Process Safety and Environmental Protection 155 (2021) 49–60

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Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Preparation, characterization, and application of modified carbonized

lignin as an anode for sustainable microbial fuel cell
Asim Ali Yaqoob a , Mohamad Nasir Mohamad Ibrahim a,∗ , Susana Rodríguez-Couto b ,
Akil Ahmad c
a
Materials Technology Research Group (MaTRec), School of Chemical Sciences, Universiti Sains Malaysia, 11800, Minden, Penang, Malaysia
b
Department of Separation Science, LUT School of Engineering Science, LUT University, Sammonkatu 12, FI-50130, Mikkeli, Finland
c
Centre of Lipids Engineering and Applied Research, Universiti Teknologi Malaysia, Skudai, 81310, UTM, Johor, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Microbial fuel cell (MFC) is the most prominent bioelectrochemical approach in electricity generation
Received 24 February 2021 while metal removal is its secondary application. However, ongoing challenges including low electron
Received in revised form 29 August 2021 transfer rates and unstable biofilm formation on the anode surface need to be addressed. As an attempt to
Accepted 1 September 2021
overcome such drawbacks, in the present study, the anode was prepared from graphene oxide (Lg-GO)
obtained from lignin and subsequently modified with a metal oxide (i.e., TiO2 ). Thus, the plain Lg-GO
Keywords:
and Lg-GO/TiO2 delivered 57.01 mA/m2 and 70.17 mA/m2 of current density along with 85 % and 90
Microbial fuel cell
% of Pb (II) ions removal from synthetic wastewater, respectively within the 90-day operation of MFC.
Energy generation
Wastewater treatment
The recorded maximum power density at the Lg-GO anode was 0.44 mW/m2 , while the maximum PD
Anode fabrication at the Lg-GO/TiO2 anode was 0.78 mW/m2 . The prepared anodes were characterized, and the opera-
Lignin tional conditions were optimized to validate their performances. The results showed that the optimum
performance of the anode was in normal environmental conditions (e.g., pH 7, room temperature). In
conclusion, the obtained results indicated that the prepared electrodes (i.e., Lg-GO and Lg-GO/TiO2 ) are
suitable for energy generation and metal removal via MFC.
© 2021 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Recently, a complete prototype of a microbial fuel cell (MFC) was

developed to produce renewable energy and simultaneously treat
Presently, the world is facing two major problems: energy crisis contaminated water (containing heavy metal ions such as Pb(II))
and water pollution. Thus, the rapid depletion of fossil fuels in the (Clauwaert et al., 2007; Logan et al., 2006). MFC uses microbes as
modern era has led to a worldwide energy crisis. The world does catalysts to convert chemical energy into electrical energy. Its con-
not have sufficient resources to satisfy the energy demands with sists of two chambers: the anode and the cathode chambers which
increasing world population, urbanization, and industrialization contain the anode and cathode electrode, respectively (Jadhav et al.,
growth. Regarding water pollution, the presence of heavy metals 2020a). The anode serves as a surface area for the growth of
in water sources is very worrying, as it endangers human health microbes which generate electrons and protons during their res-
and the environment (Azimi et al., 2017; Yaqoob et al., 2020a). piration process. The formers are transferred to the cathode by
Currently, Malaysia faces the problem of water pollution in the using an outer circuit whereas the latter is moved from the anode
environment due to the presence of heavy metals. Therefore, about chamber to the cathode chamber via a proton exchange membrane
99 % of Malaysians use surface water and only 1% groundwater (PEM). The oxidation process occurs on the anode which simulta-
for drinking purposes (Ab Razak et al., 2015). Some heavy met- neously converts the soluble heavy metal ions into their insoluble
als such as Pb, Hg, As and Cd are known to cause severe diseases forms. The heavy metals have high redox potentials and, therefore,
(e.g. brain tumor, kidney failure, heart diseases, lung cancer, and can be used as electron acceptors to precipitate and reduce the dis-
bone deficiency) even when present at trace amounts (Ahmad et al., solved metals into their insoluble state (Choudhury et al., 2017;
2020). Habibul et al., 2016; Yaqoob et al., 2020b). In an effort to move
towards the practicality of MFC applications, several studies have
been well discussed previously (Hiegemann et al., 2019; Jadhav
∗ Corresponding author. et al., 2020b; Pant et al., 2012). Many parameters are involved in
E-mail address: [email protected] (M.N. Mohamad Ibrahim). MFC performance such as organic substrate, microbial community,

https://doi.org/10.1016/j.psep.2021.09.006
0957-5820/© 2021 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

electrodes, and cell design. Among them, the anode is an emerg- 2.3. Synthesis of Lg-GO and Lg-GO/TiO2 composite
ing interesting challenge. In particular, the design, chemistry, and
morphology of the anode material are among the most critical fac- The prepared Lg-carbon was used to synthesize the Lg-GO by
tors. Thus, several studies indicated that the properties and cost using the Hummers method (Zaaba et al., 2017) which is a very
of anode materials are challenging problems in MFC commercial- common method to synthesize graphene derivatives. Therefore, Lg-
ization efforts (Li et al., 2017; Yaqoob et al., 2020c, d). Therefore, carbon (10 g) was added to the H2 SO4 solution (300 mL) in an ice
the highly efficient anode material is required to improve electron bath, to maintain a temperature between 0–5 ◦ C, while stirring.
transportation and, thus, enhance energy generation and water After 10 min, NaNO3 (8 g) was added to enhance the interlayer
treatment efficiency. To address the above-mentioned challenges, distance and oxidation. Further, to improve the oxidation, 30 g of
several efforts using conventional carbon-based (carbon rod, cloth, KMnO4 was added and the reaction mixture was kept at constant
sheet, foam, carbon nanotubes, etc.) and metal-based electrode stirring for 2 h in an ice bath. For proper oxidation, the reaction was
strips were attempted (Yaqoob et al., 2020d). further stirred for 5 h until the colour turned from black greenish to
Conventional materials such as carbon nanotubes, graphite, car- violet-brown. At this stage, distilled water was added dropwise up
bon rod, carbon paper, carbon brush, carbon cloth, carbon felt, to 300 mL and heated at 90 ◦ C which turned the solution into dark
carbon foam, etc. are used to build anode, but some drawbacks brown. Before further adding more water (300 mL), the reaction
such as cost, toxicity, low electric conductivity, and high electronic temperature was cooled down to 25 ◦ C, and later H2 O2 (40 mL)
resistance, making them less suitable for use in MFC operations was added which resulted in the colour of the solution becoming
(Prestigiacomo et al., 2016; Adam et al., 2011; Yaqoob et al., 2020d). yellowish-brown. This colour indicated the success of GO synthesis.
According to the latest reported research, graphene derivatives are Afterward, the solution was centrifuged several times at 2147 g for
a promising material to overcome the challenges mentioned above 10 min by using ethanol and distilled water. Later, the centrifuged
(Guerrero-Barajas et al., 2021). Therefore, in this study, the pro- product was dried in an oven at 40 ◦ C for 24 h to get a powder form.
duction of graphene oxide (Lg-GO) produced from oil palm waste The Lg-GO/TiO2 composite was prepared by using the solvother-
lignin and composite with titanium oxide (TiO2 ) to build the anodes mal method (Wang et al., 2012). In this process, Lg-GO (5 g) and
for MFC was performed. Previously Mashkour et al. (2017) proved TiO2 (2.5 g) were mixed in the presence of water under constant
that GO/TiO2 modified electrode as cathode improved the catalytic stirring for 3-4 h at 24 ◦C. Afterward, the mixture was centrifuged
activities and energy efficiency in MFC. The presently prepared several times at 3354 g for 20 min to get an impurity-free composite
electrodes were used as anodes to improve the electron transfer powder. Finally, it was dried in an oven at 70 ◦C for 24 h.
rate toward the cathode. The performance of the prepared anodes
was assessed in MFC in terms of energy production and Pb (II) ions 2.4. Fabrication and characterization of anode materials
removal from synthetic wastewater at a laboratory scale.
In the fabrication of both anodes (i.e., Lg-GO and Lg-GO/TiO2 ),
graphite rods (2 mm) were used as current collectors which also
2. Materials and methods
provided the mechanical support to the self-assembled anodes.
In the fabrication process, 60 % Lg-GO was mixed with 40 % of
2.1. Chemicals and materials
polysulfones (PSF) solution to obtain a paste-liked material to coat
the current collector surface. The material was dried at 50 ◦C for
Oil palm trunk sap was a gift from the School of Industrial
8 h. After the drying process, a rod-shaped anode, known as Lg-
Technology (USM, Malaysia) and oil palm empty fruit bunches
GO anode, was obtained. A similar procedure was adopted for the
(OPEFB) were received from Sabutek (M) Sdn. Bhd, Polysulfones
preparation of the Lg-GO/TiO2 anode. Thus, 60 % of Lg-GO/TiO2 was
(Mw∼35,000, AR grade), hydrochloric acid (37 %, AR grade),
mixed with 40 % of PSF solution and the product obtained was
sulphuric acid (95–97 %, AR grade), hydrogen peroxide (30–32
used to coat the surface of the graphite rod. Both anodes had the
%, AR grade), ethanol (approx. 95 %, AR grade), glucose (AR
same size (8 cm × 1.3 cm) and surface area (0.0076 m2 ). Different
grade), dichloromethane (AR grade), phosphate buffer (pH 7) and
characterization techniques were used to study the morphology of
potassium permanganate (AR grade) were purchased from QRec
the prepared materials (i.e., Lg-GO and Lg-GO/TiO2 ) such as UV-
Chemicals (Malaysia). Sodium nitrate and lead nitrate were pur-
spectroscopy, Fourier transform infrared (FT-IR), X-ray diffraction
chased from R&M Chemicals (Malaysia) and titanium oxide from
(XRD), scanning electron microscope (SEM), transmission electron
Sigma-Aldrich (Germany).
microscope (TEM), energy dispersive X-Ray, (EDX), atomic force
microscopy (AFM), thermal gravimetric analysis (TGA), Brunauer-
2.2. Extraction of lignin and the preparation of carbonized lignin Emmett-Teller (BET) and Raman spectroscopy.

The extraction of lignin from OPEFB was carried out through a 2.5. Inoculation source pre-treatment
pulping machine as explained by Sekeri et al. (2020). In that process,
500 g of oil palm empty fruit bunches (OPEFB), NaOH (150 g/L), and In the present work, wastewater collected from a pond at the
3 L of tap water were added into a pulping machine for 3 h at 170 ◦ C. Universiti Sains Malaysia was used as an inoculation source. Before
The process produced two types of materials: black liquor and solid MFC operation, 100 mg / L of Pb (II) ions were added to the
material. The solid material was separated from the black liquor by raw wastewater. A pH meter (EUTECH instrument-700 USA), a
simple squeezing and further the black liquor was treated for lignin liquid thermometer (GH, ZEAL LTD, England), and an electrical
extraction. The black liquor obtained from the pulping process was conductivity meter (ECM) (Alpha-800 conductivity meter) were
highly basic (pH 12.9), so lignin was precipitated by adding 52 mL of used to measure the pH, the temperature, and the conductivity,
H2 SO4 to acidify the black liquor until pH 2. Then, the precipitated respectively, of the raw and Pb (II) ions supplemented wastewater
lignin was centrifuged for 15 min at 4000 rpm and the centrifuged (Table 1).
product was dried in an oven at 40−50 ◦ C for 24 h and after that
finely ground to get a fine powder (Ibrahim et al., 2010). This fine 2.6. MFC operational setup
powder was treated in an oven at a high temperature (1000 ◦C)
for 3 h to get carbonized lignin, named as Lg-carbon in the present A double chamber microbial fuel cell (DMFC) was used with each
study. of the built electrodes (i.e., Lg-GO and Lg-GO/TiO2 ). The DMFC had

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A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Fig. 1. Design of the laboratory-scale MFC used in the present study (a) MFC model; (b) Operating mode of the MFC.

Table 1 surface. CV was carried out at different time intervals of operation

Properties of the collected wastewater before and after the addition of 100 mg/L of
through a potentiostat system at a scan rate of 20 mV/s within a
Pb (II) ions.
potential range from +0.8 to −0.8 V. A platinum wire was used as
Parameters Raw wastewater Pb (II) a counter electrode and Ag/AgCl was used as a reference electrode.
supplemented
By using the CV data, the specific capacitance (Cp ) was measured
wastewater
according to the following equation (Yaqoob et al., 2020b):
Colour Light yellowish Light yellowish
Electrical conductivity 62 ␮S/cm 87 ␮S/cm A
Cp = (1)
Temperature Room temperature Room temperature 2mk (V2 − V1 )
pH 6.98 6.56
Odor Strong pungent Strong pungent where Cp is a term of integration over the entire set of data per unit
Pb (II) 0 mg/L 100 mg/L of area of both anodes (Lg-GO and Lg-GO/TiO2 ), V = V2 -V1 is the
voltage range, m is the loaded sample in grams (g), k is the scan
rate of CV in mV/s and A is the curve area.
anode and cathode chambers separated by a PEM (Nafion-117) as Electrochemical impedance spectroscopy (EIS) measurement
shown in Fig. 1. The PEM was used to pass the protons from the was carried out to analyze the effect of the resistance from the elec-
anode to the cathode while the electrons travelled through the trolytic solution of the cathode and anode. The EIS measurement
outer circuit. Copper wire was used to develop the outer circuit was done at the end of the MFC process to describe the electro-
in the presence of external resistance (1000 ). A simple graphite chemical limits as an effect of the biocatalyst improvement. EIS
rod (GR, FUDA 2B Lead, NY, USA) was used as a cathode electrode measurement was carried out in functioning mode within the 100
in both cases with the same size as the fabricated Lg-GO and Lg- kHz-100 mHz frequency range. Within 10 min, individual spectrum
GO/TiO2 anodes (i.e., 8 cm × 1.3 cm). The distance between both was done within 0.5–0.1 Hz scene series of amplitude.
electrodes was 7 cm. The anode chamber had a size of 10 cm × 9.5 The removal efficiency of the target metal (i.e., Pb) was
cm (length × width) whereas the cathode chamber was 10 cm × determined through atomic absorption spectrometry (AAS)
9 cm, and the working volume of each chamber was 1000 mL. The (PerkinElmer AAnalyst 400). For this purpose, every 20 days 1 mL
Pb (II) supplemented wastewater (350 mL) was filled in the anode of solution was taken from the anode chamber and analyzed for Pb
chamber while tap water (350 mL) was filled in the cathode cham- detection. The removal efficiency was calculated by using Eq. (2)
ber. The pH of the cathode solution was maintained at a constant
pH of 7 by using phosphate buffer solution (PBS-pH 7). The whole Tintial − Tfinal
RE = × 100 (2)
experiment was done at room temperature. During the process, Tintial
every day 3 mL of tap water was added to overcome the evapo- where RE = removal efficiency, Tinitial = initial toxic metal concen-
ration effect of water in the cathode chamber. Oil palm trunk sap tration, Tfinal = final toxic metal concentration.
was used as an organic substrate for bacterial growth. The anode SEM equipped with EDX (SEM-Zeiss, model DSM-960, Germany)
chamber was sealed while the cathode one was connected to an was used to investigate the biofilm on the anodes (Lg-GO and Lg-
aquarium pump to supply the oxygen required for the reduction GO/TiO2 ). The SEM study was done with and without biofilm to
process. The design of the MFC used in the present study is shown differentiate the bacterial communities. A sterilized blade was used
in Fig. 1. All the experiments were done in duplicate to verify the to scratch the biofilm from the anodes to carry out the EDX analysis
results. (Khan et al., 2018). The EDX analysis was done to determine the
biocompatibility and the adsorption effect of Pb toward the anode
2.7. MFC characterization biofilm in the MFC operations.

To characterize the MFC operation, different electrochemical 2.8. Parameter optimization

and biological analyses were done. The voltage was recorded every
day until the completion of the operation. A digital multimeter was The pH, the temperature, and the organic substrate were opti-
used to record the potential between the anode and the cathode. mized for the power generation and metal removal efficiency in
To determine the current efficiency (power density (PD); current MFC for both built anodes (i.e., Lg-GO and Lg-GO/TiO2 ). For this, the
density (CD)), the Ohm law was used. The cyclic voltammetry (CV) pH was varied from 3 to 10. The pH was adjusted by using 1 M NaOH
technique was used to analyze the redox reaction on the electrode’s or 1 M HCl solution. The energy generated and removal efficiency

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A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Fig. 2. (a-b) Fourier transform infrared (FT-IR) spectra of Lg-GO and Lg-GO/TiO2 composite; (c) X-ray diffraction (XRD) spectra of Lg-GO and Lg-GO/TiO2 composite; (d)
Uv-absorbance spectra of Lg-GO and Lg-GO/TiO2 composite; (e) Raman spectra of Lg-GO and Lg-GO/TiO2 composite.

were determined after 10 days of operation for each pH range. Sim- spectrum which corresponded to the 002 peak and graphite oxi-
ilarly, the temperature was evaluated at 20, 25, 30, and 35 ◦ C at pH dation, but it did not confirm the synthesis of GO. Another peak

7 and using oil palm trunk sap as the organic substrate. The energy appeared at 2 = 10.25 confirming the successful synthesis of
was obtained after 24 h but the removal efficiency was determined Lg-GO. This peak also showed the complete oxidation of the car-
after 10 days of operation because the bacterial community takes bonized lignin as the brown colour material (inset in Fig. 2d) after
time to show its removal efficiency. Glucose and oil palm trunk 
completion via the Hummers method. The peak 2 = 10.25 also
sap were evaluated as organic substrates while keeping the pH at showed that there were several oxygen functional groups because
7 and room temperature. Both energy and removal efficiency were the interlayer spacing of Lg-GO (0.84 nm) was higher than that of
determined after 10 days of operation for each substrate. graphite (0.34 nm) which also confirmed the successful synthesis
    
of Lg-GO. Likewise, the 2 at 25.29 , 38 , 48 , 55 and 63 in Lg-
3. Results and discussion GO/TiO2 corresponded to the crystal planes of anatase TiO2 (Zhang
et al., 2018). After the solvothermal preparation of Lg-GO/TiO2 com-
 
3.1. Material characterization posite, the peak near 2 = 9.8 to 10.29 disappeared due to the
destruction of the regular stack of the Lg-GO structure as a result
3.1.1. Fourier transform infrared spectroscopy (FT-IR) of the intercalation of the TiO2 .
The prepared materials (Lg-GO and Lg-GO/TiO2 ) were analyzed
with FTIR spectroscopy. The FTIR spectrum of Lg-GO exhibited 3.1.3. UV-spectroscopy (UV)
peaks at 1050, 1350, 1590, and 3450 cm−1 which were ascribed The UV–vis absorbance spectroscopy was explored to study the
to the deformation and stretching vibrations of C OH, OH, COH, optical activities of the prepared materials as shown in Fig. 2d. Lg-
and CO groups, respectively (Fig. 2a). The prepared Lg-GO had GO showed a strong absorption at 240 nm with a flat shoulder
oxygen-based functional groups on the edges and basal planes of peak at 302 nm. The 240 nm absorption peak corresponded to the
its structure which increased its interlayer spacing and hydrophilic graphite ␲-plasmon excitation. These peak in Lg-GO was ascribed
properties. The peak at 1050 cm-1 was ascribed to C OH bend- to the aromatic CC bonds ð→ð* transition and C O bonds n→ð*
ing with mixed stretching CO vibrations and the peak at 1603 transitions. The spectrum of the Lg-GO/TiO2 composite showed a
cm-1 corresponded to C C skeletal vibrations. The broad peak at peak at 350 nm which indicated the TiO2 adsorption on the surface
3450 cm-1 corresponded to CO H hydroxyl stretching vibrations of the Lg-GO (Fig. 2d). The calculated band gaps of Lg-GO and Lg-
(Durmus et al., 2019). The presence of C O and −OH group stretch- GO/TiO2 were 5.17 and 3.54 eV, respectively, which suggested that
ing vibrations confirmed the presence of the carboxyl group in the the low bandgap of Lg-GO/TiO2 facilitated a good electric conduc-
Lg-GO structure. These polar functional groups offer attaching sites tivity.
for TiO2 adsorption on the surface of Lg-GO. In Fig. 2b one can
observe that the −OH group was also present in the Lg-GO/TiO2
3.1.4. Raman spectroscopy
composite. A minor absorption band at 525 cm-1 corresponded
Raman spectroscopy of Lg-GO and Lg-GO/TiO2 composite was
to the Ti-O which confirmed the presence of Ti in the Lg-GO/TiO2
explored in the range of 200 to 2500 cm−1 . In Raman spectra,
composite.
two bands appeared named as D-band and G-band (Fig. 2e). The
D band corresponded to the irregular and structural defects in the
3.1.2. X-ray diffraction (XRD) layer of graphite. Similarly, the G band showed the sp2 vibration
The XRD patterns of Lg-GO and Lg-GO/TiO2 composite are of the carbon atom which is associated with crystallization and

shown in Fig. 2c. A strong peak appeared at 2 = 24.1 in the Lg-GO symmetry of carbon atoms. The D band peak shifted from 1365

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A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Fig. 3. Scanning electron microscopy (SEM) images of (a) Lg-GO and (b) Lg-GO/TiO2 composite and transmission electron microscopy (TEM) images of (c) Lg-GO and (d)
Lg-GO/TiO2 composite.

Table 2 SEM image (Fig. 3b) specified that the TiO2 particles on the surface
Results from the Brunauer–Emmett–Teller method.
of the Lg-GO material were less than 100 nm in size (Ealias and
Fabricated anode BET surface area Pore size (Å) Pore volume Saravanakumar, 2017).
(m2 /g) (cm3 /g) EDX was performed to study the chemical/elemental compo-
Lg-GO 281.12 31.40 0.25 sitions of Lg-GO and Lg-GO/TiO2 materials. In Fig. S1 50.60 % of
Lg-GO/TiO2 225.00 41.49 10.23 carbon and around 40 % of oxygen are shown clearly indicating the
oxidation of graphite in the Lg-GO. Similarly, Lg-GO/TiO2 compos-
ite showed 45 % of carbon, 32 % of oxygen, and 22 % of Ti. Overall,
to 1357 cm−1 and the G band shifted from 1600 to 1595 cm−1 the results of the prepared materials confirmed the presence of
in the Lg-GO/TiO2 composite spectrum, indicating the presence required elements contained in the electrodes.
of oxygen-based functional groups in Lg-GO during the oxidation
of graphite. The carboxyl and hydroxyl functional groups were 3.1.7. Transmission electron microscopy (TEM) and atomic force
attached to boundary layers of Lg-GO showing its structural defects. microscopy (AFM)
The calculated intensity ratio of the Lg-GO/TiO2 composite was The TEM images of Lg-GO and Lg-GO/TiO2 composite material
higher than that of the Lg-GO meaning that the introduction of showed a high translucency level of structure. The morphology of
TiO2 in Lg-GO may increase its defects likely due to the chemical the materials indicated a high degree of oxidation. The surface of Lg-
bonding between TiO2 and Lg-GO. GO seems to be very cohesive and smooth due to the fine powder of
lignin used in the Lg-GO synthesis as shown in Fig. 3c. Similarly, the
3.1.5. Brunauer–Emmett–Teller (BET) Lg-GO/TiO2 composite presents a smooth surface where the TiO2
The synthesized Lg-GO and Lg-GO/TiO2 composite were charac- particles were attached (Fig. 3d). The overall composite particle
terized by using nitrogen absorption–desorption (BET) to measure range was less than 100 nm as shown in SEM images.
the definite surface area, pore size, and pore volume (Durmus et al., Additionally, AFM was carried out to examine the surface mor-
2019). The surface area offers a place for bacterial growth and an phology such as roughness, surface uniformity, etc. of the materials
optimized pore size promotes the reduction of pollutants instead used as shown in Fig. S2. Thus, Lg-GO showed a smooth surface
of adsorbing the organic substrate on the surface of the anode with irregular particle arrangement (Durmus et al., 2019) while
(Kirubaharan et al., 2015). The Lg-GO material presented a higher the Lg-GO/TiO2 composite surface was very compact.
surface area than that of the Lg-GO/TiO2 one due to it had a smaller
pore size (Table 2). The high surface area makes the present mate- 3.2. Performance of the prepared anodes in MFC
rial preferable to use as an anode.
3.2.1. Study of voltage generation trends and polarization
3.1.6. Scanning electron microscopy (SEM) and Energy-dispersive behavior
X-ray (EDX) To examine the electric potential of MFC using the fabricated
The SEM technique was used to study the morphological prop- anodes (i.e., Lg-GO and Lg-GO/TiO2 ), a 90-day operation was
erties of the prepared materials. Both Lg-GO and Lg-GO/TiO2 SEM performed as shown in Fig. 4a. A quite highvoltage generation dif-
images were taken at different magnification scales as shown in ference was observed at the beginning of the operation. The Lg-GO
Fig. 3(a-b). Fig. 3a revealed that Lg-GO presented a simple shape anode produced 1 mV on the first day while 2 mV was attained
due to an effective exfoliation which showed that the size of the Lg- by the Lg-GO/TiO2 anode in the same period. Both electrodes were
GO particle was up to 3 ␮m at different positions. Similarly, another operated in three cycles to validate the voltage generation trend in

53
A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Fig. 4. (a) Voltage trends of Lg-GO and Lg-GO/TiO2 with Pb (II) supplemented wastewater; (b) Polarization behavior of the Lg-GO anode; (c) Polarization behavior of the
Lg-GO/TiO2 composite anode; (d) CV profile of MFC with the Lg-GO anode; (e) CV profile of MFC with the Lg-GO/TiO2 composite anode; (f) Nyquist curves of the Lg-GO and
Lg-GO/TiO2 composite anodes.

MFC (Fig. 4a). In the three cycles, Lg-GO exhibited its highest voltage imum PD = 0.78 mW/m2 and CD = 70.17 mA/m2 at 1000  as shown
(113 mV) on the 25th day while Lg-GO/TiO2 showed its highest volt- in Fig. 4(b-c). The highest external resistance (10 k) delivered a
age (190 mV) on the 26th day. At the beginning of each cycle, both low current efficiency because voltage stabilization was high. The
electrodes showed an increasing trend until the 25th day due to the potential drop and slow stabilization at lower external resistances
presence of a fresh inoculum source. At a specific point, the volt- might be due to an effective discharge of electrons. The high exter-
age started to decrease because some bacteria entered the death nal resistance did not allow the electrons to move rapidly toward
phase as described by Yaqoob et al. (2020b). The continuous supply the cathode which generated low power because the external resis-
of organic substrate empowered some bacterial species to gener- tance increases the electron resistance against electron mobility
ate voltage. Thus, the second-highest voltage point was observed (Abazarian et al., 2016; Penteado et al., 2017). The observed internal
which is known as the second cycle and the achieved voltage was resistances were 1074  and 875  for the Lg-GO and Lg-GO/TiO2
184 mV and 111 mV for Lg-GO and Lg-GO/TiO2 , respectively. Then, anodic MFC operation, respectively. The Lg-GO/TiO2 anode showed
it started to decrease again but to validate the MFC performance the lowest external losses, the lowest internal resistance, and the
a continuous supply of organic substrate was done. After reach- lowest activation energy compared to the Lg-GO anode. The present
ing the lowest voltage point on the 56th day, it increased again setup with the lowest internal resistance showed the highest rate
in both cases, but the transferring rate of electrons was different of electron transportation which led to the highest current gener-
in each case. The results showed that the Lg-GO/TiO2 composite ation. The internal resistance of an MFC depends on (i) the nature
presented a higher electron transfer rate than that of the Lg-GO. and surface area of the electrode, (ii) the conductivity of the elec-
However, again, on the 3rd cycle, the highest voltage of 105 mV trode, (iii) the distance between the anode and the cathode, (iv) the
(Lg-GO) and 181 mV (Lg-GO/TiO2 ) were recorded on the 68th and reaction on the surface of the electrode and (v) the concentration
75th days, respectively. After that, the voltage decreased sharply in and the nature of the electrolyte (Sajana et al., 2017). Furthermore,
both cases to a value of 20 mV. Among the three cycles, the high- in the present work, an external oxygen supply was provided to
est voltage was attained on the first cycle which was related to the stabilize the voltage.
presence of fresh inoculum with mixed culture bacterial species.
All cycles showed the highest voltage stability at 1 k (external
3.2.2. Cyclic voltammetry (CV) and electrochemical impedance
resistance) because the lowest external resistance failed to stabi-
spectroscopy (EIS) studies
lize the voltage trend. In summary, both electrodes (i.e., Lg-GO and
The electrochemical behavior and electron transfer rate of the
Lg-GO/TiO2 ) showed high Pb (II) ions removal efficiency (85 % and
prepared electrodes were analyzed by using the CV and EIS tech-
90 %) and good electron transferring power but the presence of TiO2
niques. In Fig. 4(d-e) the performances of Lg-GO and Lg-GO/TiO2 at
significantly improved the electron transfer rate.
different time intervals in the forward scan (FS), as well as reverse
To assess the fabricated anodes’ performances, their polar-
scan (RS), are shown. For each operation, the maximum FS was
ization behaviours were studied at a varied range of external
2.3 × 10−5 ␮A for Lg-GO and 7.0 × 10-6 ␮A for Lg-GO/TiO2 and
resistances (from 150  to 10 k). This study helped to evaluate
the maximum RS was -4.1 × 10−5 ␮A for Lg-GO and -1.0 × 10−5
the cell design point (CDP) to obtain the maximum PD. The CDP is
␮A for Lg-GO/TiO2 . The oxidation peaks of Lg-GO and Lg-GO/TiO2
one of the most significant parameters to evaluate the performance
anodes were observed on the 20th day (0.80 V and 0.79 V, respec-
of an MFC. In the Lg-GO anode, the CDP was observed at 1000 
tively), 40th day (0.79 V and 0.80 V, respectively), 70th day (-0.1 V
with a maximum PD of 0.44 mW/m2 and the maximum recorded
and 8.20 V, respectively), and 90th day (-0.4 V and 8.4 V, respec-
CD was 57.01 mA/m2 while the Lg-GO/TiO2 anode showed its max-
tively). The observed reduction peaks of Lg-GO and Lg-GO/TiO2

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A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Table 3
The capacitances of the fabricated anodes with the exoelectrogens community on
the 20th, 40th, 70th, and 90th days in MFC.

Measurement duration (day) Capacitance (F/g)

Lg-GO Lg-GO/TiO2
th
20 0.00004 0.00003
40th 0.00008 0.00003
70th 0.00010 0.00011
90th 0.00008 0.00004

anodes were observed on the 20th day (-0.79 V and -8.0 V, respec-
tively), 40th day (-0.80 V and -0.79 V, respectively), 70th day (-0.81
V and -0.80 V, respectively), and 90th (-0.82 V and -0.81 V, respec-
tively). Therefore, the highest oxidation and reduction peaks were
observed on the 90th day which indicated a reverse transfer of elec-
trons. The oxidation/reduction peaks were high due to the extra
supply of oxygen in the cathode chamber which further neutral-
ized the electrons before entering the anode and also improved the
electron discharge rate (Liu et al., 2016). The reason for a high oxi- Fig. 5. Thermal gravimetric analysis (TGA) curve of Lg-GO and Lg-GO/TiO2 compos-
dation process in cells might be due to the presence of an organic ite anodes after 90 days of operation of MFC.

substrate that promotes the respiration rate. A highly conductive

electrode such as Lg-GO/TiO2 captures the electrons effectively and of the anodes were evaluated by EDX which results are shown
enhances their transfer rate (Zhou et al., 2011). In the present study, in Fig. S3. Recently, several studies have used this technique to
both electrodes showed excellent electron movement as well as confirm the presence of Pb ions on the anode surface. They con-
oxidation/reduction rates. cluded that if there is the presence of Pb ions on the anode surface,
In Table 3 the calculated Cp values from the CV curves are shown. then it means there is a toxic effect on the catalytic activity of the
The Cp value increased from the beginning up to a certain point and bacteria (Daud et al., 2021; Fadzli et al., 2021). The EDX analy-
afterward it decreased likely due to the destruction of the biofilm ses of the Lg-GO and Lg-GO/TiO2 anodes did not show any toxic
at the end of the reaction. According to Eq. (1), the Cp value for elements on the surfaces of the anodes which confirmed that
Lg-GO was 0.00004 F/g (20th day) and it increased with time up the cell environment was favourable to the bacterial community.
to 0.00010 F/g (70th day) and then it decreased to 0.00008 F/g on Based on this EDX study, it can be hypothesized that the Lg-GO
the 80th day. Similarly, the Lg-GO/TiO2 anode achieved its high- and Lg-GO/TiO2 anodes do not show metal ion adsorption during
est Cp value on the 70th day (0.00011 F/g) which showed healthy MFC operation. Similarly, to analyze the thermal and mechanical
biofilm developed on the surface of the anode but on the 90th day strengths of the fabricated anodes, TGA analysis was performed. In
it decreased showing that the bacteria entered the death phase. Fig. 5, both anodes showed good stability after 90 days of contin-
Hong et al. (2011) increased the anode capacitance by improving uous operation. However, the Lg-GO/TiO2 anode showed slightly
the oxidative/reductive peaks or the electron transfer mechanisms higher thermal stability than the Lg-GO. At 800 ◦ C Lg-GO and Lg-
and found a similar trend in the performance of biofilms via CV. GO/TiO2 showed 61 % and 66 % residue, respectively. The same
The EIS technique was used to measure the charge-transfer results were obtained after the 90-day operation of Lg-GO and
resistances of Lg-GO and Lg-GO/TiO2 anodes by using the fuel Lg-GO/TiO2 anodes.
cell circuit (Fig. 4f). The Nyquist curves were explored from 100 The durability was analyzed by operating the anodes at a con-
kHz to 100 mHz frequency range at 1.0 mV AC amplitude. The stant external resistance of 1000  during three operation cycles.
EIS Nyquist curves bent lines at high frequency referred to the According to Fig. 4a, Lg-GO reached a maximum voltage of 113 mV
high rate of electron transfer and a straight line at low frequency on the 25th day and Lg-GO/TiO2 of 190 mV on the 26th day. The
displayed a good capacitive behaviour (Hung et al., 2019). The suddenly increasing trend of voltage was due to the fresh inocu-
Lg-GO/TiO2 anode demonstrated higher electronic mobility and lum and rapid transfer of electrons. From that point onwards, the
lower charge resistance to the electrolyte than the Lg-GO. The voltage decreased in both cases but the Lg-GO/TiO2 anode showed
higher internal resistance (1074 ) in the case of the Lg-GO anode a lower decreasing trend than that of the Lg-GO anode. This means
resulted in poor electronic mobility activity between the electrode that the Lg-GO/TiO2 anode offered a more compatible surface area
and the redox solution. However, in the Lg-GO/TiO2 anode, the for bacterial growth than the Lg-GO anode. The observed biofilm
lower internal resistance (875 ) led to a higher transfer rate of on Lg-GO/TiO2 was denser than that of the Lg-GO. This confirmed
electrons within the redox reaction and the electrodes. The lower that the continuous organic substrate feeding empowered the bac-
charge transfer resistance in the modified anode increased the terial community to generate the electrons. Similarly, a third cycle
kinetic rate and simultaneously decreased the electron-transfer was operated with both electrodes, and 181 mV for Lg-GO/TiO2 and
resistance. 105 mV for Lg-GO anodes were attained. During the three opera-
tion cycles, both electrodes showed stable performances without
3.2.3. Stability and durability studies of electrodes any destruction of biofilm or material. The Lg-GO/TiO2 electrode
The stability and durability of the electrodes are among the most showed better performance than that of Lg-GO because TiO2 helped
important aspects of MFC for energy generation and wastewater increased electron transportation and reduced the accumulation
treatment. In the present study, the stability (chemical, biocom- of undesirable materials. However, both fabricated anodes showed
patibility, thermal) and durability of the fabricated anodes were good durability up to 90 days. Mishra et al. (2017) also studied
assessed. The SEM images of the anode biofilm, taken after 90 the stability of the prepared electrodes based on electrochemical
days of MFC operation, showed that the fabricated anodes were results after continuous MFC operation and found the durability
biocompatible and chemically stable. To further confirm the tox- period of their electrodes for 45 days. Senthilkumar et al.(2020) on
icity effect of the Pb (II) ions after remediation on the surfaces the other hand, reported a durability period of 15 days for waste-

55
A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Table 4
A comparative profile of prepared anodes in MFC.

Anode electrode Electrode size Inoculation source Durability (days) Current density References
(mA/m2 )

ACa /PANIb /D-CSAc /GFd Length:100–200 nm, Mix culture bacteria 6.2 110 mA/m2 (Scott et al., 2007)
Diameter: 80 nm
CPe /HAPNWf 3.14 cm × 2.5 cm Shewanella loihica 2.2 2.9 mA /cm2 (Zhao et al., 2011)
Fe3 O4 /ACa /SSMg 4 cm × 3 cm Pre-acclimated effluent 5 1.9 mA/m2 (Peng et al., 2013)
Graphene/PEDOTh /CPe 2 cm × 2.5 cm Escherichia coli 24 3.59 mA/m2 (Wang et al., 2013)
Fe3 O4 /CPe 2.5 cm × 4.5 cm Mix culture bacteria species 16.5 – (Kim et al., 2005)
CNTi /CCj 6 cm × 3.5 cm Mix culture 8-9 65 mA/m2 (Tsai et al., 2009)
NGNSk 1 cm × 1.5 cm Escherichia coli 4.1 – (Kirubaharan et al., 2015)
PEIl /GFd – Saccharomyces cerevisiae 5 – (Christwardana et al., 2018)
Cellulose-derived GO 7.5 cm × 1.2 cm Synthetic wastewater 40 24.56 mA/m2 (Yaqoob et al., 2021)
Lg-GO 8.0cm × 1.3cm Synthetic wastewater 90 57.01 mA/m2 Present work
Lg-GO/TiO2 8.0cm × 1.3cm Synthetic wastewater 90 70.17 mA/m2 Present work
a
Activated carbon.
b
Polyaniline.
c
D-camforsulfonic acid.
d
Graphite felt.
e
Carbon paper.
f
Hydroxylated and aminated polyaniline nanowire.
g
Stainless steel meshes.
h
Poly(3,4-ethylenedioxythiophene).
i
Carbon nanotubes.
j
Carbon cloth.
k
N doped graphene nanosheets.
l
Polyethyleneamine.

derived anodes. A comparison of the proposed systems is shown in ation (57.01 mA/m2 and 70.17 mA/m2 for Lg-GO and Lg-GO/TiO2 ,
Table 4. respectively).

3.2.5. Biofilm morphological studies

3.2.4. Effect of the prepared electrodes on the removal efficiency The biofilm was formed on the surface of the anodes as well as
of Pb (II) ions on the cathode during 90 days of MFC operation. In Fig. 6 the pres-
The electrodes also directly play a vital role in wastewater ence of bacterial communities on the surfaces of both anodes after
treatment. The anodic biofilm-based bacteria converted the metal 90 days of MFC operation are shown where the Lg-GO/TiO2 being
ions present in wastewater into their insoluble forms via oxida- denser. The SEM image of the untreated anodes however showed
tion/reduction mechanisms (Asim et al., 2021; Luo et al., 2009). that there was no presence of bacteria was observed. The forma-
Several studies reporting the removal of toxic metals from wastew- tion of biofilms on the cathodes was also observed, but it was not as
ater by using different electrode materials in MFC are shown in dense as that of the anodes. Further, according to the SEM images
Table S1. In the present study, waste-derived modified graphene of biofilms, the filamentous appendages shaped bacterial colonies
oxide was used to build anodes (Lg-GO and Lg-GO/TiO2 ) for MFC were present on the surfaces of the anodes. There are many studies
which were further applied to remove Pb (II) ions (100 mg/L) from on biofilm morphology but very few showed the presence of con-
synthetic wastewater. Based on the previous evidence, for exam- ductive filamentous appendages (He et al., 2011). According to the
ple, Massadeh et al. (2005) studied the removal efficiency of Pb SEM findings, a hypothesis can be formulated that the observed
and Cd by using different concentrations (100 and 500 ppm). They conductive filamentous appendages (conductive pili) of bacteria
achieved a maximum of 89.48 % removal efficiency at 100 ppm in are capable of transferring electrons. The conductive pili are usually
the presence of different bacterial species. Similarly, several other the dominant mechanism to transfer electrons in bacterial species
studies stated that bacterial species can degrade the sole Pb ions but there are also other mechanisms such as long-range electron
from wastewater up to 100 ppm effectively (Chimhundi et al., 2021; transfer, short-range electron transfer, and electrode transfer by
Sinha and Biswas, 2014). However, there are some pieces of evi- electrons shuttles. Several earlier studies indicated the presence of
dence to suggest that concentrations up to 50 ppm/L are toxic conductive pili in bacterial species such as Klebsiella pneumoniae,
to bacterial species (Mwandira et al., 2020; Sobolev and Begonia, Enterobacter, Bacillus, Acinetobacter, etc. A depth discussion on the
2008). For example, Mwandira et al. (2020) carried an experiment mechanism of electron transfer was reported in the previous works
to remove the Pb ions at 50 ppm/L but the inoculation source also (Yaqoob et al., 2020b, 2021).
contained Zn (II) ions (50 ppm/L) which were also toxic. Therefore,
it might affect the overall removal efficiency rate. According to the 3.3. Multiple parameters optimization by using the prepared
current scenario, the inoculation contains only Pb (II) ions, and fur- anode in MFC
ther, the bacteria are energized by a rich carbohydrate source (oil
palm trunk sap) to maintain and improved the bacterial strength For optimization purposes, three main parameters which are
against the toxic effects of Pb (II). In the present work, Lg-GO/TiO2 temperature, pH, and organic substrate were considered to achieve
showed a higher removal efficiency than Lg-GO. It was observed the maximum performance of MFC in terms of energy generation
that the Lg-GO anode removed 22 % of Pb (II) ions and Lg-GO/TiO2 and metal removal.
removed 26 % of Pb (II) ions within 20 days of MFC operation. At the
end of the process, both anodes attained a maximum removal effi- 3.3.1. Effect of pH on energy generation and metal removal
ciency higher than 80 % as shown in Table 5. Both fabricated anodes efficiency in MFC
showed excellent Pb (II) removal efficiency but the Lg-GO/TiO2 It was found that the pH range (3–10) was directly proportional
composite anode manage to produce much higher energy gener- to the energy output in MFC operation (Fig. 7a). An acidic environ-

56
A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Table 5
Pb (II) ions removal performances of the present study.

Anode Cathode Size of anodes Surface area Inoculation Initial Target pollutant Time interval Removal
(cm2 ) source concentration (days) efficiency (%)
(mg)

0 0
20 22
Synthetic Pb 40 50
Lg-GO Graphite rod 8 cm × 1.3 cm 76 100
wastewater (II) 60 70
80 81
90 85
0 0
20 26
Synthetic Pb 40 55
Lg-GO/TiO2 Graphite rod 8 cm × 1.3 cm 76 100
wastewater (II) 60 73
80 86
90 90

Fig. 6. Scanning electron microscopy (SEM) photographs of Lg-GO and Lg-GO/TiO2 anode before and after a 90-day operation and their respective graphite rod cathode
electrodes after a 90-day operation.

Fig. 7. Effect of (a) pH and (b) temperature on energy generation and removal efficiency of Pb (II) by using the prepared anodes (Lg-GO and Lg-GO/TiO2 anodes) in MFC.

57
A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

ment was not favourable due to the formation of acidic products.

Thus, at pH 3, 7 mV in the case of Lg-GO and 11 mV for Lg-GO/TiO2
were achieved. Similarly, alkaline conditions also offered very low
energy output (i.e., at pH 10, the 5 mV for Lg-GO and 7 mV for Lg-
GO/TiO2 were obtained). In moderately alkaline conditions, such as
pH values of 8 and 9, it offered better voltage generation as com-
pared to acidic conditions. Yuan et al. (2011) reported moderate
biofilm formation on the surface of the anode under alkaline con-
ditions (pH 8, 9). In the present study, 48 mV (Lg-GO) and 55 mV
(Lg-GO/TiO2 ) were achieved at pH 7. He et al. (2008) studied the
pH effect in MFC and stated that the power generation was low
at pH 5 and 6 as compared to pH 7 and 8. They concluded that
pH 7 was the most preferable one for the living bacterial respira-
tion process. Huang et al. (2012) also discovered that pH 7 was
appropriate for the rapid generation of electrons from bacteria.
Similarly, maximum Pb (II) ions removal efficiency was obtained
in both cases (Lg-GO and Lg-GO/TiO2 ) at pH 7. In acidic condi-
Fig. 8. Effect of oil palm trunk sap and glucose on energy generation and Pb (II) ions
tions, both electrodes showed less removal efficiency due to the removal by using Lg-GO and Lg-GO/TiO2 prepared anodes in MFC.
poor oxidation/reduction process of bacteria. At pH 7 the maxi-
mum removal efficiencies of Pb (II) of 18 % for Lg-GO and 20 % for
Lg-GO/TiO2 within a 10-day MFC operation were achieved. Typi- by using a glucose solution. It was found that the waste-derived
cally, pH 7 is suitable for maximum removal efficiency by bacterial organic substrate was more effective than glucose to enhance the
species. Therefore, it is very important to maintain the pH at 7. bacterial growth and the oxidation process. Similarly, higher Pb (II)
removal efficiency was achieved in the case of oil palm trunk sap
3.3.2. Effect of temperature on energy generation and metal than glucose. Thus, the achieved Pb (II) removal efficiency was 11 %
removal efficiency in MFC for Lg-GO and 13 % for Lg-GO/TiO2 after 10 days of MFC operation by
Temperature values of 20, 25, 30, and 35 ◦ C were used to eval- using oil palm trunk sap and 9 % for Lg-GO and 13 % for Lg-GO/TiO2
uate the performance of the prepared anodes (Fig. 7b). The results with glucose (Fig. 8). In addition, some efforts have been made for
showed that there was no temperature effect on anodes mor- the use of organic substrates derived from waste to achieve high
phologies due to their high thermal stability. Further, the effect MFC performance but still insufficient due to poor use of electrode
of temperature on cell performance was observed. At 25 ◦ C the materials. In this study, a combination of better materials for the
maximum energy generation for both electrodes (i.e., 48 mV for electrode as well as oil palm trunk sap showed much better voltage
Lg-GO and 57 mV for Lg-GO/TiO2 ) were observed. As the tempera- efficiency was successfully obtained. Several waste-derived organic
ture increased to 30 ◦ C and 35 ◦ C, the energy generation efficiency substrates and their performances are shown in Table S2.
was reduced. Similarly, a temperature of 20 ◦ C also does not offer
a stable environment for bacterial growth and the respiratory pro- 4. Conclusion
cess.
The temperature also had a direct effect on the removal effi- To address current challenges to electrode performance in
ciency of Pb (II) ions. Thus, as the temperature increased, the Pb MFC, biomass-derived modified graphene oxide (GO) anodes have
(II) removal efficiency also increased up to a certain point, then it been explored as an advanced material to enhance electron trans-
showed a decreasing trend. The highest removal efficiencies were fer. The use of waste materials to generate energy as well as
18 % (Lg-GO) and 20 % (Lg-GO/TiO2 ) within 10 days at 25 ◦ C but water treatment is an attractive approach in the modern world
at 30 ◦ C and 35 ◦ C, the removal rates were quite low due to the because of its cost-effectiveness. Composites between GO produced
destruction of biofilm at higher temperatures. Temperature affects from biomass with TiO2 metal oxide brought success especially
the morphology of the biofilm so that one may not be able to obtain in increasing the rate of electron transfer and biofilm formation.
the results as expected. TiO2 , used as a modifier due to its electronic and high conduc-
tivity, helped to improve the performance in energy generation
3.3.3. Effect of the organic substrate on energy generation and as well as the removal of Pb (II). The Lg-GO generated 57.01
metal removal efficiency in MFC mA/m2 current density with 85 % removal efficiency of Pb (II) while
The organic substrate is also known as organic fuel and it is an Lg-GO/TiO2 generated 70.17 mA/m2 with 90 % Pb (II) removal effi-
important part of bioelectrochemical cells. The organic substrate ciency in the 90-day operation of MFC. In the Lg-GO anode, the
promotes the oxidation process in the anode chamber which pro- observed maximum was PD of 0.44 mW/m2 and the Lg-GO/TiO2
duces electrons and protons (Barbosa et al., 2017). Several types of anode showed maximum PD = 0.78 mW/m2 . In conclusion, both
organic substrates for MFC have been studied such as glucose, acetic electrodes showed excellent removal efficiencies because they are
acid, carbohydrates, proteins, etc. (Gezginci and Uysal, 2016; Pant biocompatible and chemically stable. The operations showed no
et al., 2010; Singh and Songera, 2012). The utilization of a cost-free toxicity to bacterial species that successfully converted Pb (II) into
organic substrate is very attractive because it can reduce the overall an insoluble form. The anodes showed no effect of metal adsorption
cost of the MFC operation. In the present work, oil palm trunk sap on them. However, there was a big difference in energy generation.
which is a biomass waste material extracted from oil palm trunk The Lg-GO/TiO2 composite produced 7 times more energy than the
was used as an organic substrate. The achieved results (energy gen- Lg-GO anode due to the presence of TiO2 which increased the elec-
eration and metal removal) were quite high in both cases (Lg-GO tron transfer rate. The study also emphasizes the optimization of
and Lg-GO/TiO2 ). However, to validate the efficiency of the organic several key parameters (pH, temperature, and organic substrate) to
substrate derived from oil palm waste, it was compared using com- validate the performance of the prepared electrodes. Finally, based
mercial glucose. By using oil palm trunk sap, 48 mV for Lg-GO and 56 on the results obtained, the presently prepared anodes are suitable
mV for Lg-GO/TiO2 were achieved after 10 days of MFC operation, and recommended for metal ion removal and power generation via
while 45 mV for Lg-GO and 51 mV for Lg-GO/TiO2 were recorded MFC.

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A.A. Yaqoob et al. Process Safety and Environmental Protection 155 (2021) 49–60

Authors contributions Durmus, Z., Kurt, B.Z., Durmus, A., 2019. Synthesis and characterization of graphene
oxide/zinc oxide (GO/ZnO) nanocomposite and its utilization for photocatalytic
degradation of basic Fuchsin dye. ChemistrySelect 4, 271–278.
Mohamad Nasir Mohamad Ibrahim: Conceptualization, Asim Ali Ealias, A.M., Saravanakumar, M., 2017. A review on the classification, characterisa-
Yaqoob: Methodology, writing-original drat preparation, visualiza- tion, synthesis of nanoparticles and their application. IOP Conf. Ser. Mater. Sci.
tion, investigation. Susana Rodríguez-Couto, Akil Ahmad: Writing Eng. 263, 032019.
Fadzli, F.S., Rashid, M., Yaqoob, A.A., Ibrahim, M.N.M., 2021. Electricity generation
Reviewing and Editing, Mohamad Nasir Mohamad Ibrahim: Super- and heavy metal remediation by utilizing yam (Dioscorea alata) waste in benthic
vision, funding acquisition. This article has been read and approved microbial fuel cells (BMFCs). Biochem. Eng. J. 172, 108067.
by all listed authors. Gezginci, M., Uysal, Y., 2016. The Effect of different substrate sources used in micro-
bial fuel cells on microbial community. JSM Environ. Sci. Ecol. 4, 1035.
Guerrero-Barajas, C., Yaqoob, A.A., Ibrahim, M.N.M., 2021. Modern trend of anodes
Declaration of Competing Interest in microbial fuel cells (MFCs): an overview. Environ. Technol. Innov. 23, 101579.
Habibul, N., Hu, Y., Sheng, G.-P., 2016. Microbial fuel cell driving electrokinetic reme-
diation of toxic metal contaminated soils. J. Hazard. Mater. 318, 9–14.
The authors declare that they have no known competing finan- He, Z., Huang, Y., Manohar, A.K., Mansfeld, F., 2008. Effect of electrolyte pH on the
cial interests or personal relationships that could have appeared to rate of the anodic and cathodic reactions in an air-cathode microbial fuel cell.
Bioelectrochemistry 74, 78–82.
influence the work reported in this paper. Furthermore, Prof. Dr.
He, G., Gu, Y., He, S., Schröder, U., Chen, S., Hou, H., 2011. Effect of fiber diameter on
Rokiah Hashim’s research group had no role in the design of the the behavior of biofilm and anodic performance of fiber electrodes in microbial
study; experiment, collection, analysis, or interpretation of data; in fuel cells. Bioresour. Technol. 102, 10763–10766.
Hiegemann, H., Littfinski, T., Krimmler, S., Lübken, M., Klein, D., Schmelz, K.G., Ooms,
writing the manuscript, or in the decision to publish the results.
K., Pant, D., Wichern, M., 2019. Performance and inorganic fouling of a submergi-
ble 255 L prototype microbial fuel cell module during continuous long-term
operation with real municipal wastewater under practical conditions. Bioresour.
Acknowledgments
Technol. 294, 122227.
Hong, Y., Call, D.F., Werner, C.M., Logan, B.E., 2011. Adaptation to high current using
This research article was financially supported by Univer- low external resistances eliminates power overshoot in microbial fuel cells.
Biosens. Bioelectron. 28, 71–76.
siti Sains Malaysia, Malaysia. The author (Prof. Dr. Mohamad
Huang, L., Chai, X., Quan, X., Logan, B.E., Chen, G., 2012. Reductive dechlorination and
Nasir Mohamad Ibrahim) gratefully acknowledges Prof. Dr. Rokiah mineralization of pentachlorophenol in biocathode microbial fuel cells. Biore-
Hashim’s research group from the School of Industrial Technology, sour. Technol. 111, 167–174.
Universiti Sains Malaysia, Malaysia for providing the oil palm trunk Hung, Y.-H., Liu, T.-Y., Chen, H.-Y., 2019. Renewable coffee waste-derived porous car-
bons as anode materials for high-performance sustainable microbial fuel cells.
sap. ACS Sustain. Chem. Eng. 7, 16991–16999.
Ibrahim, M.N.M., Ahmed-Haras, M.R., Sipaut, C.S., Aboul-Enein, H.Y., Mohamed,
A.A., 2010. Preparation and characterization of a newly water soluble lignin
Appendix A. Supplementary data graft copolymer from oil palm lignocellulosic waste. Carbohydr. Polym. 80,
1102–1110.
Supplementary material related to this article can be found, in Jadhav, D.A., Carmona-Martínez, A.A., Chendake, A.D., Pandit, S., Pant, D., 2020a.
Modeling and optimization strategies towards performance enhancement of
the online version, at doi:https://doi.org/10.1016/j.psep.2021.09. microbial fuel cells. Bioresour. Technol. 320, 124256.
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