comprehensive review and compilation of treatment for azo dyes using microbial fuel cells

8
Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells V. Murali 1 , Soon-An Ong 1* , Li-Ngee Ho 2 , Yee-Shian Wong 1 , Nasrul Hamidin 1 ABSTRACT: Microbial fuel cells (MFCs) represent an emerging technology that focuses on power generation and effluent treatment. This review compiles articles related to MFCs using azo dye as the substrate. The significance of the general components in MFCs and systems of MFCs treating azo dye is depicted in this review. In addition, degradation of azo dyes such as Congo red, methyl orange, active brilliant red X-3B, amaranth, reactive blue 221, and acid orange 7 in MFCs are summarized. Further exploration and operational modifica- tion are suggested to address the challenges of complete removal of azo dye with maximum power generation in an MFC. In addition, a sequential treatment system with MFCs is suggested for complete mineralization of azo dye. Water Environ. Res., 85, 270 (2013). KEYWORDS: microbial fuel cell, azo dye, decolorization, power generation, substrate. doi:10.2175/106143012X13503213812481 Introduction Microbial fuel cells (MFCs) represent the most recent technology to convert degradable organics into useful electrical energy. The main components of MFCs are electrodes, membranes, and substrate. In general, electrode materials exhibit characteristics such as good conduction, good chemical stability, high strength, and so on. Moreover, significant characteristics of the electrode are good biocompatibility and efficient electron transfer between the bacterial and electrode surface (Wei et al., 2011). A physical separator between the anode and cathode is called a membrane. The main function of the membrane is to transfer protons that have developed in the anode to the cathode. As an optional component, one significant problem in the absence of membrane is that when oxygen and substrate diffusion increases, it lowers the Coulombic efficiency and biocatalytic activity of the anode microorganisms (Hou et al., 2011a). Jang et al. (2004) conducted a study of membrane-less MFCs and witnessed a poor cathode reaction caused by a large quantity of oxygen to diffuse toward the anode. Substrate is an important factor that supports biological activities in the MFC. Acetate, glucose, lignocellulosic biomass, industrial wastewaters, and synthetic wastewaters are the main substrates used in MFCs in recent years (Pant et al., 2010). Several reviews of MFCs have been published in recent years, each with a different emphasis. Wang et al. (2010) discussed the advantages, characteristics, fabrication methods, and perfor- mances of microsized MFCs including milliliter and microliter scale. Lefebvre et al. (2011) debated the challenges of MFC technology in relation to energy self-sufficiency. Qian and Morse (2011) compiled the challenges and future prospects for miniaturized MFCs. Li et al. (2011) discussed the different types and recent advances in membranes in MFCs. Huang et al. (2011) amassed electron transfer mechanisms and performance of biocathode MFCs. Osman et al. (2011) studied recent develop- ments and challenges toward the microbial activities in MFCs. Oh et al. (2010) conferred about the various dominant microorganisms in different MFCs treating wastewaters and its ecology. Sharma and Kundu (2010) summarized the various biocatalysts or microorganisms used in both anodes and cathodes in MFCs. Pant et al. (2010) reviewed the different substrates and the power output achieved by these substrates in MFCs. Wei et al. (2011) summarized the performance and cost of the different materials used for electrodes in MFCs. Recently, efforts have been made to use the azo dye as substrate in MFCs for color removal and electricity generation. For color removal of azo dyes, much research has so far focused on biological studies. Among this research, Kim et al. (2008) conducted a study of color removal of azo dye using the anaerobic process. The authors used an anaerobic reactor with a mechanical stirrer. The result obtained was 94% color removal in 72 hours of retention time along with the consumption of 964 mg/L of glucose. Senthilkumar et al. (2011) conducted color removal from textile wastewater using a biphasic upflow anaerobic sludge blanket reactor along with sago wastewater as co-substrate; the authors reported that maximum color removal was 91.8% at 24 hours of hydraulic retention time (HRT). Dos Santos et al. (2007) reviewed the advantages and disadvantages of various color removal methods, more specif- ically, of biological treatment methods. In terms of the trend of treating azo dyes using biological methods, a recent upgradation is treating azo dye using MFCs. Simultaneous power generation and color removal can be achieved in this biochemical process. This article presents a review of azo dye treatment using MFCs. Microbial Fuel Cell System Using Azo Dye as Substrate Dimensions and materials for electrodes and membranes differ from one another in a MFC system using azo dye as substrate. The various materials used as electrodes and membranes are summarized in Table 1. Li et al. (2008) conducted anaerobic and aerobic systems of treatment for azo dyes using two-chambered MFCs. In this study, the authors 1* School of Environmental Engineering, University of Malaysia, Perlis, 02600, Arau, Perlis, Malaysia; e-mail: [email protected] 2 School of Materials Engineering, University of Malaysia, Perlis; Arau, Perlis, Malaysia 270 Water Environment Research, Volume 85, Number 3

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Page 1: Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells

Comprehensive Review and Compilation ofTreatment for Azo Dyes Using Microbial Fuel Cells

V. Murali1, Soon-An Ong1*, Li-Ngee Ho2, Yee-Shian Wong1, Nasrul Hamidin1

ABSTRACT: Microbial fuel cells (MFCs) represent an emerging

technology that focuses on power generation and effluent treatment.

This review compiles articles related to MFCs using azo dye as the

substrate. The significance of the general components in MFCs and

systems of MFCs treating azo dye is depicted in this review. In addition,

degradation of azo dyes such as Congo red, methyl orange, active

brilliant red X-3B, amaranth, reactive blue 221, and acid orange 7 in

MFCs are summarized. Further exploration and operational modifica-

tion are suggested to address the challenges of complete removal of azo

dye with maximum power generation in an MFC. In addition, a

sequential treatment system with MFCs is suggested for complete

mineralization of azo dye. Water Environ. Res., 85, 270 (2013).

KEYWORDS: microbial fuel cell, azo dye, decolorization, power

generation, substrate.

doi:10.2175/106143012X13503213812481

IntroductionMicrobial fuel cells (MFCs) represent the most recent

technology to convert degradable organics into useful electrical

energy. The main components of MFCs are electrodes,

membranes, and substrate. In general, electrode materials

exhibit characteristics such as good conduction, good chemical

stability, high strength, and so on. Moreover, significant

characteristics of the electrode are good biocompatibility and

efficient electron transfer between the bacterial and electrode

surface (Wei et al., 2011).

A physical separator between the anode and cathode is called

a membrane. The main function of the membrane is to transfer

protons that have developed in the anode to the cathode. As an

optional component, one significant problem in the absence of

membrane is that when oxygen and substrate diffusion

increases, it lowers the Coulombic efficiency and biocatalytic

activity of the anode microorganisms (Hou et al., 2011a). Jang et

al. (2004) conducted a study of membrane-less MFCs and

witnessed a poor cathode reaction caused by a large quantity of

oxygen to diffuse toward the anode.

Substrate is an important factor that supports biological

activities in the MFC. Acetate, glucose, lignocellulosic biomass,

industrial wastewaters, and synthetic wastewaters are the main

substrates used in MFCs in recent years (Pant et al., 2010).

Several reviews of MFCs have been published in recent years,

each with a different emphasis. Wang et al. (2010) discussed the

advantages, characteristics, fabrication methods, and perfor-

mances of microsized MFCs including milliliter and microliter

scale. Lefebvre et al. (2011) debated the challenges of MFC

technology in relation to energy self-sufficiency. Qian and Morse

(2011) compiled the challenges and future prospects for

miniaturized MFCs. Li et al. (2011) discussed the different types

and recent advances in membranes in MFCs. Huang et al. (2011)

amassed electron transfer mechanisms and performance of

biocathode MFCs. Osman et al. (2011) studied recent develop-

ments and challenges toward the microbial activities in MFCs.

Oh et al. (2010) conferred about the various dominant

microorganisms in different MFCs treating wastewaters and its

ecology. Sharma and Kundu (2010) summarized the various

biocatalysts or microorganisms used in both anodes and

cathodes in MFCs. Pant et al. (2010) reviewed the different

substrates and the power output achieved by these substrates in

MFCs. Wei et al. (2011) summarized the performance and cost

of the different materials used for electrodes in MFCs.

Recently, efforts have been made to use the azo dye as

substrate in MFCs for color removal and electricity generation.

For color removal of azo dyes, much research has so far focused

on biological studies. Among this research, Kim et al. (2008)

conducted a study of color removal of azo dye using the

anaerobic process. The authors used an anaerobic reactor with a

mechanical stirrer. The result obtained was 94% color removal in

72 hours of retention time along with the consumption of 964

mg/L of glucose. Senthilkumar et al. (2011) conducted color

removal from textile wastewater using a biphasic upflow

anaerobic sludge blanket reactor along with sago wastewater

as co-substrate; the authors reported that maximum color

removal was 91.8% at 24 hours of hydraulic retention time

(HRT). Dos Santos et al. (2007) reviewed the advantages and

disadvantages of various color removal methods, more specif-

ically, of biological treatment methods. In terms of the trend of

treating azo dyes using biological methods, a recent upgradation

is treating azo dye using MFCs. Simultaneous power generation

and color removal can be achieved in this biochemical process.

This article presents a review of azo dye treatment using MFCs.

Microbial Fuel Cell System Using Azo Dye as SubstrateDimensions and materials for electrodes and membranes

differ from one another in a MFC system using azo dye as

substrate. The various materials used as electrodes and

membranes are summarized in Table 1. Li et al. (2008)

conducted anaerobic and aerobic systems of treatment for azo

dyes using two-chambered MFCs. In this study, the authors

1* School of Environmental Engineering, University of Malaysia,Perlis, 02600, Arau, Perlis, Malaysia; e-mail: [email protected] School of Materials Engineering, University of Malaysia, Perlis;Arau, Perlis, Malaysia

270 Water Environment Research, Volume 85, Number 3

Page 2: Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells

conducted two different MFCs with different electrodes. In the

first reactor, the electrodes were carbon felt in both the anode

and cathode. The second reactor was fixed with carbon felt in

the anode and graphite granule in the cathode. In both reactors,

known concentrations of glucose with anaerobic and aerobic

sludge were inoculated in the anode and cathode, respectively.

After the initial run, Congo red was introduced to the anode and

the treated effluent transferred to the cathode to remove

aromatic amines generated from azo dye reduction. The study

suggested that the second reactor with different electrodes was

more efficient compared to the first reactor. Moreover, the study

was conducted with different concentrations of glucose and

different HRT. The authors observed that the maximum power

density obtained at 1000 mg/L of glucose concentration and the

optimized HRT for electricity production was 14.8 hours.

Ding et al. (2010) conducted a study based on azo dye removal

using two-chambered MFCs with rutile cathode. The anodic

electrode was an unpolished graphite electrode and the cathode

was a polished graphite electrode. A cation exchange membrane

was used as a separator. Another set of experiments was

conducted by replacing the polished graphite electrode with the

rutile cathode. Rutile cathode is a semiconductor mineral

(TiO2)-coated cathode. During startup, the anodic chamber of

the MFC was inoculated with the anaerobic sludge. The cathodic

chamber was initially filled with electrolyte and then replaced

with methyl orange before monitoring started. Visible light

responsiveness was selected as the cathodic catalyst. Rutile

electrode irradiated by visible light shows maximum power

generation and color removal.

Fu et al. (2010) investigated the combination of the two-

chambered MFC and Fenton system using amaranth as the

substrate. Granular graphite and spectrographic pure graphite

were used as the anode and cathode electrodes. The separator

between the anode and the cathode was the proton exchange

membrane. Two types of experiments were conducted: one was a

conventional Fenton system with MFC and the other was an

electrochemical Fenton system with the MFC. In the conven-

tional system, after the production of hydrogen peroxide caused

Table 1—Electrodes, membranes, and performance of MFCs.

Type of MFC Anode material Cathode material Type of membrane

Two-chamber Carbon felt R1, carbon felt; R2, graphite granule PEM

Two-chamber Unpolished Graphite electrode Rutile cathode electrode andgraphite electrode

Cation exchange membrane

Two-chamber Granular graphite Spectrographic pure graphite PEM

Two-chamber Porous carbon papers (withoutwaterproofing)

Porous carbon papers (withoutwaterproofing)

PEM

Two-chamber Graphite bars Graphite bars PEMTwo-chamber Granular activated carbon packed in

a cylindrical stainless cage meshused as anode. A graphite rodwas inserted in the anode.

Granular activated carbon packed ina cylindrical stainless cage meshused as electrode. A graphite rodwas inserted in the cathode.

The bottles are joined by a glassbridge containing a glass wool(Pyrex; Corning Incorporated,Corning, New York)

Two- chamber Carbon felt Carbon felt Cation exchange membrane

Two-chamber Activated carbon fiber withelectrochemical active bacteria

Carbon paper (4 3 4 cm2; TorayIndustries, Inc., Tokyo, Japan) orthionine-modified carbon paper

PEM (Nafion 117; DuPont,Wilmington, Delaware)

Single- chamberair cathode

Porous carbon papers projectedsurface area of 6x 6 cm2

Air cathode consisted of a catalystlayer (containing 0.5 mg /cm2 ofPt) on the water-facing side and aPTFE diffusion layer on the air-facing side

MFM (0.22 lm in pore size) wasapplied directly onto thewater-facing side of thecathode.

Single-chamberair cathode

Non-wet proofing carbon papers Cathode was prepared by coating0.5 mg cm2 of Pt on a wetproofing carbon paper

MFM (0.22 lm in pore size)

Single- chamberair cathode

Non-wet proofed porous carbonpapers (no catalyst) with aprojected surface area of 3 3 3cm on one side

Dim similar to anode prepared bycoating 0.5 mg/cm2 of Pt on wet-proofed porous carbon papers

MFM, PEM, UFM-1K,UFM-5K,UFM-10K

Single-chamberair cathode

Plain porous carbon papers (3 3 3cm, without wet proofing orcatalyst)

Coating 0.5 mg/cm2 of Pt on 3 3 3-cm wet-proofed porous carbonpaper

MFM (0.22 lm in pore size)

Single-chamberair cathode

25 g granular graphite with agraphite rod (8 mm in diameter)

Carbon paper Catalyst layer (containing 0.5mg/cm2 of Pt)

Murali et al.

March 2013 271

Page 3: Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells

by the neutral catholyte, the dye effluent transferred to the

Fenton reaction. In the electrochemical Fenton system, Fe3þwas

introduced as a catalyst inside the cathode after the production

of hydrogen peroxide. Based on the results of the experiment,

power production was higher in the electrochemical Fenton

system (28.3 W/m3) than the conventional Fenton system (11.1

W/m3). Amaranth dye removal efficiency was higher in the

conventional Fenton system (82.59%) than the electrochemical

Fenton system (76.43%).

Sun et al. (2011a) used porous carbon papers as the electrodes

in both the anode and cathode. A proton exchange membrane

was used as a separator in this two-chambered MFC. Aerobic

biocathode and anaerobic anode MFC was used with active

brilliant red X-3B as substrate. The maximum power density

obtained was 50.74 mW/m2 and 81.56% of the color was

removed from the source.

In a study by Bakhshian et al. (2011), graphite bars were used

as electrodes and proton exchange membrane as separator.

Experiments performed with molasses as the energy source in

the anaerobic anode and commercial laccase with phosphate

buffer and reactive blue 221 were added in the cathode of the

two-chambered MFC. Color removal and chemical oxygen

demand (COD) reduction from molasses were monitored. After

the addition of molasses, the maximum voltage observed was

305 mV; it was stable for 30 hours. A color removal rate of 87%

was achieved in the cathode chamber and 84% COD removal

was observed in the anode chamber.

Granular activated carbon was packed in a cylindrical stainless

steel mesh cage and a graphite rod was inserted. This

combination was used as an electrode, and glass wool was used

as a membrane in a two-chambered MFC used by Kalathil et al.

(2011). The experiment was conducted using real dye wastewa-

ter on both the anode and cathode. The high power density

observed was 1.7 W/m3. Color removal was 73% in the anode

and 77% in the cathode at a duration of 48 hours.

Liu et al. (2009) used carbon felt as an electrode and cation

exchange membrane as a separator for a two-chambered MFC.

Glucose was added to the anode chamber and catholyte

Table 1—Extended.

Dye used Color removal Electricity generated References

Congo red 69.3 to 92.7% at a glucose concentration of4000 mg/L

387 mW/m2 at a glucose concentration of1000 mg/L

Li et al., 2008

Methyl orange Graphite electrode, 37.8%; Rutile cathodeelectrode, 47.4%; rutile cathode electrodeirradiated by visible light, 73.4%;disconnected circuit, 17.8%; connectedcircuit, 73.4%

Highest current density obtained in theirradiated rutile cathode electrode

Ding et al., 2010

Amaranth Conventional Fenton system, 82.59%,electrochemical Fenton system, 76.43%

Electrochemical Fenton system, maximumpower density of 28.3 W/m3; conventionalFenton system, 11.1 W/m3

Fu et al., 2010

Active brilliant red X-3B 81.56% In 38 days, 0.35V (R 500X); maximumpower, 50.74 mW/m2

Sun et al., 2011a

Reactive blue 221 83% 305 mV Bakhshian et al., 2011Real wastewater Anode 73% at 48 hours, cathode 77% at 48

hoursHigh power density 1.7 W/m3 Kalathil et al., 2011

Orange I, acid orange 7,and methyl orange

Nearly 99% 250 6 15 mV Liu et al., 2009

Methyl orange 99% 1.4 mW/m2 Liu et al., 2011

Active brilliant red X-3B MFC (48 hours), 100%; anaerobic reactor,80.1%

Glucose produced the highest powerdensity, followed by sucrose and dilutedconfectionery wastewater. The lowestpower density was observed in theacetate-fed MFC.

Sun et al., 2009

Congo red Congo red decolorization resulted in a largechange in the oxidation peak position ofthe bioanode.

Addition of Congo red did not result in anynoticeable decrease in the peak catalyticcurrent until a Congo red concentrationup to 900 mg/L.

Sun et al., 2011b

Congo red UFM-10K ¼ 4.77 mg/L�h; MFM ¼ 3.61 mg/L�h; UFM-5K ¼ 2.38 mg/L�h; UFM-1K ¼2.02 mg/L�h; PEM ¼ 1.72 mg/L�h

Highest power UFM-1K ¼ 324 mW/m2 Hou et al., 2011b

Congo red More than 90% decolorization at a dyeconcentration of 300 mg/L was achievedwithin 170 hours.

MFCs simultaneously ¼ 192 mW/m2; MFCssequentially ¼ 110 mW/m2

Hou et al., 2011a

Acid orange 7 Degradation (97%) was achieved after 168hours of operation.

Power density obtained was 5.0 W/m3 Zhang and Zhu, 2011

Murali et al.

272 Water Environment Research, Volume 85, Number 3

Page 4: Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells

containing azo dyes was added to the cathode chamber. Azo dyes

used in this investigation were orange I, acid orange 7, and

methyl orange. The MFC produced a relatively stable voltage of

250 6 15 mV for about 2.7 hours and, beyond this period, a

sharp drop in voltage was noticed. Three dyes were completely

reduced to amines in the cathode.

Liu et al. (2011) used an activated carbon fiber with

electrochemical active bacteria as the anode electrode, carbon

paper as the cathode electrode, and the proton exchange

membrane as a separator in a two-chambered MFC. Phosphate

buffer containing methyl orange was filled in the cathode and

autoclaved medium and methyl orange was filled in the anode.

Higher color removal efficiency (99%) was obtained in the

cathode chamber than the anode chamber. Maximum power

density was determined as 1.4 mW/m2.

The single chamber air cathode consisted of a catalyst layer

(containing 0.5 mg/cm2 of Pt) on the water-facing side and a

polytetrafluoroethylene (PTFE) diffusion layer on the air-facing

side. The anode electrode was porous carbon paper and

microfiltration was applied directly onto the water-facing side

of the cathode in a MFC used by Sun et al. (2009). In addition to

active brilliant red X-3B (ABRX3), glucose, acetate, sucrose, and

confectionery wastewater with an initial concentration of 500

mg/L COD were used in co-metabolism. The following series of

experiments were conducted: (a) comparison of the color

removal performance of MFC, autoclaved sludge containing

MFC, and the anaerobic batch reactor; (b) the MFC was further

tested at different dye concentrations and with different external

resistance; (c) suspended solids were removed from the anodic

chamber of the MFC at the end of one batch test for evaluation

of suspended solids contribution to dye decolorization and

electricity generation; and (d) 300 mg/L of ABRX3 was added to

three individual MFCs along with different organic carbon

sources like acetate, sucrose, and confectionery wastewater,

respectively, to investigate the effect of the organic carbon

source on dye decolorization and electricity generation in the

MFC. Glucose produced the highest power density, followed by

sucrose, diluted confectionery wastewater, and acetate-fed MFC.

Color removal obtained in the anaerobic reactor was 80.1% and

anaerobic autoclaved sludge MFC was 11.2%. Dye concentra-

tions of 300 mg/L and 600 mg/L obtained 100% color removal

compared to other concentrations. Among the organic carbon

sources used, maximum color removal was obtained in glucose

and the minimum was obtained in acetate.

Sun et al. (2011b) used the air cathode single chamber with

non-wet proofing carbon papers as the anode; the cathode was

prepared by coating 0.5 mg/cm2 of Pt on a wet proofing carbon

paper. A microfiltration membrane was used as the separator

and Congo red was used in the bioanode. Results show that

Congo red did not affect the peak catalytic current up to 900

mg/L among the various concentrations.

Hou et al. (2011a) investigated different separators used in a

single-air-cathode MFC. Non-wet-proofed porous carbon paper

was used for the anode electrode and a coating of 0.5 mg/cm2 of

Pt on wet-proofed porous carbon papers was used in the

cathode. Experiments were conducted to assess the performance

of color removal and power generation using the following

different membranes: microfiltration membrane (MFM), proton

exchange membrane (PEM), and ultrafiltration membranes

(UFMs) with different molecular cutoff weights of 1 K (UFM-

1K), 5 K (UFM-5K), and 10 K (UFM-10K). Results showed that

the MFC with an UFM-1K produced the highest power density

of 324 mW/m2. The MFC with UFM-10K achieved the fastest

decolorization rate for Congo red. Hou et al. (2011b) also

published another paper using the same MFC setup. Two

different experiments were conducted with glucose and Congo

red in which glucose and Congo red were added to the MFCs

sequentially (EP1) or simultaneously (EP2) and were tested.

Results showed that the experimental procedures had a

negligible effect on color removal. Both the test achieved more

than 90% color removal at dye concentration of 300 mg/L within

170 h. Maximum power production obtained in EP2 and EP1

was 192 mW/m2 and 110 mW/m2, respectively.

Zhang and Zhu (2011) conducted a study in a single-

chambered air cathode MFC using 25 g of granular graphite

with a graphite rod as the anode and carbon paper as the

cathode. A catalyst layer containing 0.5 mg/cm2 of Pt was used

as the separator. The maximum power density obtained was 5.0

W/m3 for single-chamber MFCs using glucose with acid orange

7. Nearly complete color removal (97%) was achieved after 168

hours.

The aforementioned research was conducted using two- or

single-chambered MFCs. They differentiated with each other in

dimensions and type of materials used as electrodes and

separators. Each study targeted color removal of various azo

dyes and simultaneous energy recovery.

Azo Dye Removal in Microbial Fuel CellsCongo red, methyl orange, amaranth, active brilliant red X-

3B, reactive blue 221, orange I, and acid orange 7 were the azo

dyes used in MFC treatment. This section reviews the general

degradation of azo dye and degradation using MFC. Table 2

shows the chemical structures of these azo dyes.

Congo Red. Congo red is a diazo dye with two numbers of

sulfoante groups that ensure high aqueous solubility (Dos Santos

et al., 2007). Gopinath et al. (2009) studied biological

degradation of Congo red using Bacillus sp. This mutated

Bacillus sp. was more effective at the degradation of Congo red

compared to the wild species. Telke et al. (2009) also studied the

biological degradation of congo red using bacterium Pseudomo-

nas sp. Namasivayam and Arasi (1997) conducted an adsorption

study for the removal of Congo red. Waste red mud, an

industrial byproduct, generated during the processing of bauxite

ore was recycled for the adsorption of Congo red from aqueous

solution. Somasekhara Reddy et al. (2011) also conducted a

study of the removal of Congo red using physical adsorbent.

Indian Jujuba seeds were used as adsorbent in this study and

results show that the maximum adsorption capacity was 55.56

mg/g.

Li and Jia (2008) studied color removal of Congo red dye

using two systems: decolorization by Schizophyllum sp. and

biosorption by rice hull. Sansiviero et al. (2011) investigated

photodegradation of Congo red using various layers of thin TiO2

films. Isik and Sponza (2005) studied decolorization of Congo

red through an upflow anaerobic sludge blanket (UASB) reactor.

Reactor performance in terms of color, COD, and total aromatic

amine (TAA) removal was evaluated. Results of the experiment

show that 58% COD, 100% color, and 39% TAA removal

efficiencies were obtained in a 100 mg/L COD concentration

with glucose as co-substrate, while 25% COD, 99% color, and

40% TAA removal efficiencies were observed in a 100 mg/L

COD concentration without co-substrate. These aforementioned

Murali et al.

March 2013 273

Page 5: Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells

Table 2—Dyes and their structure (dye structure drawn using ChemSketch software).

Dye Structure

Congo red

Methyl orange

Amaranth

Active brilliant red X-3B

Reactive blue 221

Acid orange 7

Orange I

Murali et al.

274 Water Environment Research, Volume 85, Number 3

Page 6: Comprehensive Review and Compilation of Treatment for Azo Dyes Using Microbial Fuel Cells

studies and articles are examples of degradation of Congo red

using different methods.

In the studies and articles reviewed in this paper, most MFCs

used Congo red as a substrate. Li et al. (2008) investigated the

removal of azo dye in both the anode and cathode for anaerobic

and aerobic treatment. By using two-chambered MFCs, the azo

bond cleaved under the anaerobic anode chamber and aerobic

cathode chamber. The aromatic amine was removed from the

aerobic cathode chamber. Hou et al. (2011a) used a single-

chamber air cathode MFC to investigate the interception of

Congo red dye decolorization on power generation. The results

showed that Congo red decolorization did not have exhibit a

noticeable decrease in peak catalytic current until concentra-

tions of dye up to 900 mg/L. Hou et al. (2011b) used different

single-chamber air cathodes to assess the performance of

various membranes for removing Congo red. The authors

observed the following points in their research: the diffusion

coefficient of oxygen and diffusion coefficient of substrate were

two important factors needed to consider the performance of

different membranes for the color removal of azo dye; if the

diffusion coefficient of oxygen is high, it affects the anaerobic

condition of the anode chamber; because the diffusion

coefficient of oxygen transfers oxygen from the cathode to the

anode, this may not be a favorable condition for decolorization

in the anode chamber; and, if the diffusion coefficient substrate

is high, it supports decolorization resulting in a lower internal

resistance, which may increase the substrate conversion rate.

Results obtained with respect to these factors show that UFMs

with molecular cutoff weights of 10 K (UFM-10K) could be the

most suitable membranes in terms of Congo red decolorization.

The same authors (Hou et al., 2011b) conducted experiments

using an MFM as a separator in a single-chamber air cathode

MFC for Congo red decolorization. Microbial species that were

responsible for the decolorization of Congo red in MFCs were

identified.

Methyl Orange. Methyl orange belongs to the mono azo dye

group. Most of the studies on degradation of methyl orange were

based on the photocatalyst method. Chen et al. (2006) studied

the degradation of methyl orange by the photocatalyst method

using pelagite as the source material; pelagite is the ore of

manganese obtained from deep-sea beds. Jiang et al. (2011) used

monoclinic bismuth vanadate, a metallic element, as a

photacatalyst. Lin et al. (2008) used bi-based photocatalyst

Bi3SbO7 for the degradation of methyl orange. Guettai and Ait

Amar (2005) used titanium oxide as a photocatalyst for the

degradation of methyl orange. Activated carbon, nanosized

cadmium sulfide, and chitosan composite were used for

adsorption of methyl orange and visible light photocatalyst as

used for the removal of methyl orange. Chitosan is a substance

derived from the chitin of crab and other crustaceans (Jiang et

al., 2010). Decolorization of methyl orange using two-cham-

bered MFCs along with the photocatalytical effect was studied

by Ding et al. (2010). In this study, electrons from the anode

were transferred to the cathode, which contained methyl orange

as the electron acceptor. The conduction band potential of rutile

material used as the electrode was much more negative than

methyl orange; rather, it was favorable to the reduction of methyl

orange. Liu et al. (2011) conducted a study using two-chambered

MFCs. In the aerobic cathode chamber, 90% of the methyl

orange decolorized in 2 days, increasing to 99% in 4 days. In an

anaerobic anode, methyl orange remains as it. Liu et al. (2009)

used three different azo dyes (methyl orange, orange I, and

orange II) in a two-chambered MFC. Experiments were

conducted with each dye in cathode chambers. The final

products obtained after the reduction of these dyes were

identified in their study.

Active Brilliant Red X-3B. Active brilliant Red X-3B also

belongs to the mono azo dye group. The articles cited herein are

about the removal of active brilliant red X-3B using different

methods. Tao et al. (2010) conducted a study on photocatalytic

degradation of active brilliant red X-3B using a composite

material of titanium doped molecular sieves. Decomposition of

Fe (IV) results in a composite ferrate solution that was used for

the degradation of active brilliant red X-3B by Xu et al. (2009).

Dong et al. (2007) conducted a study on the removal of active

brilliant red X-3B using catalytic ozonation. Sun et al. (2009)

used a single-chamber air cathode MFC for the removal of

Active brilliant red X-3B. Bioadsorption and biodegradation are

reasons for color removal in biological systems. In this study,

biodegradation was the cause of color removal. Anaerobic

biodegradation is intercepted by aniline and sulfonated aromatic

amines. Sun et al. (2011a) conducted a study of the removal of

active brilliant red X-3B in a biocathode using a two-chambered

MFC. The authors reported that dissolved oxygen plays an

important role in the complete removal of this azo dye.

Amaranth. Amaranth is a mono azo dye with high aqueous

solubility. A recent study of the degradation of amaranth dye was

conducted by Chan et al. (2012). Inoculating specified micro-

organisms with amaranth dye in microaerophilic condition and

consecutive aerobic biodegradation. Fu et al. (2010) investigated

a double-chambered MFC for the removal of this mono azo dye.

In this study, the Fenton system was accompanied by MFC for

color removal. Degradation of this azo dye was carried out by

hydroxyl radicals in two steps. In the first step, cleavage of the

azo bond to form aromatic ring molecules by hydroxyl radicals

and the aromatic ring was broken by the oxidative ring opening

reaction. In the second step, carboxylic acid formed in the

previous step was oxidized by hydroxyl radicals produced in the

Fenton reaction. Fu et al. (2010) determined a maximum

amaranth removal of 82.59% and a power density of 28.3 W/m3.

Reactive Blue 221. Alkan et al. (2005) studied the adsorption

reactive blue 221 using sepiolite mineral and reported that the

adsorption was high with respect to ionic strength and

temperature. The optimum calcination temperature of this

mineral for the highest adsorption capacity was 200 8C. Another

adsorption study was conducted by Karaoglu et al. (2010) for

Reactive Blue 221 using kaolinite. Bakhshian et al. (2011)

conducted a biocathode study in a two-chambered MFC

performing enzymatic decolorization using commercial laccase

without any mediators. Laccase acts as a catalyst for oxygen

reduction in color removal and achieved 87% decolorization.

The article reported that power density increased up to 30%

using enzymatic decolorization.

Acid Orange 7. Elias et al. (2012) used the titanium doped

molecular sieves for the photodegradation of acid orange 7. Hu

et al. (2011) investigated another photodegradation using Cu2O/

CeO2 under visible light irradiation. Konsowa et al. (2011) used

the aerobic bioreactor for the degradation of this azo dye. The

experimental setup consisted of a bioreactor with air diffuser

and submerged microfiltration. Yang et al. (2010) conducted

oxidation using persulfate and granular activated carbon as the

catalysts for degradation of acid orange 7. Chou et al. (2011)

Murali et al.

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conducted electrooxidation for the removal of this mono azo

dye. Zhang and Zhu (2011) used a single-chamber air cathode

MFC for the removal of acid orange 7. This study concludes that

the single-chamber MFC was more advantageous compared to

the two-chamber MFC for color removal of acid orange 7. This

could be attributed to the fact that the electrons generated in the

anode transferred to acid orange 7 easily in the single chamber.

ConclusionsAvailable literature shows that researchers are targeted to

treat the azo dye with simultaneous power generation. The

anaerobic and aerobic biological methods may be appropriate

for the treatment of azo dye containing wastewaters (Pandey et

al., 2007). Anaerobic and aerobic environment is available in a

two-chambered MFC, which can be used for the complete

mineralization of azo dye. Reduction of azo bond in the azo dye

may be performed in the anaerobic chamber (anode) and the

degradation of aromatic amine may be carried out in the aerobic

chamber (cathode). Some specific articles focused towards bio-

cathode MFC and the challenges need to overcome is lower

power production of bio-cathode MFC comparatively chemi-

cally catalyzed cathode. In a single chamber MFC sequential

with aerobic treatment may perform the complete mineraliza-

tion of the azo dye.

In this review, it is difficult to compare with each other. The

reason behind this is, all the articles differentiate to each other in

the type of materials used for the electrodes and membrane, co-

substrate and the substrate used. The substrate used in each

MFC may come under the major classification of azo dye. A

further exploration are needed to focus about the MFC using

azo dye reduction using same type of MFC in dimension and

materials along with the same co-substrate for the different azo

dyes as substrate is hopeful to address the challenges in the azo

dye reduction MFC along with maximum power generation.

AcknowledgmentsThis research work was funded by the Fundamental Research

Grand Scheme provided by the Ministry of Higher Education

Malaysia. The authors would like to thank them for their

support.

Submitted for publication February 18, 2012; accepted for

publication July 26, 2012.

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