international journal of hydrogen energy xxx (xxxx) xxx

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Amplifying power generation in microbial fuel cells

with cathode catalyst of graphite-based
nanomaterials

T. Sathish a,*, Ravishankar Sathyamurthy b, S. Sandeep Kumar c,

Gia Bao Huynh d,**, R. Saravanan a, M. Rajasimman e
a
Department of Mechanical Engineering, Saveetha School of Engineering, SIMATS, Chennai, Tamil Nadu, India
b
Department of Mechanical Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi
Arabia
c
Department of Computer Science Engineering, Koneru Lakshmaiah Education Foundation, Vaddeswaram 522302,
Andhra Pradesh, India
d
Department of Chemistry Education, School of Education, Can Tho University, Can Tho City, 94115, Viet Nam
e
Department of Chemical Engineering, Annamalai University, Annamalai Nagar-608002, India

highlights

Nano-cathode catalysts rGOHI-AcOH and rGO/Ni tested for boost-up MFCs power output.

Long-lasting eco-friendly Cathode catalyst rGOHI-AcOH for reliable operation of MFC.

Single double and Triple load considered with rGOHI-AcOH & rGO/Ni cathode catalysts.

MFC produced maximal power densities at 1691 ± 34 mW/m2 with DL rGOHI-AcOH cathodes.

rGOHI-AcOH cathode cost is 73% less than the Platinum/Carbon cathode.

article info abstract

Article history: Low catalytic activity, scarcity of resources, design complexity, high cost, and unfavourable
Received 10 October 2022 nature of non-traditional metal and its composites limit their utilization as cathodes in
Received in revised form microbial fuel cells (MFCs). This research aimed to identify the most effective new cathode
30 November 2022 catalyst for use in one chamber air cathode microbial fuel cells by comparing two graphite-
Accepted 6 December 2022 based nanomaterials of Reduced Graphene Oxide Hydrogen iodide - Acetic acid (rGOHI-AcOH)
Available online xxx and Reduced Graphite Oxide Nickel Nanoparticles (rGO/Ni) composite. The behavior of
microbial fuel cells was calculated using cyclic voltammetry (CV) and electrochemical
Keywords: impedance spectroscopy (EIS). Since the rGOHI-AcOH cathodes were more efficient, the MFCs
Cathode produced maximum power (>37%) than the rGO/Ni Nanoparticles cathode MFCs. The
Eco-friendly double loading (DL) rGOHI-AcOH cathodes in the Microbial Fuel Cells produced the maximal
Graphite power densities at 1691 ± 34 mW/m2 (CE ¼ 73 ± 5%), covering 78% of the power densities
Green catalyst calculated for Platinum/Carbon (Pt/C) (2203 ± 52 mW/m2; CE ¼ 82 ± 3%). With a double
Hydrogen iodide catalyst load, MFCs using rGO/Ni Nanoparticles composite anodes produced more power
Microbial fuel cells than the others (1016 ± 31 mW/m2, CE ¼ 71 ± 3%). Excellent concordance was seen between
CV and EIS and the MFC findings. Based on the results of this research, the rGOHI-AcOH
cathode loaded with two catalysts has the potential to produce long-lasting,

* Corresponding author. Department of Mechanical Engineering, Saveetha School of Engineering, SIMATS, Chennai, Tamil Nadu, India.
** Corresponding author. Department of Chemistry Education, School of Education, Can Tho University, Can Tho City, 94115, Viet Nam.
E-mail addresses: sathish.sailer@gmail.com (T. Sathish), hgbao@ctu.edu.vn (G.B. Huynh).
https://doi.org/10.1016/j.ijhydene.2022.12.077
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Sathish T et al., Amplifying power generation in microbial fuel cells with cathode catalyst of graphite-based
nanomaterials, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2022.12.077
2 international journal of hydrogen energy xxx (xxxx) xxx

environmentally friendly materials at low cost and maintain consistent power output and
the reliable operation of MFCs throughout their useful lifetimes.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

For example, reductants show slow or stop the growth of

Introduction aquatic species, leading to their eventual death. The exposure
of humans to these reductants leads to cancer [22].
Globally adopted sustainable development goals (SDGs) are to When metal Nanoparticles are introduced between rGO
be achieved in multiple ways through research. Achieving is sheets, they function as spacers to keep the sheets from
prime important and indispensable in environmental adhering to one another during the drying process [23,24].
research. This research was also motivated by the above-said Furthermore, the inexpensive cost and high availability of Ni-
reason and made an attempt to develop a long-lasting, envi- Nanoparticles make them an alternative. However, rGO/Ni
ronmentally friendly cathode catalyst for enhancing the per- composites have not been reported for use as a catalyst in
formance of microbial fuel cells (MFCs) in terms of consistent Microbial Fuel Cells [25]. Despite this, research into Reduced
power output with reliable performance. Using MFCs to Graphite Oxide Nickel Nanoparticles composites as a cathode
deliver energy from organic waste is a new, sustainable, and catalyst remains crucial. In this way, learning about the syn-
feasible technology [1]. Carbon dioxide (CO2) and biomass are ergistic impact of graphite and Ni Nanoparticles is essential
produced as byproducts of organic materials' microbial for the catalytic activity and selectivity of the composite
oxidation in the anodic compartment [2,3]. Electrons are catalyst [26,27].
moved to cathode region by an exterior circuit after interact- Hence the research gap could be derived that, It is possible
ing through electron acceptors, produce the electric current to enhance the efficiency of the MFC by using single and more
[4]. Due to their low power output, MFCs are not generally conductive graphite materials as a different cathode catalyst
adopted. Because of the slow kinetics of oxygen drop in the by avoiding the limitations of the stimuli. This investigation
standard [5], cathodes are considered to the obstruction of the aims to produce highly conductive rGO using a reducing agent
microbial fuel cells performance along with the substrate, cell called Reduced Graphene Oxide Hydrogen iodide - Acetic acid
design, surface area of anode and bacterial inoculum [6]. (rGOHI-AcOH), which is powerful, safe, and flexible. Improving
Catalyst materials with a cheap cost, higher surface area, good the performance of MFC requires the evaluation of Reduced
stability, high conduction, and higher catalytic activities are Graphite Oxide Hydrogen iodide and acetic acid. For
preferred for MFCs' cathode reaction [7e9]. addressing this issue, it is planned in this investigation that
Nanoparticles crafted from noble metals, like platinum, the feasibility and potential effectiveness of using rGOHI-AcOH
gold, palladium, and their alloys show as catalysts for oxygen and Reduced Graphite Oxide Nickel Nanoparticles as the
reduction reaction [10]. In fuel cells, platinum (Pt) is employed cathode catalyst in air-cathode Microbial Fuel Cells to
almost exclusively as a cathode catalyst. However, catalyst generate energy to be investigated. The commercial Platinum/
toxicity, high prices, and scarcity work against widespread use Carbon catalyst was used as a standard for performance. EIS
in the real world [11]. An electrochemical reaction named and CV were used to evaluate the electrochemical behavior of
oxygen reduction reaction (ORR) has wide application like MFC.
decoration or chemical doping. Many studies have focused on
cost-effective catalysts to enhance ORR reactivity at the
cathode surface [12]. These studies show that low-cost metal Experimental methods
catalysts may effectively replace Pt without reducing power
production [13,14]. It was demonstrated that modifying the Preparation of catalysts
electrodes was a viable option for improving the MFCs' effec-
tiveness and showed the erratic behavior of different Reduced Graphite Oxide Hydrogen iodide, acetic acid, and
electrodes. Reduced Graphite Oxide Nickel Nanoparticles composite cat-
In contrast, oxygen electro-reduction is hardly facilitated alysts were prepared and characterized in detail [28]. Fig. 1
by these carbonaceous molecules [15,16]. Due to the shows a simplified process flow for creating triggers. In a
maximum surface area, higher electrical conduction, excel- nutshell, GO was synthesized by performing a simple room-
lent chemical stabilization, and higher mechanical properties, temperature method on natural graphite powder. The rGO
graphite nanosheets have recently arisen as a unique way to catalyst was prepared by a single-step chemical reduction
exploit two-dimensional carbon materials as a catalyst [17]. using HI-AcOH. Consequently, acetic acid diluted some GO
Numerous studies have examined the use of graphite and N (0.4 g) (150 ml). 8 ml of HI were added and stirred for 24 h at
functionalized graphite as MFC cathodes in conjunction with 40  C. Impurities were removed by filtering out the product
Iron, Manganese dioxide, and Platinum/Cobalt alloy nano- and washing it in a series of saturated NaHCO3, C3H6O, and
composites [18,19]. distilled water. After being vacuum dried at 40  C, the product
Furthermore, reductants (such as N2H4 and NaBH4) might was stored in a cool place. The reduced graphite oxide Nickel
be hazardous to the environment and human health [20,21]. nanocomposite catalyst with mass ration of 1:1 and heated

Please cite this article as: Sathish T et al., Amplifying power generation in microbial fuel cells with cathode catalyst of graphite-based
nanomaterials, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2022.12.077
 international journal of hydrogen energy xxx (xxxx) xxx 3

Fig. 1 e The process flow diagram for producing Reduced Graphite Oxide Hydrogen iodide and acetic acid and Reduced
Graphite Oxide Nickel Nanoparticles catalysts.

with NiCl26H2O and heated with N2H2 up to 150  C for 12 h to black in 3.31 ml isopropyl alcohol, 0.83 ml distilled water, and
activate the reaction. 6.67 ml Nafion solution for 30 min yielded an ink catalyst,
A monochromatic source of 40 mm in diameter and 30 eV which was then coated onto carbon fabric (liquid side). Wet-
in pass energy was used to obtain the XPS data, and the results proofed carbon cloth of 8 cm2 (DL) and 1.6 mg/cm2 (SL) and
were examined with an XPS instrument. Images of Raman 1.1 mg/cm2 (triple loading) was used to keep the catalyst
spectra were obtained with the help of a Raman spectrometer. loading at 0.5 mg/cm2.
In this piece of research there is no human samples involved
for investigation. So, there is no specific ethical approval MFC construction
required for this investigation.
Liquid chamber dimensions of 5 cm in span and 1.5 cm in
Synthesis of electrodes radius (fluid volume of 29 ml) were used to make cylindrical
Microbial Fuel Cells (made of acrylic glass) with an air cathode,
The electrodes were sonicated for 15 min in acetone, 1 M as previously described [31,32]. A vertical membrane sepa-
Hydrochloric, de-ionized water, and C2H5OH; after that, it was rated the cathode from the anode brush and was arranged flat
dried to clean the surfaces. A graphite brush (1.25 cm in on the other side of the cavity. A separate load was connected
radius, 2.6 cm in length, 0.23 m in surface area, 96% porosity, to the circuit using titanium wire.
and 7.2 mm in average fiber diameter) was employed as an
anode [29]. The air cathode was made using a previous Microbial fuel cells processing
research method [30]. The cathode electrode was the back-
bone of the cell, accounting for 30 wt % of the total exposed An anaerobic mud was added with the composites at a 1:9
surface area. Sonicating (1 mg of catalyst) with 10% carbon ratio and then frequently supplied over 120 h to develop

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nanomaterials, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2022.12.077
4 international journal of hydrogen energy xxx (xxxx) xxx

biofilm growth on the anode surface of the Microbial Fuel Maximum voltages of 134 ± 0.6 mV for Single Load,
Cells. The culture medium was made by combining 50 mM 178 ± 0.2 mV for Double Load, and 166 ± 0.5 mV for Triple Load
phosphate buffered solution with 12.5 ml of metal and then cathode catalysts were achieved in rGO/Ni Nanoparticles
adding sodium acetate (1 g/L). The exact concentrations of MFCs.
each ingredient in the 50 mM PBS solution were as follows: Fig. 3 shows power density and polarization curve to the
0.14 g/L KCl, 3.34 g/L Sodium dihydrogen phosphate (NaH2- current density for various microbial fuel cells. With the
PO42H2O), 10.33 g/L Sodium phosphate dibasic dodecahydrate Platinum/Carbon cathodes, the MFCs can produce a higher
(Na2HPO412H2O). Each MFC was operated in group mode at power density (2203 ± 52 mW/m2, 1.03 ± 0.02 mA/cm2). The
30.1 . The anode biofilm produced a small amount of voltage, main reason for this difference is that on a Pt/C catalyst, ORR
and the voltage steadily grew more saturated with electro- positively proceeds via the four-electron reduction pathway.
chemically active bacteria. The voltage dropped below In contrast, on graphite-based materials, ORR happens via the
5e10 mV every time the chamber was refilled. After the ex- two-electron reduction pathway [36]. The exceptional perfor-
periments, the best MFC gives a standard growth comprising mance of Microbial Fuel Cells with a Reduced Graphite Oxide
one g/L glucose to facilitate a fair comparison with other MFCs' Hydrogen iodide and acetic acid catalyst on the cathodes is
growth under optimal conditions. highlighted in comparison to Microbial Fuel Cells using
Reduced Graphite Oxide Nickel Nanoparticles cathodes.
Investigative methods rGOHI-AcOH's excellent qualities make it well suited for MFC
system expansion [37,38].
A multimeter and data recorder was used to obtain the voltage The crumpling features with visible layers seen in the SEM
of the experimental cell. The output power was determined by image in the SEM image may be responsible for area and
using the ohms law (P]IV), and the flowing current was nanostructure (345 m2/g), as shown in Fig. 4a (i). Furthermore,
measured using formula I ¼ V/R. By using a single-cycle scanning electron microscopy images revealed the formation
approach, maximum power density for the MFC was achieved. (stacking randomly) of spherical-like Nickel Nanoparticles
Polarization of MFC during their steady state was mapped with exact size on the Reduced Graphite Oxide layers, which
out after open circuit potential (OCP) was stabilized through may inhibit aggregation (247 m2/g). As shown in Fig. 4b, the
reducing resistance from 10,000 to 20 (over 30 min) [33]. A broad scan XPS spectra of the as-prepared catalysts suggest
drenched silver/silver chloride (3 M Potassium Chloride) is that C, O, and Ni are the primary species. The oxygen-to-
placed in the reactor nearer to the cathode to measure the carbon (C/O) atomic ratio of rGOHI-AcOH is 5.17 using XPS.
voltage using a multimeter, and the potential difference of Due to their high current conductivity, graphite materials with
each electrode is recorded. a high C/O percentage propose an effective reduction tech-
The coulomb efficiency was determined by subtracting the nique. Graphite Oxide/Nickel Nanoparticles composite may
total coulomb from the theoretical quantity of the coulomb have been introduced through surface oxidation when the
based on the chemical oxygen demand eliminated from MFC sample was transported from deposition chamber to X-ray
[34,35]. A HACH DR 2500 spectrophotometer was employed to photoelectron spectroscopy, or it may have been adsorbed
measure the COD levels in both the effect and the runoff. The during the manufacture of the composite. Raman spectra
anode, counter electrode, and reference electrode connections (Fig. 4c) showed the expected 2D, D, and G bands at 1352, 1595,
were made to the cathode, while the working electrode and 2924 cm1.
connector was connected to the anode. CV was conducted at
scan rates of 10 mV/s over a potential range of þ1 V to 1 V
R
AUC ¼ V1 IðVÞdV. The EIS was performed at an amplitude of
0.05 mV, spanning the frequency range of 0.1 Hze1 MHz.

Results and discussion

Microbial fuel Cell's behavior

The output voltages of MFC across four cycles are shown in

Fig. 2. The consistent voltage generating cycles after warming
up was shown in all the microbial fuel cells. When a new
culture medium was introduced, the voltage raised sharply,
stayed at a constant level for some time, and then decreased
as substrate. Ni < rGOHI-AcOH < Pt Nanoparticles rGO catalyst
cathode MFCs revealed similar trends of increase and
decrease in voltage profile, though at varying magnitudes.
Accordingly, the voltage generating cycle was close to 25 h
long. The average maximum voltage for Pt/C MFCs over four
cycles was 264 ± 0.9 mV. Maximum voltages for rGOHI-AcOH Fig. 2 e Differences in voltage output (with an external
cathode catalyst MFCs were 175 ± 2.3 mV for Single Load, resistance of 47U) between Microbial Fuel Cells made with
233 ± 0.9 mV for Double Load, and 213 ± 2.1 mV for Triple Load. various cathodes.

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 international journal of hydrogen energy xxx (xxxx) xxx 5

Graphite Oxide Hydrogen iodide and acetic acid-Triple

Loading cathodes (1456 ± 31 mW/m2, 20.84 ± 0.01, those with
rGOHI-AcOH-DL cathodes surpassed the competition in both
catalytic (Table 1). Results suggest that rGOHI-AcOH - Double
load can be a suitable cathode catalyst for Microbial Fuel Cells,
with 78% of the expected power density equated to Platinum/
Carbon. It was found that the power density produced by
rGOHI-AcOH-SL MFCs and Microbial Fuel Cells with Reduced
Graphite Oxide Nickel Nanoparticle-Triple Load cathodes was
compared, with the rGOHI-AcOH-SL MFCs by 9% more efficient.
The power density of the Reduced Graphite Oxide Nickel
Nanoparticle-DL MFCs was higher than that of the other MFCs
with Reduced Graphite Oxide Nickel Nanoparticle cathodes.
Ni Nanoparticles deposited on graphite sheets improve the
ability of the material to capture and accept electrons,
increasing the mass transport ith double-catalyst-loading
cathodes operate well because the catalysts are distributed
evenly across the electrode, resulting in a uniformly thick
catalyst layer with minimal catalyst aggregation [39e41].
However, the cathode's electron transmission and electro-
chemical reactions were hampered.
Electrode potentials. (Both cathode and anode) are plotted
against current densities in Fig. 3c. Differences between MFCs
in cathode potential were more noticeable than differences
between MFCs in anode potential. Each MFC had a more
consistent anode voltage than the cathode. Differences in
cathode potential were explained by the effectiveness of
various effectiveness and their loading in reducing oxygen.
Microbial fuel cells with Pt/C cathode achieved a OCP of
821 ± 13 mV, indicating the intrinsic catalytic activity. All
other non-traditional (metal) cathode Microbial Fuel Cells had
OCPs lower than those of the Microbial Fuel cells using
Reduced Graphite Oxide Hydrogen iodide and acetic acid-
Double loading (728 ± 8 mV) and TL (727 ± 13 mV). The Open
Circuit Potential of Microbial Fuel Cells with Reduced Graphite
Oxide Nickel Nanoparticles Double Loading (684 ± 12) and TL
(681 ± 8) cathodes were similar. Single loading Reduced
Graphite Oxide Hydrogen iodide and acetic acid (667 ± 12) and
Reduced Graphite oxide Nickel Nanoparticles (603 ± 8) cath-
odes produced MFCs with lesser OCPs than DL and TL of the
similar cathode materials produced by microbial Fuel cells
with higher OCPs. Platinum/Carbon cathode MFCs have much
higher CEs (ca. 80%) due to their increased catalytic activity
and current generation. Maximum power densities and cata-
lyst loading for rGOHI-AcOH and rGO/Ni Nanoparticles catalysts
yielded similar CEs (70%). Because of this, it is concluded that
the oxygen diffusion rate of CE and other features were not
considerably affected by the different cathode materials
under the conditions tested here or that the anode's perfor-
mance is primarily governed by the CE. The kinetics reaction
Fig. 3 e (a) Power densities curvatures about the cathode in of the anodes used in this investigation was very similar.
MFCs with varying current densities, (b) potential
curvatures about the cathode in MFCs with varying current Electrochemical analysis
densities, and (c) electrode potential curvatures about the
cathode in MFCs with varying current densities. All MFCs with cathodes are made of nonprecious metals that
showed a clear redox peak in the CV measurements (Fig. 5a
Changing the amount of catalyst on the cathodes also af- and Fig. 5b). The existence of the redox species is denoted by
fects the performance of Microbial Fuel Cells with Reduced the appearance of separate anodic peaks in the microbiome.
Graphite Oxide Hydrogen iodide and acetic acid-Single Load Although current-voltage studies of MFCs with Pt/C cathodes
cathodes (989 ± 34 mW/m2, 0.70 ± 0.004 mA/cm2) and Reduced did not identify any clear redox peaks, the high current

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6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e (a) SEM images of (i) Reduced Graphite Oxide Hydrogen iodide and acetic acid catalysts and (ii) Reduced Graphite
Oxide Nickel Nanoparticles composite catalysts, (b) X-ray Photoelectron spectroscopy survey spectrum, and (c) X-ray
Photoelectron spectroscopy Raman spectrum.

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 international journal of hydrogen energy xxx (xxxx) xxx 7

Table 1 e Analyzing the effects of various cathodic catalysts on MFC performance.

Factors Microbial Fuel Cells (MFCs)
Pt/C rGOHI-AcOH rGO/Ni Nanoparticles
Single Load Double Load Triple Load Single Load Double Load Triple Load
(SL) (DL) (TL) (SL) (DL) (TL)
OCP (mV) 821 ± 13 667 ± 12 728 ± 8 727 ± 13 603 ± 8 684 ± 12 681 ± 8
Maximum potential (mV) 216 ± 2.30 145 ± 1.60 189 ± 1.40 175.9 ± 1.60 137.8 ± 2.30 181.9 ± 2.60 171.3 ± 2
Maximum current (mA) 8.19 ± 0.07 5.46 ± 0.06 7.28 ± 0.05 6.84 ± 0.06 3.96 ± 0.05 3.95 ± 0.05 4.72 ± 0.05
Maximum Volumetric power density 56 ± 1.21 27 ± 0.53 43 ± 0.62 37 ± 0.68 16 ± 0.52 26 ± 0.73 24 ± 0.52
(W/m3)
Maximum power (mW) 1.55 ± 0.04 0.68 ± 0.03 1.19 ± 0.02 1.03 ± 0.02 0.42 ± 0.01 0.72 ± 0.03 0.64 ± 0.02
Maximum current density (mA/cm2) 1.03 ± 0.02 0.70 ± 0.008 0.92 ± 0.007 0.84 ± 0.009 0.43 ± 0.008 0.57 ± 0.009 0.54 ± 0.007
Maximum. Power density (mW/m2) 2203 ± 52 989 ± 21 1691 ± 34 1456 ± 31 585 ± 21 1016 ± 31 905 ± 32
Maximum. volumetric current 257 ± 3.63 173 ± 2.82 225 ± 2.62 209 ± 2.92 107 ± 1.72 141 ± 3 134 ± 1.62
density (A/m3)
Coulombic efficiency (%) 82 ± 3 76 ± 4 73 ± 5 74 ± 2 73 ± 3 71 ± 3 71 ± 1

response (AUC ¼ 15.23 IV, limiting current ¼ 8.01 mA) sug- In contrast, R is the gas constant in Joules per molecule Kelvin,
gested both the catalytic activity of the Platinum/Carbon T is the absolute temperature in Kelvin, and A is the cathode
catalyst (Fig. 5a). The total area of MFCs with rGOHI-AcOH electrode's surface area in square centimeters (Fig. 5f).
cathodes was higher (8.16 IV AUC for Single Load, 10.14 IV AUC The increased conductivity of the Platinum/Carbon cata-
for Double Load, and 9.26 IV AUC for Triple Load) than that of lyst would lead to transfer resistance at less charge and
MFCs with rGO/Ni Nanoparticles cathodes (5.23 IV AUC for greater electrolyte diffusion by giving the transporting charge
Single Load, 7.12 IV AUC for Double Load, and 6.12 IV AUC for of electrons to the electrode with more energy. Regarding the
Triple Load). Similar to rGO/Ni Nanoparticles-cathode MFCs impedance of Platinum/Carbon Microbial Fuel Cells, the
had a limiting current of 6.05 mA for Single Load, 6.31 mA for rGOHI-AcOH cathode Microbial Fuel Cells showed lesser ohmic
Double Load, and 5.82 mA for Triple Load (Fig. 5c), rGOHI-AcOH resistance, lower charge transfer resistance, and quicker
MFCs had a limitation current of 6.31 mA for Single Load, electrolyte dispersal compared to the Reduced Graphite Oxide
6.31 mA for Double Load, and 5.73 mA for Triple Load (3.76 mA Nickel Nanoparticles MFCs. The graphite observed in rGOHI-
for Single Load, 5.08 mA for Double Load, 3.92 mA for Triple AcOH catalysts compared to rGO-based materials synthesized
Load (Fig. 5 (b)). The improved surface area and electric con- with hydrazine are likely responsible for maximum conduc-
duction of the Reduced Graphite Oxide Hydrogen iodide and tivity and catalytic activity, as shown in Fig. 4.
acetic acid catalyst are two factors. When equated to other The Reduced Graphite Oxide Hydrogen iodide and acetic
non-traditional (metal) cathode MFCs, Reduced Graphite acid Microbial Fuel cells had the best electrolyte diffusion
Oxide Hydrogen iodide and acetic acid-Double Loading Mi- (9.26  1010 cm2 s1), and the minimal ohmic resistance
crobial Fuel Cells showed maximum responses. Higher cur- (19.06U) of any MFCs tested, the tiny (invisible) charge-transfer
rent is noticed in the Reduced Graphite Oxide Nickel resistance (0.86 U). Compared to Pt/C MFCs, charge-transfer
Nanoparticle Double Loading Microbial Fuel Cells compared to resistance is low. When using more catalytic material, the
the Reduced Graphite Oxide Nickel Nanoparticles Single Load available surface area for charge transference process among
and Triple Load Microbial Fuel Cells. The current responses the material and the electrolyte was improved [43]. The
were diminished when a non-traditional (metal) catalyst was impedance study confirms the superior performance of the
used on the cathodes, even at increased concentrations. The Microbial Fuel Cells with Reduced Graphite Oxide Nickel
minimal reactions were seen in Microbial Fuel Cells with a Nanoparticles cathodes in terms of ohmic resistance (21.62U).
single catalyst loading at the cathode. Increasing the catalyst load (TL) exhibited a little detrimental
Fig. 5d shows several representative Nyquist graphs of the impact on the impedance of Microbial Fuel cell-related factors
EIS for Microbial Fuel cells with various cathode electrodes. due to catalyst layer depth and catalyst accumulation. Mi-
Due to diffusion, all plots feature a single, perceptible semi- crobial Fuel Cells with SL catalyst cathodes exhibited poor
circle in the higher frequency zone, followed by a straight line performance characteristics of impedance.
in the low-frequency area (Warburg diffusion). Each imped-
ance was calculated by fitting a linear model to the Nyquist Stabilization of the rGOHI-AcOH catalyst
plot data (Fig. 5d). Ohmic resistance of microbial fuel cells is
shown by the point where semicircle and its axis connect. These results suggest that the Reduced Graphite Oxide
Differences in ohmic resistance may be traced back to con- Hydrogen iodide and acetic acid (especially with DL) could be
ductivity and catalyst type [42] since all MFCs were run under used in place of platinum as a cathodic catalyst in MFCs. To
the same circumstances (Fig. 5 e). The RCT between an elec- verify the long-term stability of rGOHI-AcOH of the catalyst, a
trode and electrolyte is directly related to diameter of semi- steady-state stability test was conducted using sodium ace-
circle. Substrate diffusion coefficient into the cathode tate as the substrate (Fig. 6). In a 30-day timeframe, the Mi-
electrode can be evaluated using formula D ¼ 0.5 (RT/AF2sC)2. crobial Fuel Cells with the rGOHI-AcOH-DL cathode produced

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8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 5 e (a). Cyclic voltammetry performance of Platinum/

Carbon, (b). Cyclic voltammetry performance of rGOHI- Fig. 5 e Continued
AcOH at various loads, (c). Cyclic voltammetry performance
of rGO/Ni at various loads (bottom), (d). Nyquist curvatures
for rGOHI-AcOH and rGO/Ni at various loads, (e). Microbial around 27 cycles. The power density of MFCs was not affected
fuel cell cathode impedance analysis for ohmic and Charge while using the rGOHI-AcOH-DL cathode. These results
transfer resistance, (f). Microbial fuel cell cathode demonstrate the remarkable consistency and reliability of the
impedance analysis for electrolyte diffusion. cathode material evaluated in rGOHI-AcOH.

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 international journal of hydrogen energy xxx (xxxx) xxx 9

From the above discussion, the results exemplify that

rGOHI-AcOH cathode catalyst MFCs had maximum voltages of
175 2.3 mV for single loads, 233 0.9 mV for double loads, and
213 2.1 mV for triple loads. The power density and polarization
curve to the current density for various microbial fuel cells are
revealed by the results [48e50]. The power density of the MFCs
can be improved when using Platinum/Carbon cathodes (2203
52 mW/m2, 1.03 0.02 mA/cm2). The performance of Microbial
Fuel Cells with Reduced Graphite Oxide Hydrogen Iodide and
Acetic Acid-Single Load cathodes and Reduced Graphite Oxide
Hydrogen Iodide and Acetic Acid-Triple Loading cathodes
(1456 31 mW/m2, 20.84 0.01, those with rGOHI-AcOH-DL
cathodes outperformed the competition) is also affected in
both catalytic. Fuel cells with hydrogen iodide, acetic acid, and
reduced graphite oxide: double loading (728 8 mV) and TL (727
13 mV). The Open Circuit Potential of Microbial Fuel Cells with
Double Loading (684 12) and TL (681 8) cathodes with Reduced
Fig. 6 e Long-term steady-state behavior of Microbial Fuel
Graphite Oxide Nickel Nanoparticles was comparable. In
Cells with rGOHI-AcOH -Double Loading cathodes, measured
comparison to MFCs with rGO/Ni Nanoparticles cathodes, the
against an external resistance of 47U.
total area of MFCs with rGOHI-AcOH cathodes was greater (8.16
IV AUC for Single Load, 10.14 IV AUC for Double Load, and 9.26
IV AUC for Triple Load) (5.23 IV AUC for Single Load, 7.12 IV
Pre-evaluation of capital cost AUC for Double Load, and 6.12 IV AUC for Triple Load). Where
AUC is meant that Area under the ROC Curve.
Depending on the material and market conditions, the costs of The calculation confirmed the benefits of employing the
concentrating MFCs might range from negligible to prohibi- Reduced Graphite Oxide Hydrogen iodide and acetic acid as a
tive. The primary economic analysis was performed for a low-cost catalytic cathode in Microbial Fuel cells. Stainless
reduced substrate using the data from bench-scale experi- steel mesh coated with rGOHI-AcOH might be employed as
ments. Capital costs for 1 m3 of fed-substrate are estimated at primary cathode electrode in microbial fuel cells due to its
7971.24 ₹/m2 for rGOHI-AcOH-DL catalyst and 223194.72 ₹/m2 ability to enhance power output while lowering the entire
for Pt/C catalyst on the cathode electrode. This suggests that a cathode cost. The drawbacks of stainless-steel composite
rGOHI-AcOH-DL, which is 95% cheaper than a Pt/C catalyst, cannot be ignored. As an added complication, it is not always
could make the MFC process greener if utilized at the cathode possible to extrapolate from MFCs conducted at the laboratory
electrode. According to published research [40], the cost of an bench to the industrial level. Due to scale and edge effects,
activated carbon cathode is estimated at 1195.69 ₹/m2, laboratory studies conducted at a smaller scale (such as a
whereas the price of a Pt/C cathode was predicted to be laboratory bench) frequently produce better results than
144598.29 ₹/m2. Cathodes are produced by the dispersal car- larger-scale field tests. This technology's future pilot and field
bon (8.9 mg/cm2) and Platinum/Carbon (0.6 mg/cm2) catalysts tests require a thorough examination of its price tag.
on stainless-steel and carbon fabric (30%). More significant
catalyst loadings were opted to compensate for the limitations
of the stainless-steel mesh. Conclusion
There is a possibility that the stainless steel mesh, which
is less expensive and has higher conduction than other This study investigates the feasibility of replacing graphite
carbon-based composites, will be employed as the primary Nanoparticles composites (rGO/Ni) with highly conductive
material for the MFC cathode [44]. However, using stainless graphite materials with Reduced Graphene Oxide Hydrogen
steel mesh in MFCs might deteriorate, increasing ohmic iodide - Acetic acid (rGOHI-AcOH) for MFC cathodes. The per-
resistance and decreasing efficiency. The carbon cloth is a formance of graphite and graphite-based catalyst cathode
robust synthetic matrix that is tinny, stretchy, and less MFCs was enhanced by doubling the catalytic load on the
weight; it has a higher porosity and good electrical conduc- cathode (1 mg/cm2). Cathode catalyst load has a substantial
tion and provides a significant benefit when employed as the effect on MFC behavior. In comparison to other non-
backbone of cathode electrodes in Microbial Fuel cells [45]. traditional (metal) cathode MFCs, the double-loaded rGOHI-
2
After being loaded onto electrode-based materials, activated AcOH cathodes generate more power (1691 ± 34 mW/m ,
carbon forms aggregates, making a sizable portion of its CE ¼ 73 ± 5%) and 78% of the power density reported for
carbon atoms inaccessible to the ions in the electrolyte [46]. Platinum/Carbon Microbial Fuel Cells (2203 ± 52 mW/m2,
Because of a single atomic layer, it is more eco-friendly than CE ¼ 82 ± 3%). They performed well during 30 days of opera-
other catalysts, easier to transport, and more efficient than tion (27 cycles) and had a cathode cost 73% less than the
others in weight savings, catalytic loading, and aggregation Platinum/Carbon cathode. Reduced Graphene Oxide
[47]. Aggregation suppression in a catalyst material increases Hydrogen iodide - catalytic AcOH's activity may result from its
its surface area with the solution, leading to improved cata- highly graphitized, large surface area. Power densities of
lytic activities. 1016 ± 31 mW/m2 (CE ¼ 71 ± 3%) were achieved in MFCs with

Please cite this article as: Sathish T et al., Amplifying power generation in microbial fuel cells with cathode catalyst of graphite-based
nanomaterials, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2022.12.077
10 international journal of hydrogen energy xxx (xxxx) xxx

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Energy Storage 2022;55. https://doi.org/10.1016/
The authors declare that they have no known competing
j.est.2022.105375.
financial interests or personal relationships that could have
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Please cite this article as: Sathish T et al., Amplifying power generation in microbial fuel cells with cathode catalyst of graphite-based
nanomaterials, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2022.12.077