10% (Fig. 5), indicating that a small amount of

H2O2 that was produced in our coupling electrochemical contributed to MO

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decolorization. In fact, high concentration of H2O2 could have a negative impact on

decolorization due to its ·OH scavenging effect [57]. Slight decrease in MO

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decolorization was also observed when ·OH was eliminated in the dye solution (Fig.
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5), which indicated that Fenton reaction took place in the proposed system and the
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generated ·OH participated in the decolorization process. Notably, the contributions of

H2O2 weakened in AER powered by MFC only as reported in previous study [23],

probably due to its in situ consumption. In other words, the generated H2O2 should

react first with Fe2+ in Fenton reaction rather than being directly involved in the

decolorization of MO. The most obvious decline in decolorization efficiency was

obtained when ·O2− was removed from the dye solution (Fig. 5), which demonstrated

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that ·O2− was mainly responsible for the decolorization of dye solution in the present

study. Furthermore, MO decolorization efficiency was less than 10% when the three

scavengers were added simultaneously, suggesting that other active substances

generated in Fe-C micro-electrolysis, such as [H] and H2, could play insignificant

roles on MO decolorization. Previous study also indicated that oxidative active

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substances contributed to MO decolorization significantly in Fe-C micro-electrolysis

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intensified systems [42]. Moreover, the production of the aforementioned active

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substances in the proposed system was spontaneous, which highlighted the advantage

of this system in actual applications.

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The UV-visible spectra of the MO solution at an initial pH of 3.0 were recorded
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(Fig. 6). Two absorbance peaks, at 272 nm and 506 nm, were identified, which

corresponded to aromatic rings and azo band, respectively. Both of these peaks
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declined distinctly with time, suggesting the destructions of aromatic rings and azo

band during the decolorization of MO [58]. These results indicated that the great
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majority of dye molecules were destroyed by electrochemical oxidation in the

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proposed electrochemical system. Of note, the maximum absorption wavelength of

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MO shifted with varying pH. The MO molecule in pH range of 4.1 - 9.5 was

characterized by a band in the range of 485 - 465 nm, while more intense absorption

band shifted to a longer wavelength (appears at 506 nm) under more acidic conditions

[59]. Additionally, GC-MS analysis revealed that the main reduction products of MO

were indolizine, hydrazide and thione (Table 1). The above results suggested that MO

molecules were simply decomposed into smaller organic molecules in our system.

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Species of intermediates detected in this study were more complex than those

identified in our previous research [24], implying the effective decomposition of MO,

as well as the potential bonding between intermediates.

4. Conclusions

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Effective electrochemical MO decolorization was achieved in an AER powered

by MFC and intensified by Fe-C micro-electrolysis. Operating factors as Fe-to-C ratio,

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aeration rate, MO concentration and initial pH affected the decolorization

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performance. MO was effectively decomposed, with the generation of low molecular
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weight compounds such as indolizine and thione. Indirect oxidation by generated

oxidizing substances, especially ·O2−, was responsible for MO decolorization. This

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work proposed an effective route to dye wastewater treatment based on MFC

technology. The developed system could also be employed to remove other

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environmental contaminants, such as bio-refractory organics. As an emerging

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technology, MFC would be more promising when combined with standard techniques.
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This study provided an example and efforts should be further made to link MFC with

other existing means for efficiency improvement and cost reduction.

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Acknowledgements

This research work was supported by the National Natural Science Foundation of

China (NSFC) (No. 91647115) and Beijing Nova Program (No. Z171100001117082).

References

[1] C.M. Martinez, X. Zhu, B.E. Logan, AQDS immobilized solid-phase redox

17
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mediators and their role during bioelectricity generation and RR2 decolorization

in air-cathode single-chamber microbial fuel cells, Bioelectrochemistry 118 (2017)

123-130.

[2] J. Zhang, H. Yu, X. Quan, S. Chen, Y. Zhang, Ceramic membrane separation

coupled with catalytic ozonation for tertiary treatment of dyestuff wastewater in a

PT
pilot-scale study, Chem. Eng. J. 301 (2016) 19-26.

RI
[3] Y. Cao, Y. Hu, J. Sun, B. Hou, Explore various co-substrates for simultaneous

SC
electricity generation and Congo red degradation in air-cathode single-chamber

microbial fuel cell, Bioelectrochemistry 79 (2010) 71-76.

NU
[4] T.L. Silva, A.L. Cazetta , P.S.C. Souza, T. Zhang, T. Asefa, V.C. Almeida,
MA

Mesoporous activated carbon fibers synthesized from denim fabric waste:

efficient adsorbents for removal of textile dye from aqueous solutions, J. Clean.
ED

Prod. 171 (2018) 482-490.

[5] M.A. Selene, K.A. Bonilla, A.A. Souza, Removal of COD and color from
PT

hydrolyzed textile azo dye by combined ozonation and biological treatment, J

CE

Hazard. Mater. 179 (2010) 35-42.

AC

[6] M.H. Cui, D. Cui, L. Gao, A.J. Wang, H.Y. Cheng, Azo dye decolorization in an

up-flow bioelectrochemical reactor with domestic wastewater as a cost-effective

yet highly efficient electron donor source, Water Res. 105 (2016) 520-526.

[7] S. Figueroa, L. Vázquez, A. Alvaerzgallegos, Decolorizing textile wastewater

with Fenton's reagent electrogenerated with a solar photovoltaic cell, Water Res.

43 (2009) 283-294.

18
 ACCEPTED MANUSCRIPT

[8] V. Murali, S.A. Ong, L.N. Ho, Y.S. Wong, Evaluation of integrated

anaerobic-aerobic biofilm reactor for degradation of azo dye methyl

orange, Bioresource Technol. 143 (2013) 104-111.

[9] C. Phalakornkule, P. Sukkasem, C. Mutchimsattha, Hydrogen recovery from the

electrocoagulation treatment of dye-containing wastewater, Int. J. Hydrogen

PT
Energy. 35 (2010) 10934-10943.

RI
[10] F. Xu, Z. Mou, Geng J, X. Zhang, C.Z. Li, Azo dye decolorization by a

SC
halotolerant exoelectrogenic decolorizer isolated from marine sediment,

Chemosphere 158 (2016) 30-36.

NU
[11] E. Alventosadelara, S. Barredodamas, M. Alcainamiranda, M. Iborraclar,
MA

Ultrafiltration technology with a ceramic membrane for reactive dye removal:

Optimization of membrane performance, J. Hazard. Mater. 209-210 (2012)

ED

492-500.

[12] M. Mondal, S. De, Treatment of textile plant effluent by hollow fiber

PT

nanofiltration membrane and multi-component steady state modeling, Chem. Eng.

CE

J. 285 (2016) 304-318.

AC

[13] X.L. Xu, Y.M. Jia, L.B. Xiao, Z. Wu, Strong vibration-catalysis of zno nanorods

for dye wastewater decolorization via piezo-electro-chemical

coupling, Chemosphere 193 (2018) 1143-1148.

[14] S.H. Li, Y. Zhao, J. Chu, W.W. Li, H.Q. Yu, G. Liu, Electrochemical

degradation of methyl orange on Pt–Bi/C nanostructured electrode by a

square-wave potential method, Electrochim. Acta 92 (2013) 93-101.

19
 ACCEPTED MANUSCRIPT

[15] S.L. Lee, L.N. Ho, S.A. Ong, Y.S. Wong, C.H. Voon, F.K. Wan, Enhanced

electricity generation and degradation of the azo dye reactive green 19 in a

photocatalytic fuel cell using ZnO/Zn as the photoanode, J. Clean. Prod. 127

(2016) 579-584.

[16] L. Yue, J.B. Guo, J.L. Yang, J. Lian, X. Luo, X.N. Wang, Studies on the

PT
electrochemical degradation of acid orange Ⅱwastewater with cathodes modified

RI
by quinones, J. Ind. Eng. Chem. 20 (2014) 752-758.

SC
[17] B.G. Zhang, H.Z. Zhao, S.G. Zhou, C.H. Shi, C. Wang, J.R. Ni, A novel

UASB-MFC-BAF integrated system for high strength molasses wastewater

NU
treatment and bioelectricity generation, Bioresour. Technol. 100 (2009)
MA

5687-5693.

[18] B.G. Zhang, C.P. Feng, J.R. Ni, J. Zhang, W.L. Huang, Simultaneous reduction
ED

of vanadium (V) and chromium (VI) with enhanced energy recovery based on

microbial fuel cell technology, J. Power Sources 204 (2012) 34-39.

PT

[19] S.V. Mohan, S. Srikanth, P.N. Sarma, Non-catalyzed microbial fuel cell (MFC)
CE

with open air cathode for bioelectricity generation during acidogenic wastewater
AC

treatment, Bioelectrochemistry 75 (2009) 130-135.

[20] Sun, Z. Bi, B. Hou, Y.Q. Cao, Y.Y. Hu, Further treatment of decolorization

liquid of azo dye coupled with increased power production using microbial fuel

cell equipped with an aerobic biocathode, Water Res. 45 (2011) 283-291.

[21] B.Y. Chen, C.M. Ma, K. Han, P.L. Yueh, L.J. Qin, C.C. Hsueh, Influence of

textile dye and decolorized metabolites on microbial fuel cell-assisted

20
 ACCEPTED MANUSCRIPT

bioremediation, Bioresour. Technol. 200 (2016) 1033-1038.

[22] M. Chen, F. Zhang, Y. Zhang, R.J. Zeng, Alkali production from bipolar

membrane electrodialysis powered by microbial fuel cell and application for

biogas upgrading, Appl. Energ. 103 (2013) 428-434.

[23] Z.J. Wang, B.G. Zhang, A.G. Borthwick, C.P. Feng, J.R. Ni, Utilization of

PT
single-chamber microbial fuel cells as renewable power sources for

RI
electrochemical degradation of nitrogen-containing organic compounds, Chem.

SC
Eng. J. 280 (2015) 99-105.

[24] B.G. Zhang, Z.J. Wang, X. Zhou, H.M. Guo, C.P. Feng, Electrochemical
NU
decolorization of methyl orange powered by bioelectricity from single-chamber
MA

microbial fuel cells, Bioresour. Technol. 181 (2015) 360-362.

[25] L.Q. Wang, Q. Yang, D.B. Wang, X.M. Li, G.M. Zeng, Z.J. Li, Y.C. Deng, J.
ED

Liu, K.X. Yi, Advanced landfill leachate treatment using iron-carbon

microelectrolysis-fenton process: process optimization and column experiments, J.

PT

Hazard. Mater. 318 (2016) 460-467.

CE

[26] Y.H. Han, H. Li, M.L. Liu, Y.M. Sang, C.Z. Liang, J.Q. Chen, Purification
AC

treatment of dyes wastewater with a novel micro-electrolysis reactor, Sep.

Purif.Technol. 170 (2016) 241-247.

[27] W.W. Liu, X.Y. Tu, X.P. Wang, F.Q. Wang, W. Li, Pretreatment of coking

wastewater by acid out, micro-electrolysis process with in situ electrochemical

peroxidation reaction, Chem. Eng. J. 200-202 (2012) 720-728.

[28] H. Zhou, Y. Shen, P. Lv, J. Wang, J. Fan, Degradation of

21
 ACCEPTED MANUSCRIPT

1-butyl-3-methylimidazolium chloride ionic liquid by ultrasound and zero-valent

iron/activated carbon, Sep. Purif. Technol. 104 (2013) 208-213.

[29] X. Ning, W. Wen, Y. Zhang, R. Li, J. Sun, Y. Wang, Enhanced dewaterability of

textile dyeing sludge using micro-electrolysis pretreatment, J. Environ. Manage.

161 (2015) 181-187.

PT
[30] J. Zhang, B.G. Zhang, C.X. Tian , Z.F. Ye, Y.Liu, Simultaneous sulfide removal

RI
and electricity generation with corn stover biomass as co-substrate in microbial

SC
fuel cells, Bioresour. Technol. 138 (2013) 198-203.

[31] B.G. Zhang, Y. Liu, S. Tong, M.S. Zheng, Y.X. Zhao, C.X. Tian, H.Y. Liu, C.P.
NU
Feng, Enhancement of bacterial denitrification for nitrate removal in groundwater
MA

with electrical stimulation from microbial fuel cells, J. Power Sources 268 (2014)

423-429.
ED

[32] Z.L. Wang, B.G. Zhang, Y.F. Jiang, Y.L. Li, C. He, Spontaneous thallium (I)

oxidation with electricity generation in single-chamber microbial fuel cells, Appl.

PT

Energ. 209 (2018) 33-42.

CE

[33] Y. Liu, B.G. Zhang, C.X. Tian, C.P. Feng, Z.J. Wang, W.W. Hu, Optimization of
AC

enhanced bioelectrical reactor with electricity from microbial fuel cells for

groundwater nitrate removal, Environ. Technol. 37 (2016) 1008-1017.

[34] Y.L. Li, B.G. Zhang, A.G.L. Borthwick, Y.J. Long, Efficient electrochemical

oxidation of thallium (I) in groundwater using boron-doped diamond anode,

Electrochim. Acta 222 (2016)1137-1143.

[35] S. Haji, B. Benstaali, N. Al-Bastaki, Degradation of methyl orange by UV/H2O2,

22
 ACCEPTED MANUSCRIPT

advanced oxidation process, Chem. Eng. J. 168 (2011) 134-139.

[36] S. Caillet, S. Salmieri, M. Lacroix, Evaluation of free radical-scavenging

properties of commercial grape phenol extracts by a fast colorimetric

method, Food Chem. 95 (2006) 1-8.

[37] C.X. Tian, B.G. Zhang, A.G.L. Borthwick, W. Liu, Electrochemical oxidation of

PT
thallium (I) in groundwater by employing single-chamber microbial fuel cells as

RI
renewable power sources, Int. J. Hydrogen Energ. 42 (2017) 29454-29462.

SC
[38] Q. Lv, B.G. Zhang, X. Xing, Y.X. Zhao, R.Q. Cai, W. Wang, Q. Gu,

Biosynthesis of copper nanoparticles using Shewanella loihica PV-4 with

NU
antibacterial activity: Novel approach and mechanisms investigation, J. Hazard.
MA

Mater. 347 (2018) 141-149.

[39] H. Moon, I.S. Chang, B.H, Kim, Continuous electricity production from artificial
ED

wastewater using a mediator-less microbial fuel cell, Bioresour. Technol. 97

(2006) 621-627.
PT

[40] A. Xue, Z.Z. Shen, B. Zhao, H.Z. Zhao, Arsenite removal from aqueous solution
CE

by a microbial fuel cell-zerovalent iron hybrid procese, J. Hazard. Mater. 261

AC

(2013) 621-627.

[41] R.A. Rozendal, H.V. Hamelers, K. Rabaey, J. Keller, C.J. Buisman, Towards

practical implementation of bioelectrochemical wastewater treatment, Trends

Biotechnol. 26 (2008) 450-459.

[42] P. Li, Z.P. Liu, X.G. Wang, Y.D. Guo, L.H. Wang, Enhanced decolorization of

methyl orange in aqueous solution using iron-carbon micro-electrolysis activation

23
 ACCEPTED MANUSCRIPT

of sodium persulfate, Chemosphere 180 (2017) 100-107.

[43] M.L. Huang, C.F. Xu, Z. Wu, Y.F. Huang, J.M. Lin, J.H. Wu, Photocatalytic

discolorization of methyl orange solution by Pt modified TiO2, loaded on natural

zeolite, Dyes Pigments 77 (2008) 327-334.

[44] R.H. Liu, G.P. Sheng, M. Sun, G.L. Zang, W.W. Li, Enhanced reductive

PT
degradation of methyl orange in a microbial fuel cell through cathode

RI
modification with redox mediators, Appl. Microbiol. Biotechnol. 89 (2011)

SC
201-208.

[45] C.Y. Lai, C.H. Wu, C.T. Meng, C.W. Lin, Decolorization of azo dye and
NU
generation of electricity by microbial fuel cell with laccase-producing white-rot
MA

fungus on cathode, Appl. Energ. 188 (2017) 392-398.

[46] P.V. Nidheesh, R. Gandhimathi, N.S. Sanjini, NaHCO3, enhanced Rhodamine B

ED

removal from aqueous solution by graphite-graphite electro Fenton system, Sep.

Purif. Technol. 132 (2014) 568-576.

PT

[47] R.Q. Cai, B.G. Zhang, J.X. Shi, M. Li, Z. He, Rapid photocatalytic
CE

decolorization of methyl orange under visible light using VS4/carbon powder

AC

nanocomposites, ACS Sustain. Chem. Eng. 5 (2017) 7690-7699.

[48] A. Hájková, J. Barek, V. Vyskočil, Electrochemical DNA biosensor for detection

of DNA damage induced by hydroxyl radicals, Bioelectrochemistry 116 (2017)

1-9.

[49] Y. Wang, Y.W. Gao, L. Chen, H. Zhang, Goethite as an efficient heterogeneous

Fenton catalyst for the degradation of methyl orange, Catal. Today 252 (2015)

24
 ACCEPTED MANUSCRIPT

107-112.

[50] K. Cruzgonzález, O. Torreslópez, A. Garcíaleón, J.L. Guzmánmar, L.H. Reyes,

A. Hernández-Ramírez, Determination of optimum operating parameters for acid

yellow 36 decolorization by electro-fenton process using BDD cathode, Chem.

Eng. J. 160 (2010) 199-206.

PT
[51] X.Y. Yang, Y. Xue, W.N. Wang, Mechanism, kinetics and application studies on

RI
enhanced activated sludge by interior microelectrolysis, Bioresour. Technol. 100

SC
(2009) 649-653.

[52] K.R. Hargrave, Reactions of ferrous and ferric ions with hydrogen peroxide,
NU
Nature 163 (1951) 591-616.
MA

[53] Y.H. Lin, J. Yu, Z.P. Xing, X.L. Guo, X.J. Yu, B. Tang, J.L. Zou, Enhanced

generation of H2O2, and radicals on CO9S8 /partly-graphitized carbon cathode for

ED

degradation of bio-refractory organic wastewater, Electrochimica Acta, 213 (2016)

341-350.
PT

[54] L. Brunet, D.Y. Lyon, E.M. Hotze, P.J. Alvarez, M.R. Wiesner, Comparative
CE

photoactivity and antibacterial properties of C60 fullerenes and titanium dioxide

AC

nanoparticles, Environ. Sci. Technol. 43 (2009) 4355-4360.

[55] K.I. Ishibashi, A. Fujishima, T. Watanabe, K. Hashimoto, Detection of active

oxidative species in TiO2, photocatalysis using the fluorescence

technique, Electrochem. Commun. 2 (2000) 207-210.

[56] Y. Chen, A. Lu, Y. Li, L. Zhang, H.Y. Yip, H. Zhao, T. An, P.K. Wong,

Naturally occurring sphalerite as a novel cost-effective photocatalyst for bacterial

25
 ACCEPTED MANUSCRIPT

disinfection under visible light, Environ. Sci. Technol. 45 (2011) 5689-5695.

[57] J.H. Ramirez, F.J. Maldonado-Hódar, A.F. Pérez-Cadenas, V. Moreno-Castilla,

C.A. Costa, L.M. Madeira, Azo-dye orange Ⅱdegradation by heterogeneous

fenton-like reaction using carbon-fe catalysts, Appl. Catal. B-Environ. 75 (2007)

312-323.

PT
[58] J.X. Shi, B.G. Zhang, S. Liang, J.X. Li, Z.J. Wang, Simultaneous decolorization

RI
and desalination of dye wastewater through electrochemical process, Environ. Sci.

SC
Pollut. R. 25 (2018) 8455-8464.

[59] D.L. Gomathi, K.S. Girish, R.K. Mohan, C. Munikrishnappa, Photo degradation
NU
of methyl orange an azo dye by advanced fenton process using zero valent
MA

metallic iron: influence of various reaction parameters and its degradation

mechanism, J. Hazard. Mater. 164 (2009) 459-467.

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Schematic 1. Configuration of the proposed system as composed of a single chamber

MFC and an AER intensified by Fe-C micro-electrolysis.

Figure Captions

Fig. 1. Polarization and power density output of the MFC. The pink and green lines

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represent polarization curve and power density curve, respectively. The curves are

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obtained by measuring voltages at various external resistances (ranging from 10 to

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5000 Ω). NU
Fig. 2. Time history of decolorization of MO in the proposed system as well as in

control sets during a 180 min operation. Green and blue lines indicate the MO
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decolorization in AER intensified by Fe-C micro-electrolysis and without

intensification, respectively. Fe-C micro-electrolysis only (red line), electrolysis only

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by the bioelectricity from MFC (pink line) and aeration only (black line) for MO
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decolorization are also presented.

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Fig. 3. Effects of different operating factors on MO decolorization in the proposed

electrochemical system. (a) Fe-to-C ratio with MO concentration of 50 mg/L, aqueous

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pH of 3.0, aeration rate of 6.0 L/min; (b) aeration rate with MO concentration of 50

mg/L, aqueous pH of 3.0, Fe-to-C ratio of 1:1; (c) MO concentration with aqueous pH

of 3.0, aeration rate of 6.0 L/min, Fe-to-C ratio of 1:1; and (d) pH with MO

concentration of 50 mg/L, aeration rate of 6.0 L/min, Fe-to-C ratio of 1:1. The applied

voltage is fixed at 700 mV.

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Fig. 4. Concentrations of different Fe species and accumulations of TOS with time in

the proposed system during a 180 min operation. Green and blue lines imply the

changes of Fe3+ and Fe2+ concentrations, respectively. Variation of TOS concentration

is exhibited by the red line.

Fig. 5. Performance of MO decolorization with different scavengers in the proposed

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system during a 180 min operation. Green line represents the MO decolorization

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result without scavenger. Blue, red and pink lines illustrate MO decolorization with

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specific scavenger (Fe(II)-EDTA, isopropanol, TEMPOL) in turn. Black line indicates
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the color removal with the simultaneous addition of these three scavengers.

Fig. 6. UV-vis spectra evolutions with time in the proposed system during a 180 min
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operation. Initial condition: MO concentration of 50 mg/L, aqueous pH of 3.0,

aeration rate of 6.0 L/min, applied voltage of 700 mV, Fe-to-C ratio of 1:1.
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Table 1. Organic compounds in the original and processed solution of proposed

system after a 180 min operation.

Organic compounds Original sample Processed sample

7-Oxabicyclo[4.1.0] heptane √a -b

Pentanedioic acid, (2,4-di-t-butylphenyl) mono-ester √ -

Pentanoic acid, 5-hydroxy-, 2,4-di-t-butylphenyl esters √ -

3,5-bis(1,1-dimethylethyl)- Phenol √ -

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2-Cyclohexen-1-ol √ -

2-Cyclohexen-1-one √ -

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2,4-bis(1,1-dimethylethyl)- Phenol √ √

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5-Methyl-2-phenylindolizine - √

1H-Indole,1-methyl-2-phenyl- NU - √

3-Nitrophthalhydrazide - √

Indole-2-one,2,3-dihydro-N-hydroxy-4-methoxy - √
4-Hydroxyphenyl pyrrolidinyl thione - √
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Methyl(7-hydroxy-1H-benzimidazol-2-yl) carbamate - √

a
Detected in the sample.
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b
Not detected.
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Schematic 1. Configuration of the proposed system as composed of a single chamber

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MFC and an AER intensified by Fe-C micro-electrolysis.
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Fig. 1. Polarization and power density output of the MFC. The pink and green lines
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represent polarization curve and power density curve, respectively. The curves are

obtained by measuring voltages at various external resistances (ranging from 10 to

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5000 Ω).
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Fig. 2. Time history of decolorization of MO in the proposed system as well as in

control sets during a 180 min operation. Green and blue lines indicate the MO
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decolorization in AER intensified by Fe-C micro-electrolysis and without

intensification, respectively. Fe-C micro-electrolysis only (red line), electrolysis only

D

by the bioelectricity from MFC (pink line) and aeration only (black line) for MO
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decolorization are also presented.

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Fig. 3. Effects of different operating factors on MO decolorization in the proposed
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electrochemical system. (a) Fe-to-C ratio with MO concentration of 50 mg/L, aqueous

pH of 3.0, aeration rate of 6.0 L/min; (b) aeration rate with MO concentration of 50
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mg/L, aqueous pH of 3.0, Fe-to-C ratio of 1:1; (c) MO concentration with aqueous pH
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of 3.0, aeration rate of 6.0 L/min, Fe-to-C ratio of 1:1; and (d) pH with MO
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concentration of 50 mg/L, aeration rate of 6.0 L/min, Fe-to-C ratio of 1:1. The applied
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voltage is fixed at 700 mV.

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Fig. 4. Concentrations of different Fe species and accumulations of TOS with time in
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the proposed system during a 180 min operation. Green and blue lines imply the

changes of Fe3+ and Fe2+ concentrations, respectively. Variation of TOS concentration

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is exhibited by the red line.

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Fig. 5. Performance of MO decolorization with different scavengers in the proposed

system during a 180 min operation. Green line represents the MO decolorization
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result without scavenger. Blue, red and pink lines illustrate MO decolorization with

specific scavenger (Fe(II)-EDTA, isopropanol, TEMPOL) in turn. Black line indicates

D

the color removal with the simultaneous addition of these three scavengers.
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Fig. 6. UV-vis spectra evolutions with time in the proposed system during a 180 min
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operation. Initial condition: MO concentration of 50 mg/L, aqueous pH of 3.0,

aeration rate of 6.0 L/min, applied voltage of 700 mV, Fe-to-C ratio of 1:1.
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Highlights

 MFC powered electrochemical system was intensified by Fe-C micro-electrolysis.

 Decolorization of methyl orange (MO) was enhanced in this proposed system.
 Indirect oxidation with oxidizing substances played a key role in decolorization.
 MO was decomposed with generation of low molecular weight compounds.

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