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Energy 254 (2022) 124163

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Insights into the development of microbial fuel cells for generating


biohydrogen, bioelectricity, and treating wastewater
Shams Forruque Ahmed a, **, M. Mofijur b, c, Nafisa Islam a, Tahlil Ahmed Parisa a,
Nazifa Rafa d, Awais Bokhari e, f, *, Jirí Jaromír Klemes e, Teuku Meurah Indra Mahlia b, g
a
Science and Math Program, Asian University for Women, Chattogram, 4000, Bangladesh
b
Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney, Ultimo, NSW, 2007,
Australia
c
Mechanical Engineering Department, Prince Mohammad Bin Fahd University, Al Khobar, 31952, Saudi Arabia
d
Department of Land Economy, University of Cambridge, Trinity Ln, Cambridge, CB2 1TN, UK
e 
Sustainable Process Integration Laboratory - SPIL, NETME Centre, Faculty of Mechanical Engineering, Brno University of Technology- VUT Brno, Technicka
2896/2, 616 69, Brno, Czech Republic
f
Department of Chemical Engineering, COMSATS University Islamabad (CUI), Lahore Campus, 54000, Punjab, Lahore, Pakistan
g
Department of Mechanical Engineering, College of Engineering, Universiti Tenaga Nasional, Selangor, Malaysia

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

Article history: Bio-electrochemical systems, such as microbial fuel cells (MFCs), serve as greener alternatives to con-
Received 17 January 2022 ventional fuel energy. Despite the burgeoning review works on MFCs, comprehensive discussions are
Received in revised form lacking on MFC designs and applications. This review paper provides insights into MFC applications,
20 April 2022
substrates used in MFC and the various design, technological, and chemical factors affecting MFC per-
Accepted 29 April 2022
Available online 7 May 2022
formance. MFCs have demonstrated efficacy in wastewater treatment of at least 50% and up to 98%. MFCs
have been reported to produce ~30 W/m2 electricity and ~1 m3/d of biohydrogen, depending on the
design and feedstock. Electricity generation rates of up to 5.04 mW/m2e3.6 mW/m2, 75e513 mW/
Keywords:
Microbial electrolysis cell
m2, and 135.4 mW/m2 have been found for SCMFCs, double chamber MFCs, and stacked MFCs with the
Wastewater treatment highest being produced by the single/hybrid single-chamber type using microalgae. Hybrid MFCs may
Lignocellulosic biomass emerge as financially promising technologies worth investigating due to their low operational costs,
Anode integrating low-cost proton exchange membranes such as PVA-Nafion-borosilicate, and electrodes made
Cathode of natural materials, carbon, metal, and ceramic. MFCs are mostly used in laboratories due to their low
Hydrogen power output and the difficulties in assessing the economic feasibility of the technology. The MFCs can
Proton exchange generate incomes of as much as $2,498.77  102/(W/m2) annually through wastewater treatment and
energy generation alone. The field application of MFC technology is also narrow due to its microbio-
logical, electrochemical, and technological limitations, exacerbated by the gap in knowledge between
laboratory and commercial-scale applications. Further research into novel and economically feasible
electrode and membrane materials, the improvement of electrogenicity of the microbes used, and the
potential of hybrid MFCs will provide opportunities to launch MFCs from the laboratory to the
commercial-scale as a bid to improve the global energy security in an eco-friendly way.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction

The availability of adequate energy resources is crucial in


ensuring progress in the developmental targets of nations as
* Corresponding author. Department of Chemical Engineering, COMSATS Uni- safeguarding the sustainability of energy resources is essential for
versity Islamabad (CUI), Lahore Campus, 54000, Punjab, Lahore, Pakistan. ensuring the sustainability of investments [1]. The global energy
** Corresponding author. Science and Math Program, Asian University for Women, demand has also been increasing consistently over the last few
Chattogram, 4000, Bangladesh. decades [2], where the demand is particularly acute for developing
E-mail addresses: shams.ahmed@auw.edu.bd, shams.f.ahmed@gmail.com
(S.F. Ahmed), awaisbokhari@cuilahore.edu.pk (A. Bokhari).
nations [3]. If energy demand continues to expand at the same rate

https://doi.org/10.1016/j.energy.2022.124163
0360-5442/© 2022 Elsevier Ltd. All rights reserved.
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

Nomenclature TiO2 Titanium dioxide


CaCl2 Calcium chloride
MFC Microbial fuel cell TNT Titanium dioxide nanotube
PEM Proton exchange membrane m-MFC Microalgae-microbial fuel cell
NADH Nicotinamide adenine dinucleotide OCV Open-circuit voltage
WWT Wastewater treatment OLR Organic loading rate
SCMFC Single-chamber microbial fuel cell RDP Ribosomal Database Project
COD Chemical oxygen demand HER Hydrogen Evolution Reaction
IEM Ion-exchange membranes MEC Microbial electrolysis cell
BPM Bi-polar membrane SPW Starch processing wastewater
CEM Cation exchange membrane PVC Polyvinyl chloride
AEM Anion exchange membrane EET Extracellular electron transfer
DCMFC Double-chamber microbial fuel cell ORR Oxygen reduction reaction
BOD Biochemical oxygen demand PVA Polyvinyl alcohol
PCB Polychlorinated biphenyls SPEEK Sulphonated poly (ether ether ketone)
CO2 Carbon dioxide

[4], global energy consumption is expected to increase 30e50% by as biocatalysts. As mentioned, these organisms possess the neces-
2030 [5]. With fossil-based fuels serving as the dominant source of sary molecular machinery to move electrons to the electrodes
energy in the world [6], the global energy-related CO2 emissions without the requirement of external assistance. They are also able
stood at 33.2 Gt in 2019, a huge spike from 20.5 Gt in the year 1990 to accept electrons from the surface of the electrodes. Even though
[7]. Although there is an urgent need for large-scale negative ac- fewer in numbers, relevant studies have investigated ways to
tions through economical carbon sequestration techniques [8] such enhance biofilm electrogenicity by genetically manipulating mi-
as biochar [9] for wider acceptance and implementation [10], crobes and utilising synthetic biology [22]. MFCs also exhibit a wide
decarbonisation of the energy sector is also crucial. The renewable range of other advantages: (i) operable across various process pa-
energy sources have received much attention because of their rameters where the temperature can range between 15  C and
environmental friendliness and inexhaustible nature [11]. In 2019, 45  C, and the pH is generally neutral; (ii) able to utilise a wide
renewables met 27% [12] of the world's energy demand [7]. range of complex biomass as substrate; (iii) substrate is directly
Renewable energy is also emerging as a competitive energy source transformed to produce energy; (iv) elimination of downstream
over fossil fuels as a result of significant technological advance- processes; (v) lower amount of activated sludge results from the
ments and research in the field [13]. The fuel cell (FC) has been treatment of wastewater in comparison with conventional treat-
recognised as a promising solution to the world's energy security ment methods; (vi) unlike conventional aerobic technologies there
issues [14] and offers a wide range of advantages over other alter- is no requirement for energy for aeration; (vii) lower operational
natives [15], including the absence of pollutant emissions, effi- costs and greater economic benefits through energy and value-
ciency, and lower sound pollution [16]. Currently, the economics added products; (viii) resistance to environmental stresses; (ix)
and magnitude of generation are the limitations of FCs. possibility of both centralised and decentralised applications; and
One kind of FC is the microbial FC (MFC), which is a bio- (x) results in a moderate environmental impact according to un-
electrochemical system that employs microorganisms as bio- dertaken life cycle analyses [19]. These advantages contribute to
catalysts to transform chemical energy stored in organic matter to numerous applications of MFCs. MFCs’ highly extolled application
electrical energy directly via substrate oxidation [17]. An MFC lies cleaner alternatives for electricity/bioenergy generation, bio-
comprises two chambers, an anode and a cathode, partitioned by a hydrogen production, wastewater treatment (WWT), environ-
proton exchange membrane (PEM) [18]. In an MFC, microbes mental bioremediation, and their ability to serve as biosensors and
remain in anode compartments as biofilms and produce electrons in early warning systems in water quality applications [23].
and protons after oxidising an electron donor, usually an organic The MFC's method of electricity generation may be environ-
substrate. The anode is used by the biofilm microbe as the electron mentally friendly, cost-effective, and produce harmless products,
acceptor for anaerobic respiration, which receives electrons from but currently, it does not generate an adequate amount of energy to
the microbe after the electrons have first passed through the mi- serve as a competitive alternative to existing technologies. Even
crobe's electron transport chain by nicotinamide adenine dinucle- though MFC is an attractive alternative as an option for industrial
otide (NADH) to the terminal electron acceptors and then to the commercialisation [24], the commercial-scale use of MFCs has
microbe's outer membrane proteins [19]. The Geobacter, Shewa- largely been hindered by costly components [25]. For instance,
nella, Pseudomonas, and Rhodoferax are some of the most widely depending on the type of MFC employed, the cost-benefit ratios of
investigated exoelectrogens in MFCs [20]. These microbes produce MFCs range between 249 and 164,143, where the lowest ratio is
flavin molecules, or organic compounds based on pteridine, to perceived for hybrid constructed wetland-MFC while the highest
promote electron transfer to the anode. The electron transfer from ratio was for microalgae-MFC [26]. The greatest revenue generated
the anode to the cathode through the external circuit produces an from the former can reach up to $2,498.77  102/(W/m2) [26]. The
electric current. The generated protons drift over to the cathode sustainability of the technology depends on its profitability;
through the PEM, which prevents the movement of oxygen into the although private organisations do support innovation culture,
anode compartment to avoid the inhibition of electricity genera- knowledge generation and sharing are key in advancing green
tion. Instead, the cathode exposed to the oxygen initiates the for- entrepreneurship [27]. Further research on process optimisation,
mation of water [21]. with special attention to the types of the microbial community,
The major advantage of MFCs arises from their use of microbes substrate, and electrodes used, is important and has already been

2
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

the subject of interest of researchers working in this field. For bodies looking to utilise and scale-up MFC use.
instance, the substrate determines the microbial population
structure and its eventual activity when serving as the fuel source 2. Types of microbial fuel cell
for the microbes. The wastewater and fermentable and non-
fermentable organic materials primarily from sewage sludge have 2.1. Single-chamber system
been tested as substrates for MFCs to enhance the functioning of
MFCs and create opportunities to use waste biomass, treat waste- Single-chamber MFCs are basic anode compartments, where the
water and produce bioenergy [28]. The poor performance of anode cathode compartment is not complete, and the presence of film for
electrodes in MFCs also still remains a major disadvantage for its proton transfer is less probable [39], as shown in Fig. 1. Single-
practical application. Materials such as nanocomposites, con- chamber microbial fuel cells do not have a proton exchange
ducting polymers, stainless steel, carbon nanotube, and metal ox- membrane (PEM) that separates the anode and cathode. The pur-
ides have been investigated for their potential in electrode pose of PEMs is to keep the anodic and cathodic chambers separate
enhancement to increase efficient electricity generation by MFCs from each other by: reducing the diffusion of oxygen back to the
[29]. Various other factors can affect the performance of the MFCs, chamber of the anode from the chamber of the cathode while
including pH buffer and electrolyte, PEMs, temperature, aeration simultaneously reducing the flux of substrates from anode to
rate, and other process factors [30]. cathode; enhancing the coulombic efficiency; and ensuring that
MFCs have been the subject of much interest to researchers, operations are effective and sustainable [40]. Single-chamber MFCs
leading to the publication of over 500 journal articles per year from
2011 onwards and gradually increasing to over 1,000/y [19].
Numerous review works have attempted to compile information
and guide research and development to overcome the limitations of
current MFC models and expand their scalability. Table 1 below
shows the topics covered by some of the review papers published
in recent years and those covered by this study. As can be seen,
recent review works primarily focus on exploring specific appli-
cations, especially wastewater treatment, and the extent of their
efficiency. Comprehensive discussions are lacking on MFC types,
the numerous substrates explored for their scope of use in MFCs,
their comparative advantages, and MFC components that generally
affect MFC performance. To address these gaps, this review paper
presents the current status of MFC design and application. By first
exploring the types of MFCs currently under research and in use,
this paper reviews the potential of substrates used in MFCs, the
current applications of MFCs, namely bioenergy and biohydrogen
generation, wastewater treatment, and biosensing, and finally, the
factors that affect MFC performance. It concludes with a discussion
Fig. 1. Operation and structure of single-chamber microbial fuel cell that uses a power
of the persisting challenges that limit MFC application and di- supply to drive electron from anode to cathode [42]. Electrochemically active bacteria
rections for future research. By shedding light on the progress of growing on the anode surface degrade organic matter into electrons and CO2 in the
and challenges for MFCs, this paper will provide information to MFC process. Oxygen is utilised as the electron acceptor at the cathode in the MFC. Due
to the fact that oxygen has high redox potential than microbial anode, electrons
researchers working in the field and industries and government
simultaneously flow from anode to cathode, resulting in electricity generation.

Table 1
Topics related to MFC research and development covered in this paper and other studies published in recent years.

Study Types of Substrates utilised Application MFC components Challenges and future opportunities
MFCs affecting performance

This study ✓ ✓ ✓ ✓ ✓
Jatoi et al. [30]   (wastewater only) √ (WWT only) ✓ ✓
Chakraborty et al. [31]   (wastewater only) √ (WWT only)  √ (future directions only)
Wu et al. [32]   (water and soil only) √ (WWT and environmental  ✓
remediation only)
Do et al. [33]   (wastewater only) √ (biosensor only)  ✓
Abdallah et al. [25] ✓ ✓  ✓ ✓
Palanisamy et al. [17]   (wastewater only) √ (electricity generation and √ (electrode materials ✓
WWT only) and PEM only)
Fang and Achal [34]   (wastewater and soil only) √ (heavy metal removal only: √ (cathode materials 
WWT and soil remediation) and pH only)
Aarthy et al. [35]   (wastewater only) √ (hexavalent chromium √ (cathode materials ✓
reduction and electricity and pH only)
generation only)
Mathuriya et al. [36] ✓   ✓ ✓
Kumar et al. [37]  ✓ ✓ √ (electrode materials √ (challenges only)
only)
Choudhury et al. [21] ✓ ✓ √ (WWT) ✓ 
ElMekawy et al. [38]   (water only) √ (biosensor only)  √ (challenges only)

√: information sufficiently available;  : information not sufficiently available, or unavailable.

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S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

face problems related to back-diffusion and flux of oxygen and


substrates. As a result of oxygen back-diffusion into the anode
where bacteria consume it, single-chamber MFCs show low
coulombic efficiency [39]. The single-chamber MFCs improve the
system economy because they do not have costly polymer elec-
trolyte to separate the anode and cathode chambers [41]. They can
provide a higher power output and do not face problems related to
internal resistance.
A performance evaluation of a single-chamber microbial fuel
cell (SCMFC) system was completed by Vilas Boas et al. [43] based
on the following operational conditions: concentration of yeast
extract and batch cycle and design parameters including the
thickness of the membrane, active area, and area of the anode
electrode. The dairy-based industry was used as a source of syn-
thetic wastewater in the MFC with Lactobacillus pentosus pure
culture. The overall performance evaluation was executed based on
the power output and rate of removal of chemical oxygen demand
(COD). According to the results, a 48 h batch cycle attained higher
COD removal rates and power densities. The dry biofilm weight and
electrochemical performance of the SCMFC decreased as the anode
electrode area was decreased by 50%. The electrochemical perfor-
mance was positively affected by the concentration of yeast extract,
but it showed a decrease in the removal rate of COD. An improve-
ment was observed in the MFC's overall performance when the
Nafion 212 membrane was made thinner with a smaller area of
25 cm2. The highest power density of 5.04 ± 0.39 mW/m2 was
Fig. 2. Schematic of a double-chamber microbial fuel cell system [46].
attained with a 25 cm2 active area of Nafion 212 membrane, an
electrode area of 61 cm2 of the anode, yeast extract of 50 mg/L, and
a batch cycle of 48 h. The study mentions that the best-operating perfluorinated membrane, which has good properties but is so
conditions and designs vary depending on the MFC. costly that it crucially impacts the overall production cost of the
The SCMFC was used to investigate the copper removal and MFC. For instance, Nafion® 117 can cost approximately $1,733/m2
electricity generation [32]. The results were positive and showed [47]. Studies have been undertaken on separators to replace Nafion,
effective removal of copper in the MFC without a membrane, with like microfiltration and ultrafiltration membranes, anion and cation
98.3% removal efficiency maintaining a Cu2þ concentration of exchange membranes, sulphonated polyether ketone membrane,
12.5 mg/L. The maximum power density and open-circuit voltage forward osmosis membrane, and bipolar membrane double-
were 10.2 W/m3 and 0.78V. Another study conducted by Abour- chamber MFCs face problems with internal resistance because if
ached et al. [44] used SCMFC with an air-cathode to explore the the electrodes are kept at a long distance, the performance of the
heavy metals Cd and Zn and found that a high power generation of MFC decreases due to increased internal resistance [48]. If the
3.6 W/m2 was achieved for both elements and the removal effi- electrodes are brought too close together, higher back-diffusion will
ciencies for both were also high, Cd (90%) and Zn (97%). SCMFCs can occur from the cathode chamber to the anode chamber, which will
also be utilised as biosensors, as shown in a study where peptone also affect the production of power and power density.
and sodium-acetate were used to find out and verify the concen- A double-chamber MFC with different ion-exchange mem-
tration of biodegradable organics in water samples as an assess- branes (IEMs), bi-polar membrane (BPM), PEM, cation exchange
ment of the potential of a single-chamber MFC in its biosensor membrane (CEM), and anion exchange membrane (AEM) was used
application [45]. The MFC showed good performance at a high ac- in a study to analyse chromium removal in terms of reduction in the
etate concentration, and the current in the cell was uniform be- cathode, membrane adsorption, and membrane permeation to the
tween 25  C and 35  C with a significant decrease below 20  C. anodic chamber [49]. BPM demonstrated the most successful per-
Biosensors with this MFC design can be used to detect readily formance in the removal of hexavalent chromium with a percent-
biodegradable substrates of at least 5 mg COD/L and measure up to age of 99.4 ± 0.2% while simultaneously balancing pH and
approximately 50e70 mg COD/L of concentration. conductivity in both anode and cathode chambers. AEM
(97.9 ± 0.8%) and CEM (95.6 ± 0.8%) followed after BPM, but PEM
2.2. Double-chamber system did not maintain suitable pH and conductivity and showed the
lowest chromium removal efficiency and the least successful per-
Double-chamber MFCs can come in various shapes, such as U- formance of the anode. When using double-chamber MFCs, the
shaped or H-shaped. In U-shaped dual chambers, one arm of the performance of IEMs needs to be evaluated as they are responsible
tube is the cathode, and the other is considered the anode [39]. An for determining the MFC's overall performance. While assessing the
ion-selective membrane creates a separation between the elec- organic loading rate (OLR) (435e870 mg COD/L$d) and its impact
trodes. As illustrated in Fig. 2, double-chamber MFCs use PEM to on the recovery of nutrients for treating domestic wastewater using
separate the anode from the cathode. Unlike the single-chamber a double-chamber microbial fuel cell (DCMFC), it was found that
MFC, they do not face many problems related to back-diffusion or with an OLR range from 435 to 725 mgCOD/L$d, 90% of organics
the flux of oxygen and substrates. Each compartment can maintain were removed and a maximum power density of 253.84 mW/m2 at
different conditions without interference. The double-chamber 435 mgCOD/L$d OLR was achieved [50]. The coulombic efficiency
MFCs have some drawbacks because of the PEM, the major one was also at its highest value (25.01%) at OLR 435 mg COD/L$d.
being the overprice of a standard polymeric membrane [40].
The most common PEM used in MFCs is the Nafion ® 117 (NF), a
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S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

2.3. Stacked microbial fuel cell internal resistance, and the electricity production of the triple-
chamber MFC was affected by the anolyte and catholyte concen-
Stacked MFC is a configuration type where fuel cells are stacked tration. The stacked MFCs are more efficient than DCMFCs.
to form a battery of fuel cells, as shown in Fig. 3. This stacking can
be done in series or in parallel, each form of stacking having its own 3. Substrates utilised in microbial fuel cells
significance, and can provide great efficiency [48], as illustrated in
Table 2. Stacks connected in series yield higher voltage, and stacks 3.1. Acetate
connected in parallel yield higher current. The following factors
should be considered when designing a stacked MFC: electrode One of the most common substrates used in MFCs is acetate
type, the direction of the stack (horizontal or vertical type), the (CH3COONa), as it is a carbon source for exoelectrogenic bacteria
reactor shape, determination of connection methods, and modu- [65]. It falls into the category of non-fermentable organics. Acetate
lation. Yang et al. [51] undertook a study to understand self- is a monocarboxylic acid anion that is formed from the removal of a
sustaining pH control in stacked MFC using a hybrid MFC stack proton of a carboxyl group of acetic acids. The molecular formula of
based on single-chamber and double-chamber MFCs. The results acetate is C2H3O 2 and it has a molecular weight of 59.04 g/mol [66].
revealed that the hybrid stack showed the highest performance The metabolism process of acetate is very simple, thus making it
regarding power electricity output and efficient acetate conversion readily biodegradable by bacteria. Acetate is considered to show
compared to the stacks that consisted solely of SCMFCs or DCMFCs. the best performances as a substrate in MFCs, as shown by multiple
A multi-chamber MFC was build to investigate the cathode studies mentioned in this review.
component and four anodes separated by a membrane where the One of these studies [56] researched the response in the
electrode chambers were connected via electrical circuits in par- development of cell voltage, microbial community composition,
allel by sharing a cathode chamber [64]. Cathodic parameters like and electricity recovery during operation of the MFC using initial
the shape and area of cathode and catholyte concentrations were substrates, which included bioethanol effluent (BE) xylose, acetate,
considered as influences on the production of power. The output of and an acetate/xylose 1:1 mixture. The MFCs which were initially
the multi-anode chamber MFC are as follows: at 100 U, a maximum fed with acetate showed the best results with shorter initiation
open circuit potential of 720 ± 20 mV where the peak power time, higher coulombic efficiency, and higher average cell voltage
density was 52.8 mW/m2 (162.5 mA/m2); 8,720 mg COD/L of than those filled with acetate/xylose or xylose, the corresponding
wastewater concentration was observed with a peak power density values of which were 1 d, 31.5 ± 0.5% and 634 ± 9 mV. The MFCs
of 135.4 mW/m2 (368 mA/m2). The results prove that this scaled-up initiated by acetate exhibited a lower cell voltage of 645 ± 10 mV
MFC system design can attain a high generation of power in a small and a longer adaptation time of 21 h when a switch to xylose as the
space. substrate was made. When the substrate was switched to BE,
A similar study compared the performance of double and triple- maximum power density (362 ± 27 mW/m2), maximum current
chamber MFCs, and results showed that the power density pro- density (709 ± 27 mA/m2), highest voltage (656 mV), and
duced in the triple-chamber MFC was 1.9 times higher than the coulombic efficiency (25 ± 0.5%) was produced in MFCs initiated by
double-chamber MFC with respect to the surface area of the cath- acetate. Acetate-initiated MFCs had a less diverse microbial com-
ode [64]. This was because the compartment arrangement was munity with more electrogenic bacteria.
similar to two single cells connected as a parallel circuit by sharing Another study explored MFC performance during changes to the
the same cathode chamber. When calculated, the internal resis- influent nutrient from lactate to glucose-propionate-acetate and
tance values of the double and triple-chamber MFCs were found to back to lactate [67]. According to the results, the performance of the
be 57.8 and 81 U. The DCMFC had limitations related to high MFC showed a rapid recovery when acetate, one of the lactate's
metabolic intermediates, replaced it. A longer time was needed for
recovery in the case of acetate substrate conversion to lactate or
lactate to glucose/propionate. The following reactions occur in the
chambers a MFC uses acetate:
Anode:

CH3COO þ 4H2O / 2HCO3 þ 9Hþ þ 8e-

Cathode:

8Hþ þ 8e / 4H2

The above reactions take place at a pressure of 1 atm, 25  C, and


a pH of 7, which is the standard biological condition [42].

3.2. Glucose

Glucose is one of the three monosaccharides along with fructose


and galactose and is a simple monosaccharide that is found in
plants. It is one of the main fuels for cellular respiration, the product
of photosynthesis, and it acts as the foundational structure of
several polysaccharides like starch, cellulose, b-glucans, and
hemicelluloses. The molecular formula of acetate glucose is
C6H12O6, and it has a molecular weight of 180.156 g/mol. Cellulose,
Fig. 3. Schematic design of stacked microbial fuel cells (reprinted with the permission another potential substrate for MFCs, consists of as many as 10,000
of Elsevier from [52]. glucose polymers [68]. Glucose is an efficient substrate in MFCs but
5
Table 2

S.F. Ahmed, M. Mofijur, N. Islam et al.


Overview of the key studies on substrates utilised in microbial fuel cells.

Type of MFC Substrate Type of bacteria Main task (s) MFC construction Power generation Outcome (s) Ref.

Single-chamber The real dairy- Pure culture of The performance of an SCMFC Anode electrode area of 61 cm2, Nafion 5.04 ± 0.39 mW/m2 - The biofilm dry weight and [43]
based industry Lactobacillus pentosus was evaluated in a study based 212 membrane with an active area of SCMFC's electrochemical
as synthetic on the following operational 25 cm2, a batch cycle of 48 h, and 50 mg/ performance decreased as the
wastewater conditions: concentration of L of yeast extract anode electrode area was
yeast extract and batch cycle, decreased by 50%.
and design parameters - The electrochemical
including membrane thickness, performance was positively
active area, and area of the affected by the concentration of
anode electrode yeast extract but showed a
decrease in the removal rate of
COD
- When the Nafion 212
membrane was made thinner
with a lower area of 25 cm2, an
improvement was observed in
the MFC's overall performance
Wastewater Proteobacteria, An SCMFC was used to - Two MFCs setup: one with inoculated 10.2 W/m3 Results were positive and [53]
bacteroidetes, investigate copper removal and sludge from anaerobic sludge bed and showed efficient copper
actinobacteria and electricity generation another without inoculation and an removal in the MFC without a
acidobacteria abiotic MFC membrane with 98.3% removal
- Carbon brush anode and carbon cloth efficiency at Cu2þ concentration
with Pt catalyst cathode of 12.5 mg/L
- Microbial communities in the MFCs
were studied through 16S DNA
sequencing
Sewage Mixed bacterial culture Investigate power generation SCMFC with air cathode and anode built 3.6 W/m2 - Removal efficiencies of both [44]
6

wastewater and heavy metal removal in an of type A carbon cloth with an area of the elements were high, Zn
SCMFC 1.8 cm2. The cathode was of type B (97%) and Cd (90%)
carbon cloth and Pt coating with an area - Heavy metals affected anode
of 7 cm2 performance due to toxic
- MFC underwent inoculation with inhibition to the growth of
mixed bacterial culture anode microbes
Sewage Mixed microbial Utilising an SCMFC with a single - Graphite electrodes 1108.29 mW/m2 - Maximum voltage 2890 mV [54]
wastewater community electrode to consume sewage - Double anode and cathode connected was reached after 80 (hrs)
sludge treatment plant sludge and with a copper wire in an external series - A single-chamber single
generate electricity circuit electrode MFC system cannot
- A part of the electrode is immersed in effectively remove COD.
the substrate and is considered the
anode
- The other part that is exposed to the
atmosphere acts as the cathode
Hybrid Sunlight Mixed bacterial culture Employing a hybrid SCMFC - Carbon felt used as anode 0.0251 mW m2 - The hybrid MFC showed [55].
single-chamber Glucose consisting of a TiO2 nanotube - Wet proof carbon cloth, Pt on Vulcan, 515.18 ± 14.98 mW m2 increased power density,
array (TNT) photoanode linked Nafion perfluorinated resin solution, 670.94 ± 21.58 mW m2 voltage, and current density of
with a conventional bioanode carbon vulcan powder and 14%, 4%, and 33% and
to investigate methylene blue polytetrafluoroethylene used for air simultaneously degraded MB
(MB) dye degradation and cathode dye by 82.79% after an
improvement in the generation - Titanium foil used for preparing TiO2 operation of 3.5 h under

Energy 254 (2022) 124163


of power nanotube (TNT) array photoanodes simulated solar light
- X-ray diffraction spectroscopy was illumination
used to investigate TNT photoanode - The number of electrons
crystallinity increased under illumination
- MFC bioanodes, both hybrid and due to the TNT photoanode and
conventional, underwent inoculation conventional MFC bioanode
using wastewater pairing as it added
photogenerated electrons to
S.F. Ahmed, M. Mofijur, N. Islam et al.
the MFC's external circuit,
which consequently
accelerated the oxygen
reduction reaction at the air
cathode and enhanced the
overall performance of the MFC
Double-chamber Synthetic Mixed bacterial culture Assessing organic loading rate - Graphite felt was used to make the 253.84 mW/m2 MFC can treat municipal [50]
domestic (OLR) (435e870 mgCOD/L$d) anode, and the cathode was made of wastewater by removing 90% of
wastewater and its impact on the recovery carbon-fibre brush organics at a range of 435e725
of nutrients - Electrodes were separated by CEM mgCOD/L$d OLR
- The culture in the anode was
inoculated using synthetic domestic
wastewater
Bioethanol Diverse microbial Researching the response in the - Carbon sheet electrodes 362 ± 27 mW/m2 - The MFCs initiated by acetate [56]
effluent community (Geobacter development of cell voltage, - PEM (Nafion™ N117) exhibited a longer adaptation
Xylose sulphurreducens and microbial community - Inoculum used was domestic time (21 h) and lower cell
Acetate Desulphuromonas composition, and electricity wastewater voltage of 645 ± 10 mV when
Acetate/Xylose acetexigen) recovery due to initial - Chamber of the cathode was filled the substrate was switched to
1:1 mixture substrates, which included with potassium ferricyanide xylose.
bioethanol effluent (BE) xylose, (K3Fe(CN)6) and phosphate buffer - When the substrate was
acetate, and acetate/xylose 1:1 switched to BE, the highest
mixture (ace/xyl) during voltage (656 mV), maximum
operation of the MFC current density (709 ± 27 mA/
m(2)), maximum power density
(362 ± 27 mW/m(2)), and
coulombic efficiency (25 ± 0.5%)
was produced in the MFCs
initiated by acetate
- Acetate-initiated MFCs had a
less diverse microbial
7

community with more


electrogenic bacteria
Old and young Electrogenic bacteria Studying young and old - Carbon felt electrodes 96.8 mWm2 Power output decreased further [57]
landfill leachate (15%) Denitrifying (5%) leachate as substrates of MFC, - Cationic exchange membrane (CMI- 75 mWm2 when using old landfill
Anammox (2%) to remove pollutants and 7000) leachates
generate electricity with anodic - Effluent sludge from an anaerobic
microbiomes digester was used as the source of
carbon for enriching
- bacterial consortia
- MFC was acclimatised using glucose
- Raw gene sequence of the bacteria
was processed using the Pipeline Initial
Process tool of the Ribosomal Database
Project (RDP)
Chitin Aeromonas hydrophila Exploring the degradation of - A. hydrophila was isolated from a lab- e - The total metabolite [58]
chitin anaerobically by a scale reactor using a photometric high- concentration and electricity
chitinolytic bacterium in both throughput method identifying generation increased in the
MFC and fermentation systems. electroactive bacteria MFC system in comparison to
- The anodic and cathodic chambers the fermentation system,
were separated by a PEM of CMI-7000 proving that an electroactive
- Cathode and anode were made of bacterium can degrade chitin in
carbon felt an MFC

Energy 254 (2022) 124163


Dark Mixed consortium Selectively enriching an - An enriched thermophilic mixed 1.4 W/m3 - Fermented effluents are [59]
fermentative electrogenic mixed consortium culture capable of producing hydrogen 6.2 W/m3 acceptable substrates for
effluents in MFCs that can utilise dark was used bioanodes and there was an
fermentative effluents as - Batch fermentation for production of increase in maximum power
substrates hydrogen density from 1.4 W/m3 to
- One MFC underwent inoculation with 6.2 W/m3 after the anodic
mixed electroactive consortia taken parameters were optimised and
(continued on next page)
Table 2 (continued )

S.F. Ahmed, M. Mofijur, N. Islam et al.


Type of MFC Substrate Type of bacteria Main task (s) MFC construction Power generation Outcome (s) Ref.

from fresh fly ash leachate fermentation effluents were


- The other MFC directly functioned utilised
with the effluent that was pre-treated - The coulombic efficiency and
average COD removal efficiency
was 10.55% and 75.25%
Acetate Ethanol Mixed bacterial Exploring the effect of - MFC was operated in sequencing 513 mW/m2 - Complexity of substrates have [60]
Sucrose community sequential batch feeding by batch mode using different substrates 376 mW/m2 an effect on the MFC
Lactose using various substrates on - Cation exchange membrane (Ultrex, 388 mW/m2 performance and CE percentage
Starch power generation in an MFC. CMI-7000) 349 mW/m2 value
Methanol The power production and - Anode and cathode were made of 315 mW/m2 - MFC that was acetate-fed had
Molasses removal of COD varied based on plate bare graphite 328 mW/m2 the maximum CE and power
the complex nature of the 10 W/m2 density as acetate is the final
substrate and consequently liquid product of anaerobic
affected the MFC's overall respiration and electricity
performance production and could not be
degraded in any more products
Stack Acetate Mixed bacterial culture To understand pH control that - Hybrid MFC based on single-chamber 10.7 ± 0.3 mW - Hybrid stack showed the [51]
is self-sustaining in stack MFC and double-chamber MFCs highest performance in terms of
- The DCMFCs had two carbon cloth power electricity output and
electrodes and a PEM of Nafion 117, efficient acetate conversion in
DuPont comparison to the stacks that
- All MFCs underwent inoculation with consisted solely of SCMFCs (SS-
an acetate-fed MFC effluent SS stack) or DCMFCs (DD-DD
stack)
Wastewater Mixed bacterial culture Investigating the performance - Electrode chambers were connected 52.8 mW/m2 - 8,720 mg COD/L concentration
of a multi-chamber MFC built of via electrical circuits in parallel by 135.4 mW/m2 of wastewater [61] was
a cathode component and having a common cathode chamber to observed with a maximum
8

four anodes share power density of 135.4 mW/


- PEM (Nafion 117, DuPontTM, USA) m2 (368 mA/m2) [62]
was used for separation - The results prove that this
- Graphite electrodes scaled-up MFC system design
- Mixed bacterial culture used in the can attain high generation of
anode as a catalyst power and use less space [63]
- Cathodic chamber was filled with
potassium ferricyanide (K3Fe(CN)6) in
phosphate buffer

Energy 254 (2022) 124163


S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

not like acetate, as confirmed by multiple studies revealed in this not a suitable feedstock as these substances inhibit the microor-
review. One study [69] affirmed through its exploration of the ganisms’ metabolism. The current decreases as the electron trans-
performance of the MFC depending on organic substrate type that fer rate to the electrodes are affected. Examples of toxic substrates
acetate is the more efficient substrate in comparison to glucose and are lead, mercury, polychlorinated biphenyls (PCBs), and an
sucrose. Three mediator-less DCMFCs were used in this study, and organophosphate insecticide called Diazinon [33].
results showed that among the three different substrates, acetate The ability of microorganisms to create wastewater-generated
resulted in the best performance with 91 mW/m2 as the maximum electricity is affected by the following factors: transport phenom-
power density and maximum removal of COD of 77%. ena, biofilm formation, fluid dynamics, and the bio-electrochemical
Another study [70] evaluated the glucose degradation rate and process itself [75]. Wastewater consists of 3e10 times the energy
cell voltage in a mediator-less air cathode SCMFC. The MFC used required for its treatment, and this energy exists in the form of
glucose as a substrate inoculated with aerobic sludge. According to organic matter (~1.79 kWh/m3), nutritional elements such as ni-
the results, an increase was seen in electricity output as the glucose trogen and phosphorous (~0.7 kWh/m3), and thermal energy
concentration increased until a 5.0 g/L limit was reached when the (~7 kWh/m3) [65]. The type of wastewater used has an effect on the
current decreased due to glucose's inhibition effect in relation to substrate concentration and can create varying concentrations.
cyclic voltammetry. A maximum power density of 52 mW/m2 was Chemical energy extraction can be executed, but the same process
shown by the MFC with a stable current density of 275 mA/m2 and cannot extract thermal energy and will require a heat pump. It was
a 94.4% maximum glucose degradation rate. When glucose is used found that up to 90% of the COD was removed using an MFC with a
in MFC, the following reactions occur in the chambers [71]: Coulombic efficiency as high as 80% [76].
Anode: One study [75] was able to treat sewage and use the end
products for electricity generation in a DCMFC employed with
C6H12O6 þ 6H2O / 6CO2 þ 24Hþ þ 24ee carbon cloth electrodes and a platinum-coated cathode. Results
showed that this MFC system was able to reduce the COD content
Cathode: from 830 ± 20 mg/L to around 200 mg/L with an open circuit
voltage of 800 mV and treat the wastewater. This affirms that such
6O2 þ 24Hþ þ 24ee / 12H2O MFC systems can potentially treat wastewater and simultaneously
generate electric power with power density peaking in the range of
204 ± 0.38 mW/m2. Another study [54] utilised an SCMFC with a
single electrode for consuming sludge of the sewage treatment
3.3. Different types of wastewater plant to generate electricity. According to the results, a maximum
voltage of 2890 mV was reached after 80 (h) with 1108.29 mW/m2
Wastewater is constituted from numerous types of matter that surface power density. A single-chamber single electrode MFC
can undergo bioconversion in MFCs. Biotechnology can help build a system cannot effectively remove COD. MFC catalytic and electric
system to increase energy security by taking advantage of the rich performance was explored by Mateo-Ramírez et al. [77] using high
organic, and sometimes inorganic, contents of wastewater instead COD industrial wastewater as substrate. Results showed a COD
of having them treated with energy-intensive and overpriced conversion of 72%, 32 mW/m3 power density, and 200 mV voltage,
chemicals [72]. In MFCs, bacteria that act as catalysts oxidise the confirming that slaughterhouse wastewater is a good feedstock.
organic matter present in the wastewater, generating electricity in
the process. It is suggested to use a mixed culture rather than a pure 3.4. Non-fermentable organics
culture as a mixed culture can consume multiple types of substrates
[21]. The production of biohydrogen can occur via particular re-
Y. Park et al. [73] undertook a study to check the effect of three actions using different kinds of non-fermentable organics like
wastewater pre-acclimation strategies on electricity generation. glycerol, acetic acid, lactic acid, valeric acid, butyric acid, and pro-
The strategies were: (i) the domestic wastewater undergoes a serial pionic acid. Only electrogenic bacteria have the ability to
pre-acclimation process with acetate and glucose before being completely oxidise substrates that are non-fermentable [78], e.g.,
supplied, (ii) a one-step pre-acclimation with acetate is performed acetate, lactose, and glycerol, by the production of electricity.
on domestic wastewater before being supplied, and (iii) domestic Asensio et al. [79] focused on evaluating different types of fuels and
wastewater is supplied directly without any pre-acclimation step. their dosages in the performance of a DCMFC that had electrodes of
Strategy 1 showed the highest percentage of coulombic efficiency carbon felt and cationic membrane. Carboxylic acids were found to
(33.5%) and current generation (1.4 mA) followed by strategies 2 be more effective as fuels than alcohols (like ethanol or glycerol) or
(9.4% and 0.7 mA) and 3 (10.3% and 0.9 mA). The pre-acclimation single sugars (like fructose). In a system that was driven by acetate
strategy affected the microbial communities substantially, as solution, it was observed that the production of electricity
shown via pyrosequencing, thus suggesting that a serial pre- increased in a linear fashion when the organic load had up to
acclimation of wastewater with glucose and acetate has a signifi- 5000 ppm of COD fed into it.
cant effect in growing bacterial communities that have the Ebadinezhad et al. [60] explored the effect of sequential batch
electricity-producing ability using domestic wastewater. feeding by using a variety of substrates such as acetate, sucrose,
Some of the main sources of wastewater are from industries like ethanol, lactose, starch, methanol, and molasses in MFC power
the pharmaceutical, pesticide, cosmetic, and culinary industries, generation. The power production and removal of COD varied
along with others. The different kinds of wastewater that have been based on the complex nature of the substrate and consequently had
tested so far include domestic wastewater, refinery wastewater, an influence on the overall MFC performance. Average values of
swine wastewater, industrial wastewater, potato wastewater, food power density according to the results are as follows: acetate (513
processing wastewater, dairy manure wastewater, and winery mWm2), ethanol (376 mWm2), lactose (388 mWm2), sucrose
wastewater [74]. Municipal wastewater might not be a feasible (349 mWm2), starch (315 mWm2), molasses (328 mWm2), and
substrate due to its low biochemical oxygen demand (BOD) con- methanol (10 mWm2). Acetate had the highest power density
centration that categorises it as a low energy density carrier or value.
feedstock for MFCs [65]. Wastewater that contains toxic elements is The use of glycerol as a potential feedstock in an MFC was
9
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

investigated by Kim et al. [80] using a Shewanella oneidensis MR-1 undertaken using polarisation studies, percentage of COD removal,
and Klebsiella pneumonia J2B co-culture and an inoculated culture internal resistance, and coulombic efficiency. The maximum power
of a single species. The ability to uptake glycerol and generate output with corncob was 6.73 W/m3 at 17.28 A/m3 and with sug-
electricity was tested and compared. Results showed that the co- arcane bagasse, 8.78 W/m3 at 20.95 A/m3. The major challenge of
culture MFC metabolised glycerol successfully and then produced using lignocellulosic biomass is the recalcitrant nature of ligno-
energy, but the MFC with only MR-1 did not use glycerol. The celluloses, meaning its resistance to decomposition. But that can be
current density came out at 10 mA/m2, and the acidic by-products solved if a combination of acetic acid bacteria and cyanobacterium
lactate and acetate were consumed in the co-culture MFC. The J2B- is used.
only MFC accumulated acidic by-products. The MFC that has a co-
culture can be implemented to recover electrical energy from 3.6. Fermentation effluent
glycerol.
Fermentation effluents are a good choice of a substrate because
3.5. Lignocellulosic biomass as fermentable organics they consist of a wide range of by-products like acetate, butyrate,
ethanol, lactate, and formate, which can react further to produce
Lignocellulosic biomass or waste has been considered to be a more hydrogen. Production of biohydrogen via the process of dark
potential substrate for bioconversion because of its abundance, fermentation is a possible alternative solution to reduce the carbon
renewability, and natural source. Agricultural crops like a corncob, footprint and alleviate the energy crisis. The end products of
wheat straw, wood, and sorghum stalk consist of high amounts of fermentation must be consumed effectively for the economic
biochemical energy [81]. Lignocellulosic biomass primarily consti- feasibility of the biohydrogen production process and to avoid en-
tutes cellulose, hemicelluloses, and lignin, from which the energy ergy loss [59]. Testing included the utilisation of a single-chamber
conversion can take place [82]. In an experiment by Mohd Zaini microbial electrolysis cell (MEC), with results showing that the
Makhtar and Tajarudin [83]; three raw materials made of ligno- effluent of an ethanol-type dark-fermentation reactor can produce
cellulosic were added as substrates into a membrane-less MFC additional hydrogen [42]. In theory, 1 mol hexose can give 4 mol H2
where two bacterial species, Pseudomonas and Bacillus subtilis, via the dark fermentation process, but in practice, the maximum
were present as biocatalysts and sludge acted as the pseudomem- yield obtained has been reported to vary from 2.5 to 3.5 mol H2 per
brane. The objective was to discover which raw material produced mol hexose with the formation of few by-products due to ther-
the highest amount of electricity and whether this process is modynamical limitations [87].
feasible in the long term. The lignocellulosic raw materials were Varanasi et al. [59] conducted a study with the objective of
banana peel, palm oil mill effluent, and corn bran. The experiment selectively enriching an electrogenic mixed consortium in MFCs
outcomes revealed that the mediator-less MFC with sludge sup- that can utilise dark fermentative effluents as substrates. The
plemented with banana peel showed the highest electricity pro- influential anodic operational parameters were optimised to
duction. Palm oil mill effluent, corn bran, and banana peel produced further enhance power output using dark fermentative effluents.
138 mV (22.03 mW/m2), 176.8 mV (12.65 mW/m2), and 237.1 mV Results showed that fermented effluents are acceptable substrates
(23.75 mW/m2) of electricity. for bioanodes, and there was an increase in maximum power
Gregoire and Becker [84] explored the potential of direct density from 1.4 W/m3 to 6.2 W/m3 after the anodic parameters
lignocellulosic biomass conversion into energy in an SCMFC where were optimised and fermentation effluents were utilised. The
cellulose hydrolysis, anode respiration, and fermentation reactions average COD removal efficiency and coulombic efficiencies were
took place. Untreated corncob was able to produce energy for more 75.25% and 10.55%. Another study [88] aimed to obtain electrical
than 60 d with the addition of rumen fluid, occasional oxygen energy in an MFC from compounds that can be found in H2
exposure, and bioaugmentation with Geobacter metallireducens, fermentation effluent and successfully recovered energy from
giving out a maximum power density of 230 mW/m3. This study glucose generating H2 by using the Clostridium beijerinckii strain.
confirmed that the use of complex and solid lignocellulose as a During the fermentation procedure, 104 mmol/L H2 was produced
director is practicable for the long-term functionality of MFCs from 49.5% of the initial glucose concentration, which was
conditional on the anodic biofilm developing efficiently. It is 56 mmol/L; 5, 33, 3, and 1 mmol/L of lacetate, butyrate, lactate, and
advised that for the improved performance of MFCs, the lignocel- ethanol also came out. These end products were fed into the anodic
lulosic biomass should undergo pretreatment as raw cellulose is compartment and showed values of power density that ranged
difficult for microorganisms to degrade [82]. If the lignocelluloses between 0.6 and 1.2 W/m2.
are pretreated, many monosaccharides like glucose, and ferment-
able substances like hexose, pentose, acetic acid, can be obtained 3.7. Sunlight
from cellulose and hemicellulose hydrolysis. These products can
also be used as substrates in MFCs. This has been proved in an MFCs can function using solar energy as their energy source
experiment where a comparison was undertaken between simple [89]. A hybrid MFC (h-MFC) was used in a study [55] with a single-
sugar sucrose and lignocellulosic hydrolysates as substrates, based chamber and analysed the methylene blue (MB) dye degradation
on their electricity and hydrogen-producing ability in a single- using a TiO2 nanotube (TNT) array photoanode paired with carbon
chamber MFC and MEC using an environmentally friendly pro- felt bioanode, with both sharing a common air cathode. Results
cedure [85]. showed that this model of MFC showed increased power density,
A triple-chamber MFC was used by Krishnaraj et al. [86] to voltage, and current density of 14%, 4%, and 33%, and simulta-
degrade lignocellulosic biomass under the following conditions: neously degraded MB dye by 82.79% after an operation of 3.5 h
the presence of a freshwater cyanobacterium called Oscillatoria under simulated solar light illumination. The number of electrons
annae for the formation of glucose through cellulose hydrolysis in a increased under illumination due to the pairing of the TNT photo-
pretreatment process; electrocatalytic activity of Acetobacter aceti anode and conventional MFC bioanode as this added photo-
and Gluconobacter roseus co-culture for the oxidation of glucose to generated electrons to the MFC's external circuit, which
generate a current inside the MFC; carbon felt for the cathode and consequently accelerated the oxygen reduction reaction at the air
anode; substrates that are lignocellulosic materials such as corncob cathode, enhancing the overall performance of the MFC.
and sugarcane bagasse. The performance analysis of MFC was An MFC that requires the involvement of sunlight is a
10
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

microalgae-microbial fuel cell (m-MFC) as microalgae mediated cellulose as feedstock and the slow degradation efficiency of cel-
bio-electrochemical system for the transformation of carbonaceous lulose by the fermentative genera. Cellulomonas fimi, Cellulomonas
substances into bioelectricity [90]. MFCs convert sunlight into biazotea and Cellulomonas flavigena are microorganisms that can
electricity in microalgae cells through the natural process of degrade cellulose [96]. Their performance was compared, and re-
photosynthesis [91]. In a typical m-MFC, the production of O2 oc- sults showed that C. fimi degraded the highest quantity of cellulose
curs in microalgal cells by using solar energy, nutrients, bi- (2.5 g/L), and the highest power generation of 38.7 mW/m2 was
carbonates, and the CO2 given out by the heterotrophic bacteria attained by the MFC [96], and C. fimi can be used to produce an
[92]. These bacteria consume the O2 and the released organic electric current from cellulose in MFCs.
content. Since microalgae are photosynthetic microorganisms,
wavelength and light intensity have an effect on their growing 3.9. Landfill leachates
process and the power output. The following reactions occur at the
electrodes in an m-MFC [91]: Landfill effluents that are heavily polluted and have a complex
Anode: composition are called landfill leachates. They are constituted from
xenobiotic organic compounds, heavy metals, dissolved organic
Wastewater organics/CO2 þ e- matter, and inorganic macro-components, which are the four major
groups of pollutants [97]. Hassan et al. [57] investigated the per-
Cathode: formance of an MFC using old and young landfill leachate for its
substrate in removing pollutants and producing renewable energy.
O2 þ H þ e / H2O A power output of 96.8 m Wm2 and 90.0 ± 1.2% of COD removal
was achieved with 60% leachate in batch mode. The values
Overall reaction: decreased when employed with 100% fresh leachate in continuous
mode to a power output of 75 mWm2 and a 55.5% reduction of
Wastewater organics þ O2/CO2 þ H2O þ external power COD. The power output decreased further when using old landfill
leachates. This study proved the potential of ammonium as an
The reaction in the microalgae fuel cell: electricity-generating fuel.
The potential of an open circuit from landfill leachate was
CO2 þ H2O þ Light/ Algal biomass þ O2 investigated by Sonawane et al. [98]; using a fabricated direct air-
breathing cathode-based MFC. Three different MFCs were built
and studied under open-circuit conditions for 17 d, and the
maximum open-circuit voltage (OCV) was 1.29 V. The maximum
3.8. Cellulose and chitin cathode area-specific power density was 1513 mW/m2 in the
reactor. The feasibility of MFCs in treating landfill leachate and
There are some materials that are cheap and biopolymeric, like producing electricity was explored under the condition of high
cellulose and chitin, which can be found readily and used for conductivity (73,588 S cm1) and nitrogen concentration
generating electricity [89]. The shells of crabs and shrimps are (6,033 mg N L1) [99]. This experiment used an air-cathode MFC,
composed of chitin and are food waste. S. W. [58] reported the and biodegradable organic matter of 8.5 kg COD m3 d1 was
degradation of chitin anaerobically by a chitinolytic bacterium removed while simultaneously producing electricity of 344 mW/
called Aeromonas hydrophila, which is also electroactive, in both m3. The key studies related to the utilisation of substrates in mi-
MFC and fermentation systems. Succinate, acetate, lactate, ethanol, crobial fuel cells are summarised in Table 2.
and formate were the primary metabolites that were produced in
the MFC. The total metabolite concentration and electricity gener- 4. Effective implementation of microbial fuel cells
ation increased in the MFC system in comparison to the fermen-
tation system, proving that an electroactive bacterium can degrade The microbial fuel cell (MFC) is considered an effective long-
chitin in an MFC [93]. term solution to address rising energy demands. It is a promising
Gurav et al. [94] attempted to develop a single step process to approach with numerous applications, including energy genera-
produce electrical energy from chitin biomass. They found that a tion, wastewater treatment, biohydrogen production, and bio-
gram-positive electroactive bacterium, Bacillus circulans BBL03, is sensors. Considering its remarkable characteristics in
capable of producing electricity in an MFC with natural seawater environmental and commercial efficiency, researchers have
fed with 1% chitin. N-acetylglucosamine (GlcNAc) and metabolites tremendous interest in developing its output for other applications.
of degradation (lactate, formate, acetate, propionate, and butyrate) The following subsections of the paper provide a detailed overview
acted as electron donors and led to the production of a substantial of the diverse landscape of MFC application, as depicted in Fig. 4.
amount of electricity (26.508 mAcm2). Shewanella oneidensis MR-1
can oxidise wide ranges of fermentative organics and can degrade 4.1. Generation of electricity generated by living organisms
chitin in the MFC [95]. Experimental results revealed that the
metabolites formed during chitin degradation in the MFC were at a The world is experiencing a global energy crisis because of the
higher concentration than in fermentation systems and created degradation of non-renewable energy supplies and the constrained
additional energy. economic viability of sustainable energy technologies that
Cellulose is an abundant energy source for electricity production encompass the critical need for research and development into
in MFCs, but they need obligate anaerobes with the ability to electricity generated by living organisms. MFC technology is an
degrade cellulose and aid in transferring electrons to the electrode electricity generation alternative that uses microorganisms to
(exoelectrogens). To explore that, S. W. [95] worked on commu- convert chemical energy into electrical energy [101]. MFC may be a
nities of bacteria that can evolve in SCMFCs with air cathodes that potential solution as a novel bioremediation technique for trans-
use cellulose as substrate and how the bacterial consortium forming carbon-rich waste by harnessing the metabolic capacity of
changed over time. Further investigations are needed to find a microorganisms in real-time [102]. In contrast to other wastewater
relationship between low power production in MFCs that have treatment techniques, the catalytic function of microorganisms in
11
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

an MFC involves the unmediated transfer of chemical energy into monitoring [113]. MFCs are produced and categorised into several
electrical energy [103]. Fig. 5 illustrates the function of a microbial varieties based on electrolyte nature and membrane and electrode
fuel cell for electricity generation and wastewater treatment which alignment. The primary kinds are: (i) single-chamber MFCs, (ii) up-
does not require separate purification or conversion procedures for flow MFC stacked, (iii) stacked MFCs, and (iv) double-chamber
energy products. MFCs [41].
Chemical substances containing energy are retrieved from
wastewater using the conventional treatment method. An MFC 4.2. Biohydrogen generation
generates electricity by oxidising substrates in an anode chamber,
resulting in electron and proton transportation [104]. In compari- Another intriguing implementation of MFC technology is the
son to conventional treatment, a pilot study [105] conducted in a generation of biohydrogen. The microbial electrolysis cell (MEC), a
stackable horizontal MFC showed significant reductions in chemi- transformed MFC device, is used to produce biohydrogen. Microbial
cal oxygen demand (COD) removal (79.7%), electricity generation metabolism and electrochemistry are linked in MEC operation.
(0.47 W/m3) and total N removal (71.8%) with minimal operational MFCs can be easily adjusted or modified for hydrogen production
cost. MFCs are ecologically favourable technologies because they using an anaerobic cathode in addition to complementing the
generate and operate electricity under mild processing conditions electricity supplied by bacteria. This occurs via an external source to
such as pH and temperature. The MFCs save energy and can lessen proton quantities in the cathode cell. An exoelectrogenic
generate up to 1.8 kWh/m3 of treated effluent or 1.43 kWh/m3 of bacterium oxidises the substrate in the MEC, leading to CO2, proton,
primary sludge which is less than other technologies such as aer- and electron production [114]. Hydrogen gas is formed when pro-
obic processes [106]. The MFCs utilise only a minimal amount of tons and electrons react with catalytic function.
external energy (10% approximately) for their operation, indicating The process includes the transfer of electrons from the anode to
a significant potential for energy savings. the cathode via an electrical circuit. The hydrogen ions pass into the
Several studies estimate that MFCs are capable of producing cathode through the membrane. The electrons in the cathode
electricity from food products (2e260 kWh/t) based on the BOD portion unite with the protons to produce hydrogen gas. An
and the proportion of the waste generated [65]. Pt black was used external voltage triggers this hydrogen generation method, and the
as a catalyst and obtained a coulombic efficiency of about 97% [107]. hydrogen produced might be used to fulfil hydrogen demand [115].
The MFCs do not generate a huge amount of electricity because the Hydrogen Evolution Reaction (HER) is thermodynamically disad-
rate at which electrons are abstracted is relatively slow. In con- vantageous since it needs a 0.41V input. In contrast, microorgan-
ventional fuel cells, the highest efficiency rate is limited to the isms create an estimated 0.3 V by decomposing the substrates
Carnot limit. In MFCs, greater efficiencies of more than 70% may be found in the anode cell [116]. In practice, a MEC requires 0.25e0.8 V
obtained [108]. MFCs also demonstrate several environmental and input.
economic advantages, such as the removal of toxins, the recycling One example of biohydrogen synthesis and electric current
of nutrients, and the production of electricity from wastewater. production is a combined approach incorporating an MFC that uses
Treatment of fruit wastewater using a low priced non-woven fabric acid-rich effluent. Processed palm oil effluent containing a specific
separator is said to have provided a maximum net income of $7.1 M enzyme and surfactant has been employed to boost biohydrogen
over a 20 y period [109]. This also shows that MFC technology may synthesis and power generation [17]. Raw materials such as
recover a significant amount of energy via electricity generation. wastewater from food processing and sugar fermentation, and
The typical feedstocks such as wastewater from the mustard municipal solid waste can also generate hydrogen. Microbial elec-
tuber and cashew apple juice have created electricity in MFCs with trolysis cell (MEC) is a promising and sustainable hydrogen-
a power density of 31.6 W/m2 [110]). In another study [111], elec- producing technique because of the potential for long recovery
tricity production was measured over 195 d using highly salty rates from various natural feedstocks [117]. MFC and MEC both
mustard wastewater. The MFC performance was evaluated and consist of the same materials: an anode, a cathode, and an ion-
found to have COD and BOD removal efficiencies of 89% and 98.6%. membrane. MECs need a minor adjustment to the MFC design by
The maximum power density was reported to be 12 W/m3. Experts establishing an anaerobic cathode [118].
have been working to improve several parameters and develop the MFCs may be used to generate electricity as well as treat
MFC method towards increased sustainability. Glucose wastewater wastewater [44]. The rate of hydrogen generation in MEC is affected
was used as a substrate in an experiment in a double-chamber MFC by several aspects, including MEC construction, electrode materials,
where the power density reached 4,310 mW/m2 [90]. It was re- solution chemistry, microorganisms, and mode of operation [119].
ported that methanol is not convenient for electricity generation, Various adjustments have been shown in studies to boost hydrogen
whereas ethanol and acetate are good substrates for electricity production rates and efficiency. Using a double-chamber MEC
production. Metal catalysts are costly to use, and a natural catalyst arrangement, initial studies have shown hydrogen generation rates
composed of sugarcane debris and activated carbon cathode has in the range of 0.01e0.1 m3/d [120]. Cheng et al. [121] obtained an
been studied and proven effective [112]. This study revealed expanded production level of 1.1 m3/d. The increased outcome
maximum power and current densities, with the removal of 64% resulted from a greater anode surface area and the application of an
COD and 51% BOD. anionic exchange membrane.
MFC electricity can also be utilised to power electric equipment
or machinery and control robots. Such robots are sometimes 4.3. Biosensor production
referred to as ‘gastrobots’, which can either metabolise food or be
powered by air or water. By consuming the substrate fuel, elec- Electrochemical biosensors, particularly MFC-based biosensors,
tricity conversion occurs, which is frequently deposited in the ro- provide steady performance, feasibility, and sensitivity. They have
bots' batteries, making them into autonomous power systems. received much recognition in contrast to conventional sensors. The
Another promising invention was the ‘Gastronome’, a robot that specific biosensors benefit from anaerobic biofilms [122]. The bio-
used biomass-powered power conversion technology in an MFC anode inside a regular MFC biosensor acts as a sensing component
[37]. EcoBot II is an environmental monitoring robot outfitted with toxicity level. The biocathode functions as a transducer and has
8 MFCs functioning on raw products. Rotting fruits were used as shown more sensitivity than a bioanode. This performance
substrate fuel and showed significant operation for environmental improvement is primarily because MFC biosensors do not require
12
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

Fig. 4. Applications of the microbial fuel cell [100].

Fig. 5. Microbial fuel cell's working principle for wastewater treatment and electricity generation (reprinted with the permission of Elsevier from [17].

organic matter input [123]. The MFC has been demonstrated to be durability since exoelectrogenic biofilms prolong the longevity of
an effective biosensor for detecting wastewater organic chemicals elements and reduce the need for their replacement.
and pollutants [124]. Conventional biosensors often need a trans- The initial stage in designing the MFC-based biosensor system is
ducer; however, MFCs work as a transducer in and of itself, making to have proper cathodic and anodic reactions [126]. MFCs can be a
MFCs a cost-effective biosensor, as shown in Fig. 6. Exoelectrogens potential sensor for biological oxygen demand (BOD) [126], and it
in the anode work as generators, while electrodes and PEM serve as has been demonstrated that the BOD sensor has outstanding
a transducer. The key benefit of an MFC biosensor is its stability and operational sustainability and repeatability and can likely be

13
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

Fig. 6. Comparison between traditional whole-cell and MFC-based biosensor [125]. Traditional whole-cell biosensors typically use pigment molecules, green fluorescence proteins
(GFP), luminescence and enzyme activity as indicators.

actively maintained for 5 y [127]. A BOD sensor based on an MFC starch [149]. A study was conducted in starch processing waste-
may be more challenging to use with industrial wastewater. water (SPW) to assess the treatment effectiveness of a double-
Wastewater contains both degradable organic matter and harmful chamber MFC. Proteins, carbohydrates, cellulose, vitamins, and
contaminants. Sudden variations in BOD and toxicity may occur other substances are abundant in SPW. SPW was utilised to assess
with an MFC-based BOD sensor [44]. The current density in an the treatment effectiveness of a double-chamber MFC. After 140
MFC-based sensor reduces with increasing toxicity of the toxic d of performance, the MFC reduced COD by 98%. This was com-
chemicals, but it increases with increasing BOD. The abrupt change plemented by a 91% ammoniaenitrogen elimination efficiency.
in BOD may weaken the responses of the MFC sensor to poisoning. Another study utilising potato processing effluent obtained a 91%
Research indicates that an integrated effect of BOD with toxicity COD reduction [150]. A separate study [37] used organic-rich, non-
influenced the outcome during the utilisation of the MFC sensor toxic cocoa wastewater in a double-chamber MFC. The findings
detecting Cr(IV) [128]. Table 3 summarises the performance of revealed that following a batch mode MFC process, a maximum
different microbial fuel cells in generating bioenergy. COD of 75% was eliminated.
Animal wastewater has a high organic content as well as large
quantities of phosphate and nitrate, which cause surface water
4.4. Wastewater treatment eutrophication. A promising method for producing sorbents from
waste cellulose casings was proposed and evaluated economically
Wastewater containing various forms of the organic substrate on a pilot scale using pyrolysis and calcium chloride (CaCl2) acti-
has a high potential as an energy source. Wastewater from different vation [151]. This sorbent was capable to capture 31.8 kg P t1, with
sources holds energy in its biodegradable organic matter [144]. more than 80% of the acquired phosphorus (P) being readily
MFC technology, which was proposed for application in wastewater available as crop nutrition. The commercialisation of the novel
treatment in 1991 [145], is advantageous as a fundamentally new sorbent may be commercially viable. Few studies have shown that
technique because of its ability to generate bioenergy, reduce en- animal effluent can be treated and converted into bioenergy in
ergy loss [146] and operate in the absence of gas [147]. The MFC is a various MFCs. A study involving swine wastewater in several MFCs
viable technology for the treatment of highly contaminated obtained the highest, approximately 92%, COD removal and 83%
wastewater or industrial effluent while also reducing operational ammonia reduction following an operation for about 100 h [152].
cost, features which have high sustainability. For substrate oxida- Animal carcass wastewater can be hydrolysed by alkaline treatment
tion, the inoculum is produced from primary industrial wastewater into smaller components such as amino acids, minerals, and sugars
or specific bacterial cultures obtained from wastewater [148]. The resulting in a sterile solvent (with BOD 70 g/L, ammonia 1 g/L, COD
influence of various fundamental parameters on MFC performance, 105 g/L) known as ACW. The most significant COD loss produced
such as total solids, COD, BOD, and acidity, has been examined. was more than 50%, while the MFC's nitrate removal effectiveness
Standard methodologies are often used to assess the wastewater was approximately 80% in an up-flow tubular MFC [153].
treatment effectiveness of MFCs. MFC achieves the highest proportion of C elimination (>90%)
Compared to other industrial wastewater, food wastewater is from wastewater. Exoelectrogens produce protons and electrons in
mildly toxic, although it has an increased BOD and is abundant in
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S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

the anode by oxidising the organic elements present in waste-


[129]
[130]
[131]

Pmax ¼ 0.0249 mW cm2 Voc ¼ 0.803 V [132]

[133]

[134]
[135]

[136]
[137]

[138]
[139]
[140]
[141]

[142]
[143]
water. Protons are transmitted by the membrane, whereas the
Ref.

electrodes transmit electrons to the cathode chamber. Clean water

Ricobendazole as the precursor of Fe-


and energy are produced as a result of these procedures. Nitrogen

0.0058 mW cm2Voc ¼ 0.66 V


Cell performance (maximum power

Pmax ¼ 0.068 mW cm2Voc ¼ 0.5 V


Pmax ¼ 0.012 mW cm2Voc ¼ 0.8 V
Pmax ¼ 0.0209 mW cm2 using Fe-
often occurs in wastewater in the form of ammonium, and the
conventional removal procedure comprises successive nitrifica-
tion and denitrification. The typical procedures require a signifi-

Pmax ¼ 1,270 ± 30 mW/m2

Pmax ¼ 1,850 ± 20 mW/m2


Pmax ¼ 0.00165 mW cm2

Pmax ¼ 0.027 mW cm2

0.019 mW cm2
cant mass of organic material and increased energy and sludge for

Pmax ¼ 1,008 mW/m2

2,420 mW/m2
Pmax ¼ 1,606 mW/m2
Pmax ¼ 1,296 mW/m2

the denitrification process [154].

610 mW/m2
Researchers have investigated that integrating MFC with con-
density/voltage)

NC ORR catalyst

ventional wastewater treatment will expand its application and


treatment efficiency. Examples of such integrated MFCs are the

¼
¼
¼
¼
membrane bioreactor MFC, desalination MFC, and constructed

Pmax
Pmax
Pmax
Pmax
wet-land MFC. The COD and ammonium nitrogen removal were
98% and 95%, whereas total nitrogen removal efficiencies were
Gas diffusion cathode with Pt as oxygen

Gas diffusion electrode catalyst used:


Carbon clothes air cathode with Pt/C

approximately 89% when a baffle was used instead of an ion-


Carbon cloth with an area of 14 cm2
reduction reaction (ORR) catalyst

membrane in the MFC [155]. Specific microbial communities


Carbon cloth containing 50 mM
Carbon brush and carbon cloth
Carbon paper with Pt catalyst.

were also added to the biofilms for effective treatment and energy
Carbon felt and porous carbon Carbon felt with Pt catalyst

production. Using sophisticated techniques and technologies, MFC


potassium ferricyanide.

removes not only nutrients but also various metal ions from
Pt coated carbon felt

wastewater which are often found in petrochemical facilities,


Carbon fibre felt

tanneries, and rayon manufacturing facilities. The MFC technology


NeNieCNF/ACF
Carbon paper
Carbon cloth

Carbon cloth

appears promising for bioenergy and wastewater treatment ap-


Carbon rod
Fe-NC ORR

plications. The performance of different types of this technology


catalysts
Cathode

in treating wastewater is tabulated in Table 4.

5. Factors affecting microbial fuel cell performance


Carbon cloth with an area

5.1. Anode
Mixed microorganisms from the anaerobic digester Carbon fibre/MW CNT
Carbon fibre bundles

PPy/NFs/PET textile

Microorganisms have an essential role in generating electrons


NeNieCNF/ACF
Carbon paper
Carbon brush

Carbon brush

in the anode. Electron acceptors are lowered by using these


Carbon cloth
Carbon cloth

Graphite felt
Metal anode
Carbon felt

of 14 cm2

electrons in the cathode cell when passing through the circuit. The
Graphite
Anode

anode chamber acts as an electron receptor in the MFC reactor.


The structural and fundamental characteristics of the anodes have
a significant impact on MFC efficiency due to the efficacy of the
S.Oneidensis (lactic acid to electricity)S.Cerevisiae

substrate oxidation and its effect on bacterial adhesion [168].


These features are connected with extracellular electron transfer
Mixed microorganism Source: bottom mud

(EET) effectiveness through a higher surface area which is speci-


alised for biofilm development. The anode chamber includes all
Microorganism source: active sludge

Rapeseed straw hydrolysate Mixed microorganisms from sludge

essential requirements for biomass degradation. The components


Mixed anaerobic microorganism

of this compartment are the substrate, a mediator (optional), a


Source of inoculum/microbes

Cellulose degrading bacteria

microbe, and the anode [104].


Anodic microbial electron substitution is one of the most vital
(Glucose to lactic acid)
Artificial wastewater

components influencing MFC performance, boosting the micro-


Citrobactersp. LAR-1
Performance of different microbial fuel cells for bioenergy generation.

bial electron transfer rate using various practical methods and


Escherichia coli

Escherichia coli

adjusting electrode and cell design [169]. The electrodes are


E.coli (DH5a)

crucial components of an MFC and are vital in increasing its effi-


cacy. The several anode materials have been examined in various
studies. Suitable anode materials should be considered when
implementing a standard anode in an MFC. It should be conduc-
tive, cost-effective, non-corrosive, and with a large surface area
Sodium lignosulphonate

[101]. The corrosion continues to either increase through voltaic


Cornstalk hydrolysate
MFC configuration Type of substrate/fuel

Synthetic wastewater

current output and the large surface area or lower the current by
Sodium acetate

generating radioactive substances.


Geobacter sp.

The most common anode material is carbon-based, such as


Rice Straw

E.coli(K12)
Rice bran

graphite rod or felt, carbon brush or fibre, as well as various metal


Glucose

Glucose
Acetate

electrodes. Carbon-based electrode materials (plates or rods) are


essential materials for anode electrodes due to their low cost, easy
operation, and vast pore stability [170]. Compact substances such
Double-chamber
Single- chamber

as solid carbon are suitable for developing exoelectrogenic bac-


teria that can generate electricity from domestic wastewater
Fixed-bed

because of their enormous surface area and porosity [171]. Carbon


Table 3

felt and carbon brushes have greater power densities of 2,437 and
2,110 mW/m2 (90% COD elimination) [172]. Kaewkannetra et al.
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S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

Table 4
Performance of different microbial fuel cells for wastewater treatment.

MFC configuration Wastewater/heavy Electrode material Removal efficiency Power density Reference
metal

Single-chamber Anode: carbon fibre


Mixed wastewater 87 ± 5% COD 70e360 mW/m2 [156]
Cathode: carbon paper
with 4 PTFE diffusion layers
and a Pt catalyst layer.
Cadmium Anode: graphite rod 90% 289 mW/m2 [157]
Cathode: graphite rod
Swine wastewater Anode: Toray carbon paper 92% 282.83 mA/m2 [158]
Cathode: carbon cloth
Landfill leachates Anode: graphite (granular) 70e85% COD 20.9 W/m3 [159]
Cathode: graphite(granular)
2
Double-chamber Sewage wastewater Anode: graphite rod 97% total suspended solid 836.81 mW/m [160]
with Distillery Cathode: graphite rod (TSS), 78.66% COD, 39.66%
spent wash total dissolved solids
Slaughterhouse Anode: carbon cloth 578 mW/m2 [161]
wastewater Cathode: carbon cloth
Distillery Anode: copper wire 63.5 ± 1.5% COD 63.8 ± 0.65 mW/m2 [64,61,62]
wastewater Cathode: copper wire
Vegetable oil Anode: titanium rod 67.3% sulphate 6119 mW/m2 [63]
industrial Cathode: carbon cloth 73.6% phosphorus
wastewater 80e90% COD
Cassava mill Anode: graphite plate ~28% COD 1771 mW/m2 [162]
wastewater Cathode: graphite plate
Tubular Sewage sludge Anode: Ag/AgCl 53% TCOD 73 mA/m2 [163]
Cathode: Ag/AgCl
2
Swine wastewater Anode: graphite felt 83.8% COD, 90.8% NH4þ eN 175.7 W/m [164]
Cathode: graphite felt
2
Up-flow constructed wetland (UFCW) Wastewater from Anode: carbon felt 100% COD, 91% NH4þ, 40% NO3- 6.12 mW/m [165]
glove factory Cathode: carbon felt
Cubic two-cell Livestock Anode: carbon fibre 75e82% COD 122 mW/m2 [166]
wastewater Cathode: carbon fibre
Modularised system Municipal Anode: polyvinyl chloride (PVC) 70e90% COD 7e60 W/m3 [167]
wastewater Cathode: polyvinyl chloride (PVC)

[162] conducted a study using graphite plate electrodes in the used in an MFC cathode chamber to boost its performance.
treatment of cassava mill effluent and obtained notable outcomes Increased cathodic kinetics is often one of the most critical factors
(maximum power density of 1,771 mW/m2). The use of graphite felt in MFC technology [171]. Despite numerous advances, these elec-
with a macro-structured anode in continuous flow MFCs improved trodes have limitations such as high expense, surface toxicity of
wastewater treatment. The vertical arrangement of fins in the microorganisms, and inadequate re-oxidation, resulting in the
anode enhanced regular water flow dispersion and the interactivity standard replacement of catholyte. For these reasons, more desir-
among microorganisms and wastewater matter [173]. Several able materials have been investigated to boost MFC power gener-
studies on the suitability of anode materials have been conducted, ation. Carbon-based materials, metal oxides and complexes, and
and it has been found that improvement in MFC performance was other materials are among these. Chemical activation of electrode
accomplished primarily through a highly porous structure. Despite materials at a reduced cost improves MFC electrochemical prop-
the fact that CC is commonly used as an anode, nitrogen-doped erties by modifying the cathode layer to enhance microbial prop-
permeable carbons achieved a maximum power density of erties [178].
2777.7 mW/m2 [174]. Carbon structures have contributed to remarkable progress on
Corrosion resistance and cost-effectiveness are two advantages high catalyst activity and performance in many studies. For
of metal-based electrode materials [175]. The multi-dimensional instance, one study focused on heteroatom-doped carbon demon-
characteristics of biocompatible metal oxides can give a surface strated significant cathodic performance (1,328.9 mW/m2) similar
area that is more reactive and improves diffusion and electron to the conventional catalyst, Pt/C, which is used in cathode cells
transport [176]. Various types of anode materials are alternatives, (1,337.7 mW/m2) [179]. Cathodes produced using carbon fibre
especially carbon structured electrode materials. The anode mate- cloth, polyvinylidene fluoride and Mn, O, Fe, and C as a catalyst have
rials can be modified using metals or oxide-based nanoparticles. been proposed to be a potential cathode membrane for wastewater
This improves microbial cell adherence and ohmic consumption. treatment with low operational cost and adequate removal effi-
The power density of the anode, which consisted of iron (II, III) ciency. Research findings show that 90% COD, 80% ammonium, and
oxide (Fe3O4) and carbon nanotubes, was 830 mW/m2. When Fe3O4 65% total phosphorous were removed efficiently. Based on several
is attached to carbon nanotubes, it forms a multilayered network studies, these cathode membranes are considered prospective
that promotes microbe development and electron transmission wastewater treatment initiatives with higher commercialisation
[177]. potential [143].
Synthetic wastewater and municipal wastewater removed 85%
5.2. Cathode and 45% COD, due to loss of catalytic activity and non-electrogenic
microbe contact. An experiment was conducted in a stacked MFC
Alongside the anode, cathodes influence both energy output with a fed-batch operating duration of 48 h that achieved a
and wastewater treatment due to their impact on ORR. Ferricyanide maximum power density of 50.9 1.7 W/m3 while efficiently
and permanganate are prominent experimental electron acceptors removing 97% COD from the wastewater. The experiment used

16
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

compact electrodes of granular activated carbon (GAC) [120]., a chambers if no buffer solution is used in an operative MFC. The
Remarkable MFC performance with a power density of 1,771 mW/ operation of an MFC commences with the proton exchange mem-
m2 is achieved when graphite plates are used in both electrodes brane (PEM), forming a transport barrier for protons. The technique
[162]. The FeeN-G has been employed as a cathode catalyst sub- involves proton transport across the membrane, which is more
stitute in MFCs, attaining a power density of 1,149.8 mW/m2. The Fe passive in contrast to proton formation in the anode and proton loss
and N's functionalisation on graphite considerably improved MFC in the cathode, resulting in a pH variation [189]. The pH difference
performance [180]. increases proton distribution to the cathode from the anode
A bioreactor-MFC system integrating a relatively low-priced chamber, resulting in a dynamic equilibrium. Protons generated
membrane and a cathode membrane of carbon fibre cloth was during biodegradation act with diffused oxygen in the cathodic cell.
developed by Lin et al. [135] for wastewater treatment. GAC was Others concentrate in the anode section as they do not pass rapidly
applied to the cathode membrane to reduce biofouling and through the proton exchange membrane or salt bridge [190].
improve power output. In this experiment, the elimination of COD One study found that the pH changed at the cathode and anode
was determined to be 90% and ammonium 80%. The doped GAC on after adding a phosphate buffer, and the current output was
the cathode was used to achieve 90% oxidative elimination of boosted by 1e2 times [191]. The buffer increased the proton
tetracycline hydrochloride by reactive oxygen species. Carbon and transportation flow, increasing proton availability for the cathodic
metal nanoparticles with new combinations and diverse dimen- method. At pH 6 and 9, the current density and coulombic effi-
sional configurations have received a lot of interest [181]. A ciency are frequently reduced. The current increases dramatically
comprehensive study [182] was conducted, focusing on the use of a as the pH rises from 7.5 to 8 and drops drastically at pH 9. A sig-
biocathode for carbon and nitrogen removal while also generating nificant pH difference across the membrane occurs due to increased
power. Various studies show that S. oneidensis and electrochemical activity leading to high current flow and energy
G. sulphurreducens have potential power generation mechanisms supply [192]. Anam et al. [193] examined combining an HCl solu-
that carry electrons directly [183]. Several molecular strategies tion into the cathode, intensifying the current production nearly
have been improved in order to develop microbial catalysts and two-fold. This result indicates that proton usage at the cathode is
biocatalysts. Such approaches include chemical treatment, modi- not an expanding component of power output. Adding NaCl to
fication of microbes, and gene modification to generate MFCs increased ionic strength, which in turn boosted power pro-
biosurfactants. duction [194].
The anode chamber becomes increasingly acidic as protons
5.3. Electrode materials accumulate, making it unsuitable for bacterial growth [195]. High
pH in the cathode chamber lowers current production. Low pH
MFC performance and cost are mostly determined by the allowed for oxygen reduction and increased MFC electric current.
membrane electrode configuration, installation, and overall design. The bacteria's activities are reduced because of the anolyte's low
Using effective electrode materials can contribute to increasing pH, which has a major influence on biofilm growth and MFC power
MFC performance. This is because activation polarisation losses output [196]. This reveals that a larger concentration of protons in
depend on the type of anode materials used in a fuel cell. One of the the cathode chamber lowers the power density. When it comes to
most difficult challenges for the MFC to perform as an economical COD elimination during wastewater treatment, a higher pH in the
and accessible technology is in evaluating an efficient electrode anode chamber is beneficial, but it diminishes power.
material [184]. The Pt and Pt electrodes perform better than carbon Several factors influence the pH difference, including the type of
and graphite-based electrodes in both anode and cathode config- substrate/microbes in the anode, the catholyte material, and proton
urations, although they are significantly more expensive (S [185]. In flow across the membrane [197]. The most important effect of pH
order to identify the most effective electrode materials, it is on the electrolyte is its impact on microbial metabolism and the
important to determine their resistance power, and studies show rate of the cathodic oxygen reduction reaction. By increasing the
that the least resistant ones are the most effective [101]. Applicable acidity of the anode, the driving power for cathodic oxygen
to both anode and cathode, the ideal electrode material is non- reduction rises by 59 Mv/pH unit assuming the catalyst activity is
flammable, conductive, non-fouling, and economical. Research kept high [198]. In order to achieve better output in a microbial fuel
has proved that using a high-efficiency electrode material like cell, an optimum level of pH for microbial growth is necessary, and
platinum is not cost-effective in large-scale applications. An studies suggest that this level should be between 6 and 9.
increased cost efficiency has been a focus in MFC research.
In the domain of material characteristics, Wei et al. [186] 5.5. Proton exchange
focused on the relevance of the high conductivity and mechanical
strength necessary for successful electron transport. The surface In an MFC, anode and cathode chambers remain connected
area in the electrode should be raised and separated into numerous through the PEM [101]. The concentration polarisation degradation
forms to improve bacteria adherence [187]. According to the liter- and internal resistance of an MFC system may be influenced by a
ature, an electrode modified with nanoparticles generates more proton exchange system, which affects the overall energy output of
power than a standard electrode. A platinum-coated cathode pro- the MFC. The membrane is critical in preventing anode and cathode
duces significantly more electric current than a plain cathode with chambers from overlapping, particularly by wastewater, oxygen,
no catalyst [188]. A study was performed using G. Sulphurreducens and carbon dioxide [199]. One intriguing feature of the PEM is that
as an inoculum, and it was observed that a biofilm electrode con- it enables hydrogen ions or protons to infiltrate by generating
taining magnetic nanoparticles enhanced the electrode's electro- electricity. Protons (Hþ) are generated in an anode chamber by
mechanical conductivity by 1.22e1.88 times compared to regular exoelectrogens and transported in a cathode chamber via a PEM
carbon paper electrodes and strengthened the electron transport membrane, which influences power output and electricity gener-
mechanism [148]. ation [200]. The membrane also enhances the MFC's internal
resistance and ion/electrolyte dispersion affecting the current
5.4. pH buffer and electrolyte production of the fuel cell [101].
Factors to consider in membrane selection include biofouling,
A variation in pH is apparent between the anodic and cathodic internal resistance, oxygen diffusion, and substrate loss [201]. The
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S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

different energy levels of PEMs have been experimented with in hinder their ability to be scaled up to the industrial level. Some of
numerous studies. Due to its permeability and selectivity to the the challenges to the large-scale application of MFCs are given
proton, the most often utilised PEM in MFC technology is the Nafion below:
[202]. The Nafion also comes with several challenges, such as high
operational cost and non-biocompatible characteristics [17]. The (i) Expensive MFC components, particularly the cathodes and
Nafion-based PEM can be integrated with other materials to reduce the PEMs, are difficult to replace with low-cost and widely
operational costs. This is done by mixing different inorganic addi- available alternatives. Traditional activated sludge treat-
tives and polymers into the Nafion ionomer [203]. ments for domestic wastewater. On average, MFC are 30
A low-cost PEM in MFCs has recently been established using a times cheaper than MFCs in terms of capital cost [212].
PVA-Nafion-borosilicate membrane. An organic matter decompo- (ii) The power generated by the cell is too low to run a sensor or
sition levels in wastewater varied between 54.5% and 64.25% [204]. a transmitter continuously. This is due to the low efficiency of
Kondaveeti et al. [205] performed experiments on low-priced the process attributed to the slow reaction kinetics at the
separators for amplified power output and microbial fuel cell electrodes and losses due to high ohmic resistance, particu-
field usage, which yielded CE performance for non-woven fabric larly at high current densities. This issue can be overcome by
polypropylene (PP80) at 44%, whereas Nafion identified 50%. The a suitable power management system, where data is trans-
study was conducted using PP80with a high voltage of 0.477 V as a ferred after enough energy is stored [16].
lost cost separator (0.481 V). The non-woven fabric polypropylene (iii) Unable to operate at low temperatures as it affects the
exhibited an increased power density of 121 W/m3 when compared metabolic activities of the microbial community [33].
to Nafion's 118 W/m2. All sizes of the separators had substantial O2 (iv) Operational issues, such as electrolyte resistance, increased
mass transfer in terms of O2 diffusion, resulting in lower coulombic over-potential, voltage reversal, and unstable long-term
efficiencies (CE) and cation exchange membranes. The authors operation.
suggest that a low-cost separator might be effective for MFCs with (v) Biofouling of electrodes and PEM. Some anti-biofouling
greater cell voltage and less oxygen diffusion. strategies have been proposed, including the hydrophilicity
A new permeable clay separator was developed as a low-budget control of the binding site and surface alteration or a simple
separator using the NCE low separator by Daud et al. [206] to concentrated acid wash [213]. The prevention of biofouling
substitute the high-cost PEM. The highest power was remains a challenge for cathodes thinly layered with
2,250 ± 21 mW/m2 and the current flow recorded was 6.0 A/m2, catalysts.
with a CE of 44 ± 21%. The investigation revealed that the low-cost (vi) Absence of consensus in design and process parameters [25].
separator NCE outperformed the expensive Nafion 117, yielding Operating parameters and design affect MFC performance,
much more power, current density, and CE. Studies show that a making it difficult to identify the relationships with the po-
power output less than a significant threshold is caused by the wer outputs and efficiencies of treatment.
influence of the PEM's enormous surface area. This is due to (vii) The small electrode surface area for the microorganisms
reduced internal resistance, which expands the PEM surface area in limits biofilm production. The application of air cathodes,
the MFC [40]. stacked reactors, and cloth electrode assemblies have been
Low-cost polyvinyl alcohol (PVA) hydrogel has also been intro- suggested to increase the efficiency of oxygen use and pre-
duced to enhance the PEM in MFC [17] to enhance proton con- vent aeration of water or electrolytes [214].
ductivity and durability. To generate electricity, PVA-H was used as
a PEM with a toluene removal efficiency of more than 99% in a
tubular air-cathode MFC [207]. Various organic-inorganic polymer 6.2. Future opportunities
membranes have recently been produced by integrating different
nanofillers placed inside a polymer matrix [208]. In addition to After critically reviewing the literature and identifying chal-
removing phenol and acetone from wastewater, MFCs using sul- lenges in the scaling of MFCs, the following directions have been
phonated polyether ketone membranes have also been utilised to recommended for future research and development of MFCs:
generate energy [209].
Many other materials, particularly sulphonated polymers, have  A huge knowledge gap between laboratory to commercial
been used as membranes/separators in MFCs, substituting the implementation prevents proper evaluation of the viability of
Nafion membrane. Sulphonated poly (ether ether ketone) (SPEEK)- MFCs in real-life examples under environmental process con-
based and nanofiller-based composite membranes outperformed ditions. The large-scale application of MFC technology is
Nafion series membranes in terms of power supply. MFCs using restricted by its microbiological, electrochemical, and techno-
SPEEK and GO (graphene oxide) -SPEEK as separators achieved logical limitations. The techno-economic feasibility assessments
82.65% and 83.01% COD removal efficiency [210]. Recent research have been difficult to conduct on lifecycle cost assessments of
has focused on minimising the cost of MFCs by introducing ceramic MFCs, based on a field operation, capital, and maintenance costs,
materials to produce new types of membranes. Researchers have due to the limited examples of scaled-up applications.
assessed natural rubber as an innovative low-cost alternative Expanding our understanding to meet this gap is crucial for the
membrane [211]. This material functioned for an extended period wider acceptance and application of MFCs, such as by exploring
of time, exhibiting more durable energy than standard materials. ion transport selectivity, flow-kinetics modelling and simula-
Despite the promising outcomes, most advanced technologies are tion, preparation of cost-effective membranes, optimisation
yet to be evaluated, and this low-cost material requires compre- electrode conditions, robust field equipment, and promoting
hensive research and development. innovation in novel energy storage and harvesting methods. The
use of an experimental method design has been recommended
6. Challenges and future opportunities to optimise process parameters, as this technique saves time and
resources, enables the optimisation of many variables concur-
6.1. Challenges rently, and elucidates the effect of each variable on the overall
output [215]. Modelling techniques, namely mechanism-based
The potential applications of MFCs face various challenges that and application-based models, driven by data and advanced
18
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

computational intelligence tools allow for the identification of studies and applications have primarily used SCMFCs and
the various limiting factors of MFCs and provide insights into DCMFCs, even though hybrid stacked MFCs have often offered
MFC performance enhancements [216]. The incorporation of greater advantages in terms of substrate conversion effi-
multiple parameters in an all-inclusive indicator is necessary for ciency, tolerance to internal resistance, and electricity output.
research comparisons [25]. As much as 5.04 mW/m2,e3.6W/m2, 75e513mW/m2 and
 The development of novel electrodes and membranes is crucial 135.4mW/m2 electricity generation was reported from
for enhancing the stability of MFCs and optimising electrical SCMFCs, DCMFCs, and stacked MFCs with the highest being
conductivity and use. Increasing the surface area and electrical produced from the single/hybrid single-chamber type which
conductivity of electrodes can be achieved by using a larger employed microalgae.
surface area of nitrogen or metal-doped carbon structures and  Electrode materials and PEMs are other important compo-
integrating metal nanoparticles into the porous structures of nents which are the subject of the burgeoning research in-
metal oxides or carbon [17]. Hybrid membranes, such as terest as these play a crucial role in the efficiency of electricity
polymer-polymer cross-linked membranes, PVDF-sulphonated generation. Carbon-based electrodes are more frequently
hydrocarbon polymers, organic-inorganic hybrid composite used due to their availability and economic feasibility, but
polymer membranes, and altered biopolymer sulphonated attempts are being made to redesign electrodes to improve
biocellulose membranes with organic or inorganic additives also their permeability and efficiency, such as through the
improve performance. Low-cost materials, such as ceramics, embedding of nanoparticles. With regards to PEMs, research
cardboard, or biobased electrodes, as well as 3D printing of is being undertaken to reduce or redesign Nafions.
electrodes, are research avenues that need further investigation  In MFCs, microorganisms act as catalysts that oxidise the
[217]. organic matter present in the substrate, generating electricity
 As energy generation processes using MFCs are still ridden with in the process. Mixed cultures are more commonly utilised
limitations, hybrid MFC systems are increasingly viewed as a media for electricity generation because they provide multi-
solution to the limitations of conventional MFCs. Deriving the ple types of substrates. Since wastewater serves as the source
advantages of both MFCs and physical, chemical, and biological of a consortium of numerous substrates, wastewater is the
processes, hybrid MFC systems display greater promise than most widely used and studied substrate for MFCs, attributed
conventional MFCs. The research into hybrid constructed wet- to their promising outcomes for electricity generation and
lands (CWs)-MFC systems have emerged with the intention of remediation.
improving the WWT capacity of wetlands while simultaneously  The application of MFCs has many advantages, such as envi-
producing electrical power [218]. Nevertheless, hybrid MFC ronmental friendliness, efficiency, and operational benefits like
systems are still in their nascent phase and have inherited many low cost and the ability to function under a wide range of pa-
of the limitations of conventional MFC systems. Many significant rameters. For instance, after 30 d of operation, MFCs can pro-
issues remain to be solved, especially around system integra- duce up to 10.38 mA current and remove 94.3% of COD by
tion, process control, optimisation, maintenance, scaling up, and bacterial strains recovered from tannery waste. MFCs exhibit a
cost [219]. removal efficacy of acidity, COD, BOD, N, and other pollutants
 As the appropriate selection of microbes is an important from wastewater by at least over 50%, with the most optimistic
element in MFC technology, the development of a robust biofilm removal efficacy reaching over 97%. As much as 31.6 W/m2
able to conduct and be penetrated is required. There has been electricity and 1.1 m3/d of biohydrogen have been reported to be
much interest recently in developing biofilm communities for produced, depending on the feedstock and type of MFC used.
MFC technologies using molecular biology techniques such as The MFC-based biosensors make for more robust alternatives to
metagenomics, synthetic biology, and microbiomes to improve conventional sensors but display variable cell performance with
electron transfer rates [22]. The genetic modification of mi- power densities ranging from below 100 mW/m2 to over
crobes to enhance their electrogenecity and increase electricity 2,000 mW/m2.
generation is another avenue that is gaining traction. An algae-  The acceptability of MFCs remains limited as MFC power gen-
assisted MFCs are also being explored as self-sustainable MFCs, eration performance is still not adequate to run a sensor or a
where microalgae-assisted cathodes are used to aid redox re- transmitter continuously. The field application of MFC technol-
actions, and the generated algal biomass is recycled as feedstock ogy is narrow due to its microbiological, electrochemical, and
to the anode compartment for efficient energy generation [220]. technological limitations, exacerbated by the knowledge gap
between laboratory and commercial-scale applications. Con-
7. Conclusion crete conclusions are yet to be drawn regarding the economic
viability of industrial-scale MFC applications. Addressing these
MFCs are bio-electrochemical systems that have emerged as a gaps is necessary before launching the technology in full-scale
promising technology to address the issue of energy and climate applications with high and stable long-term performance, and
security and are being exploited increasingly for sustainable bio- cost-effective design, maintenance, and operation are possible.
energy and biohydrogen production, WWT, and biosensing. The Significant research avenues are opening up, such as the search
present paper reviewed different MFC types, technological, and for novel electrode and membrane materials, improving elec-
chemical factors affecting microbial performance, substrates used trogenesis of microbes using molecular biology, and the devel-
in MFC, as well as the applications of MFCs. The major conclusions opment of hybrid MFC systems such as CWs-MFCs that are far
of this review are summarised below: more economically feasible, which could potentially contribute
to the scaling-up of the technology.
 Different substrates and compartment designs offer different
advantages, and the selection of appropriate components and Declaration of competing interest
designs can depend on the MFC application:
 Although SCMFCs have proved to be more cost-effective The authors declare that they have no known competing
compared to DCMFCs, the latter is able to withstand issues financial interests or personal relationships that could have
of back-diffusion and flux of substrates. Regardless, most appeared to influence the work reported in this paper.
19
S.F. Ahmed, M. Mofijur, N. Islam et al. Energy 254 (2022) 124163

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