Biomass and Bioenergy 149 (2021) 106082

Contents lists available at ScienceDirect

Biomass and Bioenergy

journal homepage: http://www.elsevier.com/locate/biombioe

Microbial fuel cell for harvesting bio-energy from tannery effluent using
metal mixed biochar electrodes
M. Naveenkumar, K. Senthilkumar *
Department of Chemical Engineering, Kongu Engineering College, Erode, 638060, Tamil Nadu, India

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

Keywords: The present study aims on the ways and means of reducing the cost of electrodes and decreasing environment
Microbial fuel cell pollution using waste materials. For example, Coconut Shell (CS) materials were used for synthesizing electrodes
Wastewater through carbonization and testing it as the anode in the Microbial Fuel Cell (MFC) utilizing tannery effluent. The
Electrode
electrodes were synthesized by using activated coconut shell wastes blended with various metals such as Silicon
Coconut shell carbon
Metals
(Si0.2), Zinc (Zn0.2), and Copper (Cu0.2) with 20%. The specific surface area of CS-Si0.2 (0.1825 m2 g− 1), CS-Zn0.2
Microorganism (0.1900 m2 g− 1), and CS-Cu0.2 (0.2162 m2 g− 1) is greater than Graphite Particle (GP) (0.1890 m2 g− 1). Power
output of electrodes were CS-Si0.2 ((16.8 ± 0.5) mW m− 2), CS-Zn0.2 ((22.96 ± 0.6) mW m− 2), and CS-Cu0.2
((38.72 ± 0.5) mW m− 2) similar to GP ((30.42 ± 0.5) mW m− 2). Our outcomes exhibit that the activated coconut
shell with CS-Cu0.2 metal electrode gives the maximum power output. Therefore, CS-Cu0.2 electrodes are pro­
gressively viable, have greater biocompatibility, effective and adaptable for application in the microbial fuel cell.
Among these three proposed electrodes, CS-Cu0.2 electrode has a huge potential for maximum performance and
developing a cost-effective sustainable MFC.

1. Introduction
MFC convert the chemical energy contained in organic matter into
electrical energy with the help of microorganisms. MFC incorporates
anode and a cathode coupled with an external electrical circuit, divided
by membrane. The anode part is an anaerobic section as oxygen should
be far from the anode face, which will function as the terminal electron
acceptor for organisms associated with the MFC [1]. The cathode part is
an aerobic section. An electrochemical reaction of oxygen reduction and
other molecules associated with wastewater occurs at the cathode of
MFC [2]. In anode part, the substrate is oxidized by a monoculture
bio-film or bacterial microorganism, releasing generated electrons and
protons. The degraded organic matters are reproduced as electrons by
the metabolic activity of microorganisms [3]. During biological treat­
ment process metabolites are produced in the form of extracellular
polymeric substances (EPS) and soluble microbial products (SMP) and
they cause biofouling. NAS communities are used to reduce the
biofouling in reactor by enriched nitrifying bacteria which is existing in
activated sludge. The less fouling in NAS community accredited to small
amount production of SMP and EPS with the help of nitrifying bacteria
[4,5]. The generated electrons are passed through outside circuit to
cathode electrode and protons are passed through membrane from
anode part to cathode part to form water. In the cathode part, cathode
catalyst or catholyte solution must be used to facilitate this reaction
which yields the byproducts of small amounts of carbon dioxide, from
the breakdown of the organic content and little amount of water at the
cathode [6]. The active parts of MFC might be included in simple designs
and cost-effective materials will offer more perspective for harnessing
the energy from wastewater. However, some of the drawbacks of mi­
crobial fuel cells are high internal resistance, current instability, low
electricity production and usage of expensive materials. These are the
major practical barriers for implementing a commercial scale MFC. For
example, some of previous investigations concluded that cost of MFC is
significantly dependent on electrode materials [7,8].
The electrode material possesses one of the unique performances in
MFC for electrochemical efficiency and improving the electron transfer
[9,10]. Besides, a good electrode material should include greater
biocompatibility, high stability and durability, good electrical conduc­
tivity, specific surface area, porosity, cost-effective and ease of access
[11]. In MFC, the majority of electrode materials in commercial-scale
systems are made by employing Activated Carbon (AC) and Graphite
Particle (GP) as both materials have high conductivity, greater catalytic

* Corresponding author.
E-mail addresses: er.naveenmanick@gmail.com (M. Naveenkumar), senthilkumar.chem@kongu.ac.in (K. Senthilkumar).

https://doi.org/10.1016/j.biombioe.2021.106082
Received 19 December 2020; Received in revised form 12 March 2021; Accepted 18 April 2021
Available online 26 April 2021
0961-9534/© 2021 Elsevier Ltd. All rights reserved.
M. Naveenkumar and K. Senthilkumar Biomass and Bioenergy 149 (2021) 106082

activities even with low internal surface area [12]. The cost of these Table 1
materials will vary significantly from 15,000 to 30,000 INR kg− 1. The Physical and electrochemical properties of the four-carbon anode electrodes.
cost depends upon manufacturing products and feedstock options. The Anode Particle size Surface area Pore size Specific
industrial methods of extraction of feedstock and productions of AC and materials (mm3) (m2 g− 1) (nm) capacitance (F g− 1)
GP are energy rigorous and result in the discharge of contaminants such CS-Si0.2 55–70 0.1825 1.8 115.26
as carbon monoxide, carbon di oxide and other pollutants to the CS-Zn0.2 55–70 0.1900 2.5 102.35
environment. CS-Cu0.2 55–70 0.2162 2.9 132.41
Inventing a sustainable and environment-friendly electrode is one of GP 30–50 0.1890 2.6 125.72

the most significant components in MFC and it is prepared by using

environmental waste materials. These waste materials are decomposed
by combustion methods like thermal treatment, gasification, pyrolysis,
etc., resulting in the formation of a byproduct known as biochar and it
has achieved colossal interest in the carbon sequestration process [13,
14]. This biochar results from biomass such as organic biowaste and
inorganic wastes generated in enormous amounts by natural and arti­
ficial sources. These biochar can be more cost viable with price ranging
from 4080–30,480 INR ton− 1, almost 6 times less than that of GP [15].
Recently, many investigations have shown the viability of using biomass
waste, forestry residue, crop residue and aerobic sludge for electrode
production in MFC [16–18]. These kinds of sources are expanding the
material availability for producing electrodes continuously. These
manufacturing methods of the electrode are also reducing the final cost
when compared to other high-temperature carbonizing methods. Be­
sides, the performances of new materials are analyzed with existing
electrode material in respect of characteristics, cost and environmental
aspects. The main significance of biochar electrodes are low cost and
better performance when compared to graphite electrode. During
operation, a biochar electrode is performing very well and yield good
results. The tannery effluent used in this study because of high organic
matters makes it conducive for catalyzing microbial actions in MFC.
High amount of organic effluent produces high amount of power output
in MFC.
This present study reveals three types of metal compounds (Si, Zn
and Cu) mixed with biochar (coconut shell wastes) in a specific per­
centage ratio as electrode materials manufactured for MFC. The per­
formances of these electrodes were compared with GP electrode as
anode material. The biochar was synthesized from coconut shell waste
using carbonization at high-temperature. The electrochemical and sta­
tistical analyses for their performance and material characteristics with
respect to resistivity, power production and specific surface area in MFC
were studied. Also, we have studied the benefits and economic potential
of using biochar materials as electrodes in comparison to existing elec­
trode materials.
2.2. Construction & operation of microbial fuel cell
A dual-part H-type model reactor consisting of anode and cathode
was made employing acrylic glass [19]. It consists of 500 ml capacity of
both anode & cathode parts separated by PE membrane (poly­
benzimidazole [2,2’-(m-phenylene)-5,5′ -bisbenzimidazole]-polymer
membrane, Mirai Academy, Chennai, India). The whole setup of the
MFC reactor was sterilized in an autoclave (NSW-227). Fig. 1 illustrates
the schematic representation of MFC reactor. The anode part was fed
with soak effluent of the tannery industry collected from EKM Leather
Pvt. Ltd. Erode, India. The cathode part has 50 mM potassium ferric
solution dissolved in 50 mM phosphate buffer solution (PBS) to attain
steady power along with reduce cathode limitation on the analogy sys­
tem. The MFC operation under room temperature (37 ◦ C) with 500 Ω
resistor. The anode part was replaced by new media when the voltage
reached under 20 mV and this process was replicated to obtain steady
results.
2.3. Material characterization and analysis
X-ray diffraction (XRD) analysis was carried out using 3rd generation
Empyrean, Malvern Panalytical multipurpose diffractometer. Scanning
Electron Microscope with Energy Dispersive X-ray (SEM + EDX) images
were used to obtain surface morphology of the metal mixed compounds
of coconut shell electrodes determined by ZEISS EVO 18 research.
Fourier Transform Infrared (FT-IR) Spectroscopy was performed by
Vertex 80 V spectrometer, Bruker. Waste coconut shell of metal com­
pound electrodes pore size and surface area was measured by ASAP
2010 automatic adsorber with the help of purified N2 adsorption gas
using BET method. The specific surface area was determined by
measuring the quantity of nitrogen gas adsorbed on coconut shell carbon
materials. By increasing the electrodes surface area leads to increase in
specific capacitance value of electrode materials [20].

2. Materials and methods

2.1. Synthesis of coconut shell carbon anode electrode material

In the present work, coconut shell wastes (biochar-based carbon

materials) were used to synthesize anode electrodes. The coconut shell
waste materials were collected from the college hostel dumping yard
and dried. The dried coconut shells were broken into small pieces of 5
mm size, obtained through sieves. The material was carbonized using a
muffle furnace at a high temperature of 500 ◦ C at a rise rate of 10 ◦ C
min− 1 with a residence time of 60 min. The resulting carbon powder
material was mixed with metal compounds such as silicon, zinc and
copper in 1:5 ratio in three electrodes represented as CS-Si0.2, CS-Zn0.2,
and CS-Cu0.2 respectively. The electrodes were then filled with 15 ml of
casting epoxy resin, which works as adhesive coherent followed by
hardener to cure the resin. The hardener and casting epoxy resin used in
the electrode were in 2:1 ratio. The curing process was carried out for a
time period of 24 h under atmospheric condition. Physical and elec­
trochemical properties of the four-carbon anode electrodes with
different perspectives are mentioned in Table 1. Graphite electrode was
purchased from Mirai Academy, Chennai.
Fig. 1. Schematic representation of microbial fuel cell.

2
M. Naveenkumar and K. Senthilkumar Biomass and Bioenergy 149 (2021) 106082

2.4. Power generation measurement and calculations of MFC
MFC performance was assessed based on power density and polari­
zation. The voltage (mV) generated by MFC was measured with digital
unity multimeter by connecting electrodes (anode and cathode). Ac­
cording to Ohm’s law, the current (I) was measured by the constant
voltage generated in MFC. I– – U/R, where, I is the current, U is the
voltage and R is the resistance. Under open circuit voltage mode, voltage
was measured by external resistance and change in generated voltage
was manually noted. The polarization curve was obtained by lowering
the external resistance from 24,000 Ω–100 Ω. The power density (mW
m− 2) and current density (mA m− 2) were measured by normalizing
current (I) and voltage (U) in anode surface. Chemical Oxygen Demand
(COD) and conductivity were analyzed by standard potassium di chro­
mate method (APHA 1998) and parameter analyzer (Eutech’s Cyber­
Scan PC650) respectively. The COD removal efficiency was measured by
equation (1).
Ci − Co
ηCOD = × 100
Ci
where, Ci and Co initial and final COD effluent concentration (mg/l).
The specific capacitance was calculated by equation (2).
Csp = (I ​ × Δt ​ / ΔV ​ × M)
where, Csp is the specific capacitance, I is the current, Δt is the discharge
time, ΔV is the voltage difference in discharge and M is the mass of
active material. The coulombic efficiency (Ce) is ratio of actual current
produced to theoretical current produced in MFC was determined using
equation (3).
∫t
8 × 0 Idt
Ce = (3)
Fv ΔCOD
where, I is the current, F is the Faraday constant, v is the volume of
anode and ΔCOD is the changes in COD concentration.
3. Results and discussion
3.1. Power production performance of metal mixed coconut shell carbon
electrode
MFC performance was evaluated in terms of current and maximum
power output. Table 2 depicts the proximate and ultimate analysis of
waste coconut shell material. Activated carbon has high potential and
carbon composition. The carbon fraction was significantly increased
after carbonization in order to become activated carbon material.
Initially, COD effluent concentration of 3800 mg l− 1 soak wastewater
was fed into the anode part. The MFC performance gradually increased
with time and reached constant voltage after several hours under open
circuit voltage mode. The maximum potential of the electrode was 590,
640, 700 and 680 mV, obtained in coconut shell metal mixed carbon
electrodes namely CS-Si0.2, CS-Zn0.2, CS-Cu0.2, and the control electrode
(GP). Under closed circuit voltage mode, performance of MFC was
notably influenced towards metal mixed carbon electrodes by changing
the resistance range in order to (100 Ω - 1000 Ω) as illustrated in Fig. 2.
Maximum current and voltage was recorded as 0.28 mA (190 mV), 0.33
mA (320 mV), 0.43 mA (440 mV), and 0.39 mA (380 mV) at 1000 Ω high
resistance for CS-Si0.2, CS-Zn0.2, CS-Cu0.2, and GP respectively. MFC
system obtained maximum current and potential as 0.67 mA (50 mV),
0.72 mA (75 mV), 0.9 mA (95 mV), and 0.81 mA (85 mV) at 100 Ω low
resistance for CS-Si0.2, CS-Zn0.2, CS-Cu0.2 and GP respectively. The high
liberation of the electron was observed at lower resistances resulting in
greater potential drops and slow voltage stabilization tendency despite
the higher current generation obtained [21]. Protons neutralized by
transferred electrons from anode part to cathode part. During the
experimental batch, the voltage and current readings were varying with
(1) substrate complexity and action of microbes. In MFC, electrochemical
active bacteria are utilized to produce energy from the oxidation re­
actions of organic substance. Recent researches have shown the variety
of the microbial community in a MFC and more than 20 electrochemical
active bacteria were present. The non-electrochemical active bacteria
(2) are equally important for bioenergy production [22]. Electrochemical
active bacteria have been classified in various groups such as Alphap­
roteobacteria (Ochrobactrum anthropic, Acidiphilium cryptum and
Rhodopseudomonas palustris), Deltaproteobacteria (Desulfobulbus
propionicus, Geobacter metallireducens and Geobacter sulfurreducens)
[23].
The polarization and power density curvature of metal mixed coco­
nut shell electrodes performance are shown in Fig. 3. The peak power
density of (16.8 ± 0.5) mW m− 2, (22.96 ± 0.6) mW m− 2, (38.72 ± 0.5)
mW m− 2, and (30.42 ± 0.5) mW m− 2 with respective current density of
(58.4 ± 3) mA m− 2, (82.1 ± 2) mA m− 2, (88.2 ± 2) mA m− 2, and (78 ±
3) mA m− 2 were obtained for CS-Si0.2, CS-Zn0.2, CS-Cu0.2, and GP
respectively. Obtained results are in accordance with the study which
reported that the activated carbon electrodes produce high power den­
sity in comparison to the control electrode [24].
The coulombic efficiency (Ce) was measured based upon electrode
performance. The performance of the system depends on the electrodes
and substrates used in MFC, which shows that organic matters are effi­
ciently degraded by microbes. Table 3 depicts the MFC power produc­
tion and their performances. Presence of metal coated electrodes
improves the kinetic activity to attribute the differences in surface area

Table 2
Proximate and ultimate analysis of waste coconut shell material (mass fraction
in %).
Analysis Coconut Shell Coconut Shell Activated Coconut Shell
(CS) Carbon (CSC) Carbon (ACSC)

Proximate
Ash content 0.7 1.10 2.15
Fixed carbon 20.50 49.25 67.85
Volatile 75.34 46.80 27.16
matter
Moisture 65 35.60 1.9
content
Ultimate
Carbon 48.36 62.41 81.20
Nitrogen 0.18 0.75 1.20
Hydrogen 6.90 4.56 2.25
Oxygen 41.10 27.32 15.95
Fig. 2. Voltage (dotted lines) and current (straight lines) production range of
Sulphur 0.9 0.07 0.04
(100–1000 Ω) resistance at four electrodes.

3
M. Naveenkumar and K. Senthilkumar Biomass and Bioenergy 149 (2021) 106082

m− 2) for 3800 mg l− 1, 4900 mg l− 1, and 5706 mg l− 1 respectively. Fig. 4

illustrates the power density and polarization curve on various COD
effluent concentration. Table 3 reveals the efficiency of COD removal
and coulombic efficiency (Ce). The COD reduction in the MFC may be
due to microbial utilization and organic adsorption to the carbon and
utilized microbial action. Bacteria growth on carbon surface may
remove the organic matters present in effluent and then partly renew the
carbon stock. Additionally, to enhance the MFC performance by
increasing COD concentration of wastewater while performing MFC, the
conductivity was increased [28].

3.3. Characterization and electrochemical behavior on metal mixed

electrode materials

3.3.1. FTIR
FTIR spectra of metal mixed activated carbon of Zn, Si and Cu
samples were analyzed and shown in Fig. 5. The observed FTIR spectra
Fig. 3. Polarization behavior of control and proposed electrodes; current contain bands at 3200 cm− 1 – 3500 cm− 1 for (O–H) hydroxyl groups.
density vs voltage (straight lines) and current density vs power density (dotted The material structure contains several C bonds and that frequency has a
lines) curve of MFC. stretching of OH and NH2 groups lost during activation to 600 ◦ C. This
resulted in dehydration of lignin and cellulose components. CH of –CH3
is totally eliminated from activated carbon of stretching vibration of
Table 3 peak absorption in the range of 2900 cm− 1 – 2850 cm− 1. The samples
Summary of MFC power production and various performances. Zn, Si and Cu show carbonyl groups (C– – O) in 1740 cm− 1 – 1700 cm− 1
Anode Power Conductivity COD Ce Electrode anticipated from the lignin network. Nonetheless, the absence of peak
materials output (mS cm− 1) removal (%) cost (INR) shows up due to the pyrolysis process with Zn, Si, and Cu since it is
(mV) (%)
volatile. Peaks from 1200 cm− 1 – 1000 cm− 1 indicate the C–O stretching
CS-Si0.2 640 6.9 47.4 4.1 150 presence range and 830 cm− 1 shows the presence of silica [29]. Acti­
CS-Zn0.2 690 7.9 52.18 6.7 170 vated carbon was produced from waste coconut shell materials through
CS-Cu0.2 790 8.2 64.9 12.4 200
GP 730 8.1 56.18 11.2 3800
carbonization process and analyzed by FTIR and XRD methods. FTIR
results show that functional groups of spectrum raw materials were
evaporated as volatile materials when the heat was supplied to samples.
of electrode and structure [20]. Due to the use of mixed metal, the This proves that the activation process has been effectively performed
available surface area has increased and a wide biofilm has been formed and the carbon retains some IR functional groups, (C– – O) groups until
on the electrode. Proposed coconut shell electrodes have high surface the coconut shell was successfully converted to carbon [29,30]. FTIR
area and they help to reduce the internal resistance. results indicate that the activated carbon has completely switched to
carbon. The functional group adsorption peak is lost due to the clear
3.2. Effect of conductivity and COD removal process of activation and hardening of activated carbon. Hence, the
activation process has been a success and a few functional groups like
The conductivity of the proposed and control electrodes were C–O, sensitive IR has been proved [30].
measured in the anode part of MFC. Conductivity variations in all
electrodes showed small changes downward due to ionic adsorption 3.3.2. XRD
utilizing coconut shell carbon materials. Due to ion migration, the The X-ray diffraction spectrum for activated carbon metal mixed
conductivity increased about 1.5 times as reported [25]. The COD coconut shells of Si, Zn, and Cu were analyzed and shown in Fig. 6. The
effluent concentration of wastewater is one of the significant factors to
improve the microbial growth and MFC power generation performance.
The COD effluent concentration on power generation was monitored by
different range of 3800 mg l− 1, 4900 mg l− 1, and 5706 mg l− 1 using
CS-Cu0.2 electrode as anode and tannery soak wastewater as anolyte in
anode part with pH 8. The pH was monitored during the process and it
was observed that pH variation in the biofilm was occurred between 8
and 6.9 which may be due to proton fluctuation through proton ex­
change membrane. The pH variation affected bacterial respiration and
power production in the MFC [26]. A lightly alkaline pH of anodic
process may contain facilitated in the formation of electrogenic bacteria
and further necessary bacterial biofilm contributing in anode with
complex substrate, which brought about less activation losses. As a
result, more pH of anodic process in MFC attains lower internal resis­
tance [27]. Maximum open circuit voltage of (755 ± 5) mV, (770 ± 5)
mV, and (790 ± 6) mV was obtained for 3800 mg l− 1, 4900 mg l− 1, and
5706 mg l− 1 respectively. High voltage is generated due to accelerating
the reaction rate by increasing the substrate concentration. Higher
power density and current density are generated by higher COD effluent
concentration. Obtained peak power densities are 31.04 mW m− 2 (78.8 Fig. 4. Power density (dotted lines) and voltage (straight lines) polarization
mA m− 2), 38.38 mW m− 2 (101 mA m− 2), and 44.69 mW m− 2 (109 mA curve at various COD effluent concentration by CS-Cu0.2 electrode.

4
M. Naveenkumar and K. Senthilkumar Biomass and Bioenergy 149 (2021) 106082

Fig. 7. Cyclic voltammogram of biofilm grown-up and electrodes with tan­

nery wastewater.

Fig. 5. FTIR analysis of metal mixed coconut shell electrodes. improvement in electrochemical activity as evident from increased
inactivated carbon on metal. This kind of considerable alteration of
electrode surface gives better performance in MFC.

3.3.4. SEM
Scanning Electron Microscopy (SEM) instrument is utilized for
analyzing the samples surface morphology. Microstructure of the raw Si,
Zn, Cu, and GP are shown in Fig. 8. A wide range of surfaces with pores
was produced at the activation phase. The surface morphology of sam­
ples reveals surface topology variation between raw coconut shell and
activated carbon. Especially, high porosity was observed on the exterior
surface of the samples. The SEM images show noticeable pores in all the
samples namely Si, Zn, Cu, and GP. The visible pores are evident pores
that show the carbon activation process in biochar electrodes. Visible
pores are pointed out in SEM morphology.

3.3.5. EDX
X-ray Energy Dispersive Spectrometer was used for EDX analysis.
This analysis reveals the characteristic and distinct line of metals (Si, Zn,
and Cu) and oxygen signal of mixed metals in electrodes. Fig. 9 shows
the EDX spectrum of metals in electrodes. No impurities were found. The
horizontal axis shows keV (energy) and vertical axis shows number of X-
Fig. 6. XRD model of metal mixed coconut shell electrodes.
ray counts. The peak in spectra shows that Si, Zn and Cu metals and
oxygen are attributed and gives assurance that all metals and oxygen has
peak diffractions of Si, Zn, and Cu were monitored at an angle of 2Ɵ = been well identified. The elements data in the form of weight and atomic
28.5◦ , 10.0◦ , and 14.5◦ respectively. This shows the presence of metals percentage were examined using EDX spectrum as shown in Table 4.
in activated carbon electrodes. The rest of the small peaks were moni­
tored at the diffraction angle of 48.5◦ , 24.0◦ , and 31.5◦ indicating ores,
3.4. Role, economy and benefits of coconut shell electrodes
quartz, and minerals.
An electrode is one of the main components in a microbial fuel cell
3.3.3. Cyclic voltammetry (CV)
which imparts performance on bioenergy production and material cost.
Electrochemical behavior of electrode materials was measured by CV
Several investigations were reported in recent years to increase the MFC
method. It shows notable differences in discharge of electron and energy
power production and modifying the electrode material and reduce
production with function of loading activated carbon. Throughout the
operational cost in various aspects [32–34]. Electrode design is con­
scanning process of ahead and reverse, there are no clear Oxidation-
fronted to make microbial fuel cells with economic commercialization
Reduction (OR) peaks as shown in Fig. 7. Metal mixed coconut shell
technology to compete with electrodes may be broadly used to electron
electrodes produced high power as compared to control electrode.
transfer and enhancement of bacterial activity from microorganisms to
Therefore, altered anode electrodes showed more electron transfer
the surface of the electrode [35]. Recently, lots of investigations are
properties than unaltered electrode. Power generation increased with
carried out for the carbon-based electrodes as components for trans­
metal mixed loading proportions of coconut shell electrode; maximum
ferring electrons from anode to cathode part in MFC [36,37]. In MFC,
current of 0.29 mA, 0.48 mA, 1.19 mA, and 1.95 mA at 1 V throughout
conductivity and electro catalytic activity may not get increased using
onward scan process and 0.39 mA, 0.78 mA, 1.5 mA, and 2.7 mA at − 1 V
altered carbon nanotubes as electrode however, significantly it increases
throughout reverse scan process at a scanning rate of 50 mV s− 1 vary
the specific surface area. Therefore, electrode surface area can give
from − 1 V to +1 V. During the alteration of carbon mesh the same
greater connection locales to microorganism connection, and make easy
tendency of CV was examined using electrochemical oxidation [31].
substrate transfer process along with electron transfer pathway [38].
From the literature, there is an increase in anode power while increasing
Electrode with 3.9% of more N/C ratio and great surface area of 145.4
activated carbon loading at COD concentration. Hence, it shows
cm2, which improved the attachment of microbes and contributed large

5
M. Naveenkumar and K. Senthilkumar Biomass and Bioenergy 149 (2021) 106082

Fig. 8. Surface morphology of the activated carbon magnification of 5,000× (a) CS-Si0.2 (b) CS-Zn0.2 (c) CS-Cu0.2 (d) GP.

Fig. 9. EDX spectrum of metal mixed coconut shell electrodes (a) CS-Si0.2 (b) CS-Zn0.2 (c) CS-Cu0.2.

vigorous locales for Extracellular Electron Transport (EET). Interest­ used as preservative in the anode compartment for methylene blue
ingly, in anode surface riboflavin content increased, involving that the degradation. Biochar material was heated at 500 ◦ C to produce biochar
alteration of electrode with N-doped anode is a feasible approach for along with sulphuric acid treatment. In MFC, assimilation of acid treated
improving the MFC performances [39]. In MFC, biochar electrodes were biochar electrode enhanced the peak power output by 1.38 times when

6
M. Naveenkumar and K. Senthilkumar
Table 4
EDX analysis of synthesized electrodes.
Materials Weight (%) Atomic (%)
O K O K
CS-Si0.2 81.10 18.90 90.71 9.29
CS-Zn0.2 80.16 19.84 96.22 3.78
CS-Cu0.2 80.05 19.95 97.15 2.85
compared to control experimental setup worked with unalteration of
biochar material. A cost-effective electrode facilitates the applications in
various field-level MFC systems, like industrial unit of MFC need big size
electrodes. Besides, biochar electrode with capacity of adsorption is also
a further benefit for the bioremediation with the exception of specific
surface area [40]. Rabaey et al. reported the graphite material used as an
electrode material in the anode part at the beginning of the research
[41]. Aelterman et al. reveal that graphite and carbon felt materials
were used as electrodes in MFC [42]. The results comparing both ma­
terial performances show that the electrode yields highest power output
up to 386 W<superscript></superscript> m<superscript>-3
</superscript>. However, graphite material is an expensive material.
Coconut shell carbon electrodes have a mesoporous structure that effi­
ciently supports the transport of electrolytes and makes well-built bio­
film on the electrode surface [43].
The locally accessible waste biomass was utilized with small to no
commercial value as it reduces the purchase and transport cost. Coconut
shell biomass also significantly reduced carbon dioxide emissions and
resulted in biochar stored in atmospheric carbon [44]. In this proposed
study, we utilized coconut shell biomass collected from our college
hostel campus, representing a locally accessible biomass waste. The cost
associated with local accessible waste biomass-based electrodes was due
to the transportation of coconut shell wastes purchased at 3000 INR per
kg. Besides, the fabrication of electrodes needs little external energy
along with no need of pretreatment. Synthesized biochar electrodes cost
was around 200 INR per electrode. It is approximately 95% less than the
graphite electrode used in this study which was bought for 3800 INR.
The benefit of coconut shell materials in real field applications is that
coconut husks are used for the production of coconut mats and brushes.
Since more lignin contents were present in husk material, it is adhesive
in nature. Coconut shell is one of the vast sources in India and also
economical. Therefore, in this study the metal mixed coconut shell
biochar electrodes were utilized as anode in MFC and their performance
were assessed. Further research is needed to identify mechanism and
function of different types of waste carbon materials in MFC. Researches
based on different kind of waste biomass electrodes improve the MFC
performance, high surface area of electrodes and reactors with viable
designs can be made a possibility for production of bioenergy in real
field.
To build up the better information and comprehension of connec­
tions among biochar and its potential applications, steady and repeat­
able trial testing with biochar characterizations are fundamental.
Besides, there is a need to comprehend the level of regular varieties in
electrochemical and physical properties of biochar and to create stra­
tegies for moderating as well as limiting the possible effects of qualities
of biochar materials. Though much information on designs of different
scales in biomass is available, little is acknowledged with respect to the
structural features, which may be retained when biomass is changed into
biochar hydrothermally, and how their change is affected through
carbonization methods. These difficulties call for close cooperation
among researchers and designers who spend significant time in appli­
cable fields from ecological science and resources that are related with
biochemical and chemical engineering fields.
4. Conclusion
Carbon electrodes, made from waste coconut shell materials are
7
Biomass and Bioenergy 149 (2021) 106082
mixed with metals such as Cu, Zn & Si and they were tested as electrodes
in MFCs. Tested materials exhibit considerable power output in com­
parison to control electrode except for Si electrodes. The experimental
results revealed that maximum power production was observed 44.69
mW m− 2 (109 mA m− 2) in biochar electrode. Cost of coconut shell
electrode materials was substantially less than the cost of control elec­
trodes. Biochar material holds benefits like carbon sequestration, energy
positive processing, soil health improvement and high-endurance car­
bon in soil for millions of years. The synthesis of biochar electrode from
coconut shell waste, a value addition product, is an environmentally
friendly technique to replace the incineration method. It also diminishes
atmospheric pollution caused by coconut shell waste incineration. Based
on the cost effective and ease of electrode synthesis, its better perfor­
mance makes it a capable electrode for greater-performance MFC which
is further used in future scale-up and technology execution. Further
research is needed to enhance the performance of microbial fuel cell by
optimizing synthesize technique of electrodes.
Funding sources
This work was catalyzed and financially supported by Tamilnadu
State Council for Science and Technology (TNSCST), Department of
Higher Education, Government of Tamilnadu, Chennai, TN, India [Grant
Ref. No. TNSCST/RFRS/VR/11/2018–19/7363 dt.25.8.2019].
Nomenclature
APHA American Public Health Association
INR Indian Rupees
IR Infrared
References
[1] H. Wang, Z.J. Ren, A comprehensive review of microbial electrochemical systems
as a platform technology, Biotechnol. Adv. 31 (8) (2013) 1796–1807.
[2] B. Liang, C. Ren, Y. Zhao, K. Li, C. Lv, Nitrogenous mesoporous carbon coated with
Co/Cu nanoparticles modified activated carbon as air cathode catalyst for
microbial fuel cell, J. Electroanal. Chem. 860 (2020) 113904.
[3] B.E. Logan, Microbial Fuel Cells, Wiley (Wiley.com), 2008, https://doi.org/
10.1002/9780470258590.
[4] A. Sepehri, M.H. Sarrafzadeh, Effect of nitrifiers community on fouling mitigation
and nitrification efficiency in a membrane bioreactor, Chem. Eng. Process
Intensifcation 128 (2018) 10–18, https://doi.org/10.1016/j.cep.2018.04.006.
[5] A. Sepehri, M.H. Sarrafzadeh, Activity enhancement of ammonia-oxidizing bacteria
and nitrite-oxidizing bacteria in activated sludge process: metabolite reduction and
CO2 mitigation intensification process, Appl. Water Sci. 9 (131) (2019) 1–12,
https://doi.org/10.1007/s13201-019-1017-6.
[6] G. Palanisamy, H.Y. Jung, T. Sadhasivam, M.D. Kurkuri, S.C. Kim, S.H. Roh,
A comprehensive review on microbial fuel cell technologies: processes, utilization,
and advanced developments in electrodes and membranes, J. Clean. Prod. 221 (2)
(2019) 598–621.
[7] K. Rabaey, S. Butzer, S. Brown, J. Keller, R.A. Rozendal, High current generation
coupled to caustic production using a lamellar bioelectrochemical system, Environ.
Sci. Technol. 44 (11) (2010) 4315–4321.
[8] R.A. Rozendal, E. Leone, J. Keller, K. Rabaey, Efficient hydrogen peroxide
generation from organic matter in a bioelectrochemical system, Electrochem.
Commun. 11 (9) (2009) 1752–1755.
[9] M.M. Mian, G. Liu, B. Fu, Conversion of sewage sludge into environmental catalyst
and microbial fuel cell electrode material: a review, Sci. Total Environ. 666 (2019)
525–539.
[10] L. Yan, J. Yu, J. Houston, N. Flores, H. Luo, Biomass derived porous nitrogen doped
carbon for electrochemical devices, Green Energy Environ. 2 (2) (2017) 84–99.
[11] H. Yuan, Y. Hou, I.M. Abu-Reesh, J. Chen, Z. He, Oxygen reduction reaction
catalysts used in microbial fuel cells for energy-efficient wastewater treatment: a
review, Mater. Horiz. 3 (5) (2016) 365–462.
[12] J. Wei, P. Liang, X. Huang, Recent progress in electrodes for microbial fuel cells,
Bioresour, Technol. 102 (20) (2011) 9335–9344.
[13] J. Lehmann, A handful of carbon, Nature 447 (2007) 143–144.
[14] T. Cai, M. Huang, Y. Huang, W. Zheng, Enhanced performance of microbial fuel
cells by electrospinning carbon nanofibers hybrid carbon nanotubes composite
anode, Int. J. Hydrogen Energy 44 (5) (2019) 3088–3098.
[15] S. Meyer, B. Glaser, P. Quicker, Technical, economical, and climate-related aspects
of biochar production technologies: a literature review, Environ. Sci. Technol. 45
(22) (2011) 9473–9483.
[16] S. Chen, G. He, X. Hu, M. Xie, S. Wang, D. Zeng, H. Hou, U. Schroder, A three-
dimensionally ordered macro porous carbon derived from a natural resource as
M. Naveenkumar and K. Senthilkumar
anode for microbial bioelectrochemical systems, ChemSusChem 5 (2012)
1059–1063.
[17] S. Chen, G. He, Q. Liu, F. Harnisch, Y. Zhou, Y. Chen, M. Hanif, S. Wang, X. Peng,
H. Hou, U. Schroder, Layered corrugated electrode macrostructures boost
microbial bioelectrocatalysis, Energy Environ. Sci. 5 (12) (2012) 9769.
[18] Y. Yuan, T. Yuan, D. Wang, J. Tang, S. Zhou, Sewage sludge biochar as an efficient
catalyst for oxygen reduction reaction in an microbial fuel cell, Bioresour. Technol.
144 (2013) 115–120.
[19] N. Samsudeen, T.K. Radhakrishnan, M. Matheswaran, Bioelectricity production
from microbial fuel cell using mixed bacterial culture isolated from distillery
wastewater, Bioresour. Technol. 195 (2015) 242–247.
[20] G.H. Yuan, Z.H. Jiang, M. Aramat, Y.Z. Gao, Electrochemical behavior of activated-
carbon capacitor material loaded with nickel oxide, Carbon 43 (14) (2005)
2913–2917.
[21] S.V. Raghavulu, S.V. Mohan, R.K. Goud, P.N. Sarma, Effect of anodic pH
microenvironment on microbial fuel cell (MFC) performance in concurrence with
aerated and ferricyanide catholytes, Electrochem. Commun. 11 (2) (2009)
371–375.
[22] Z. Wei, G. Zheng, H. Zhen, Z. Husen, Method for understanding microbial
community structures and functions in microbial fuel cells: a review, Bioresour.
Technol. 171 (2014) 461–468.
[23] Y.C. Zhang, Z.H. Jiang, Y. Liu, Application of electrochemically active bacteria as
anodic biocatalyst in microbial fuel cells, Chin. J. Anal. Chem. 43 (2015) 155–163.
[24] X. Peng, H. Yu, X. Wang, Q. Zhou, S. Zhang, L. Geng, J. Sun, Z. Cai, Enhanced
performance and capacitance behavior of anode by rolling Fe3O4 into activated
carbon in microbial fuel cells, Bioresour, Technol. 121 (2012) 450–453.
[25] H. Luo, P. Xu, T.M. Roane, P.E. Jenkins, Z. Ren, Microbial desalination cells for
improved performance in wastewater treatment electricity production and
desalination, Bioresour. Technol. 105 (2012) 60–66.
[26] G.S. Jadhav, M.M. Ghangrekar, Performance of microbial fuel cell subjected to
variation in pH, temperature, external load and substrate concentration, Bioresour.
Technol. 100 (2009) 717–723.
[27] M. Behera, M.M. Ghangrekar, Performance of microbial fuel cell in response to
change in sludge loading rate at different anodic feed pH, Bioresour. Technol. 100
(2009) 5114–5121.
[28] Y. Feng, X. Wang, B.E. Logan, H. Lee, Brewery wastewater treatment using air-
cathode microbial fuel cells, Appl. Microbiol. Biotechnol. 78 (5) (2008) 873–880.
[29] A. Hidayu, N.F. Muhammad, S. Matali, A.S. Sharifah, Characterization of activated
carbon prepared from oil palm empty fruit bunch using BET and FTIR techniques,
Procedia Eng. 68 (2013) 379–384.
[30] R.H. Hesas, A. Arami-Niya, W.M.A.W. Daud, J.N. Sahu, Preparation and
characterization of activated carbon from apple waste by microwave-assisted
phosphoric acid activation: application in methylene blue adsorption, Bio Resour.
8 (2) (2013) 2950–2966.
Biomass and Bioenergy 149 (2021) 106082
[31] M. Zhou, M. Chi, H. Wang, T. Jin, Anode modification by electrochemical
oxidation: a new practical method to improve the performance of microbial fuel
cells, Biochem. Eng. J. 60 (2012) 151–155.
[32] T. Cai, L. Meng, G. Chen, Y. Xi, N. Jiang, J. Song, S. Zheng, Y. Liu, G. Zhen,
M. Huang, Application of advanced anodes in microbial fuel cells for power
generation: a review, Chemosphere 248 (2020) 125985.
[33] L. Jiang, J. Chen, D. Han, S. Chang, R. Yang, Y. An, Y. Liu, F. Chen, Potential of
core-shell Ni-Fe layered double hydroxide @Co3O4 nanostructures as cathode
catalysts for oxygen reduction reaction in microbial fuel cells, J. Power Sources
453 (2020) 227877.
[34] Y.E. Song, S. Lee, M. Kim, Na, J.G. Lee, Jinwon, Jinwoo Lee, J.R. Kim, Metal free
cathodic catalyst with nitrogen- and phosphorus-doped ordered mesoporous
carbon (NPOMC) for microbial fuel cells, J. Power Sources 451 (2020) 227816.
[35] B. Min, B.E. Logan, Continuous electricity generation from domestic wastewater
and organic substrates in a flat plate microbial fuel cell, Environ. Sci. Technol. 38
(21) (2004) 5809–5814.
[36] S. Chen, J. Tang, L. Fu, Y. Yuan, S. Zhou, Biochar improves sediment microbial fuel
cell performance in low conductivity freshwater sediment, J. Soils Sediments 16
(9) (2016) 2326–2334.
[37] J.J. Sun, H.Z. Zhao, Q.Z. Yang, J. Song, A. Xue, A novel layer-by-layer self-
assembled carbon nanotube-based anode, preparation, characterization, and
application in microbial fuel cell, Electrochim. Acta 55 (9) (2010) 3041–3047.
[38] C. Zhao, P. Gai, R. Song, Y. Chen, J. Zhang, J.J. Zhu, Nanostructured material-
based biofuel cells: recent advances and future prospects, Chem. Soc. Rev. 46 (5)
(2017) 1545–1564, https://doi.org/10.1039/C6CS00044D.
[39] H.R. Yuan, L.F. Deng, X. Qian, L.F. Wang, D.N. Li, Y. Chen, Y. Yuan, Significant
enhancement of electron transfer from Shewanella oneidensis using a porous N-
doped carbon cloth in a bioelectrochemical system, Sci. Total Environ. 665 (2019)
882–889, https://doi.org/10.1016/j.scitotenv.2019.02.082.
[40] R. Shen, Y. Jing, J. Feng, J. Luo, J. Yu, L. Zhao, Performance of enhanced anaerobic
digestion with different pyrolysis biochars and microbial communities, Bioresour.
Technol. 296 (2020) 122354, https://doi.org/10.1016/j.biortech.2019.122354.
[41] K. Rabaey, L. Angenent, U. Schroder, J. Keller, Bioelectrochemical Systems: from
Extracellular Electron Transfer to Biotechnological Application, first ed., IWA
publishing, london, 2009 https://doi.org/10.2166/9781780401621.
[42] P. Aelterman, M. Versichele, M. Marzorati, N. Boon, W. Verstraete, Loading rate
and external resistance control the electricity generation of microbial fuel cells
with different three-dimensional anodes, Bioresour, Technol. 99 (18) (2008)
8895–8902.
[43] X. Xie, L.B. Hu, M. Pasta, G.F. Wells, D.S. Kong, C.S. Criddle, Y. Cui, Three-
dimensional carbon nanotube-textile anode for high-performance microbial fuel
cells, Nano Lett. 11 (1) (2011) 291–296.
[44] S.P. Sohi, E. Krull, E. Lopez-Capel, R. Bol, A review of biochar and its use and
function in soil, Adv. Agron. 105 (2010) 47–82, https://doi.org/10.1016/S0065-
2113(10)05002-9.