Received: 12 January 2021 | Revised: 13 February 2021 | Accepted: 8 March 2021

DOI: 10.1002/cey2.113

REVIEW

Carbon material‐based anodes in the microbial fuel cells

Xiaoqi Fan1 | Yun Zhou1 | Xueke Jin1 | Rong‐Bin Song1 | Zhaohui Li1 |
Qichun Zhang2

1
Henan Joint International Research
Laboratory of Green Construction of Abstract
Functional Molecules and their For the performance improvement of microbial fuel cells (MFCs), the anode
Bioanalytical Applications, School of
Ecology and Environment, Zhengzhou
becomes a breakthrough point due to its influence on bacterial attachment and
University, Zhengzhou, China extracellular electron transfer (EET). On other level, carbon materials possess
2
Department of Materials Science and the following features: low cost, rich natural abundance, good thermal and
Engineering, City University of Hong
chemical stability, as well as tunable surface properties and spatial structure.
Kong, Kowloon, Hong Kong, China
Therefore, the development of carbon materials and carbon‐based composites
Correspondence has flourished in the anode of MFCs during the past years. In this review, the
Rong‐Bin Song and Zhaohui Li, Henan
major carbon materials used to decorate MFC anodes have been systematically
Joint International Research Laboratory
of Green Construction of Functional summarized, based on the differences in composition and structure. Moreover,
Molecules and their Bioanalytical we have also outlined the carbon material‐based hybrid biofilms and carbon
Applications, School of Ecology and
Environment, Zhengzhou University,
material‐modified exoelectrogens in MFCs, along with the discussion of
450001 Zhengzhou, China. known strategies and mechanisms to enhance the bacteria‐hosting capabilities
Email: [email protected] and of carbon material‐based anodes, EET efficiencies, and MFC performances.
[email protected]
Finally, the main challenges coupled with some exploratory proposals are also
Qichun Zhang, Department of Materials expounded for providing some guidance on the future development of carbon
Science and Engineering, City University
material‐based anodes in MFCs.
of Hong Kong, Kowloon, 999077 Hong
Kong, China.
KEYWORDS
Email: [email protected]
carbon materials, cell surface modification, extracellular electron transfer, hybrid biofilm,
microbial fuel cells

1 | INTRODUCTION from chemical energy in fuels.4–7 The clean by‐products

(H2O and CO2) and the renewable exoelectrogens endow
The sustainable development of the economy strongly MFCs with the great potential to become a green energy
depends on energy support, where fossil fuels continue to source. Moreover, due to their ability to use organic wastes
provide dominant contribution in the presented energy as fuels, MFCs are regarded as a promising wastewater
structure. Therefore, the ever‐increasing demand for treatment technology, which is superior to the traditional
energy has not only caused the global energy crisis, but physical and chemical methods for treating wastewater in
also brought many environmental problems such as terms of cost, reusability, and secondary pollution.8–11
serious water pollution.1–3 Microbial fuel cells (MFCs) These features ingratiated the trend of renewable energy
are a type of bioelectrochemical system, in which the development and environmental governance, making them
exoelectrogens are harnessed to produce electrical energy particularly appealing in the past decades.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2021 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.

Carbon Energy. 2021;3:449–472. wileyonlinelibrary.com/journal/cey2 | 449

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450 | FAN ET AL.

S C H E M E 1 Schematic of the contributions of various kinds of carbon material‐based anodes for the enhanced MFC performance.
EET, extracellular electron transfer; MFC, microbial fuel cell

The origin of MFC technology could be dated back to for the development of cathode materials and the config-
1911 when Potter used the microbes to produce uration in MFCs; however, these theories and experiences
electricity.12 As the direct transfer of electrons from about the anode of traditional fuel cell are not suitable
bacteria to anode is easily hampered by the non- for the MFC anodes, thus requiring intensive research
conductive lipid membrane of bacterial cells, the electron studies.30–32
mediators have usually been involved in the earlier Carbon is an Earth‐abundant element in nature,
MFCs, which can accelerate electron transfer through which possesses the following features: low cost and high
the capture of electrons from the interior of bacterial cells chemical and thermal stability.33 Moreover, the surface
and their release to anode.13–15 Considering the cost, morphologies and structural forms of carbon materials
toxicity, and the need for constant replenishment, the can be adjusted in an unusually broad range, leading to
addition of mediators seems not to be sustainable. the presentation of the desired physicochemical proper-
Therefore, the MFC technology was found to be stag- ties for any particular application.34 Naturally, carbon
nated until 1999, when the exoelectrogens that directly materials have become an intrinsic part of the anode
transfer electrons to electrodes were gradually revealed.16 materials in MFCs. The classical carbon materials used in
After that period, the MFC technology entered a high‐ MFC anodes mainly refer to commercially available
speed development period, resulting in the diversity of carbon electrodes, including carbon paper (CP), carbon
research activities. The research, which is focused on cloth (CC), carbon felt (CF), graphite rod, and flake
MFC, now covers anode materials,17–19 cathode materials,20 graphite. These commercially available carbon electrodes
separator materials,21,22 configuration,23 and so on.24–29 are posited in the anodic chamber, and then the exoe-
Among them, the anode material is the most frequently lectrogens attach to them for the formation of natural
investigated object. On the one hand, MFC anodes provide biofilm. Although these carbon electrodes inherit the
the space for bacterial attachment and affect the microbial abovementioned characteristics of carbon element, they
extracellular electron transfer (EET), which is highly asso- usually exhibit relatively poor performance when used in
ciated with MFC performance. On the other hand, the MFC anodes. The deficiencies in the biofilm formation
theories and experiences from the investigations of tradi- and EET between carbon electrodes and exoelectro-
tional fuel cells can offer abundant importuned reframes gens are counted as the main contributing factors.35–38
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FAN ET AL. | 451

With the advancement of nanotechnology, extensive ef- As to the anode materials, the presented reviews only
forts have been devoted to the creation of various novel focus on the design of materials but neglect the differ-
carbon‐based nanomaterials for offsetting the aforemen- ence with regard to the type of biofilms. In this review,
tioned deficiencies (Scheme 1). The modification of these considering the biofilm types and anode materials, we
carbon‐based nanomaterials can enlarge the surface area first divide the carbon material‐based bioanodes on the
of commercial carbon electrodes, leading to the increased basis of the difference in the types of biofilms. Then, we
spatial positions for bacterial attachment and biofilm outline important strides in the creation of each type of
formation. Besides, the surface properties can be regu- carbon material‐based anodes in MFCs and highlight the
lated to increase the anode/bacteria interactions, thus enhancement strategies used in the design of these car-
enhancing the EET and the formation of biofilm.39–42 bon material‐based anodes. We hope that this review will
Most of the commercial carbon electrodes belong to provide a comprehensive grasp of the main development
planar electrodes, where the biofilm formation and line of carbon material‐based anodes in MFCs, as well as
electron transfer are confined to the outer surface. To offer valuable guidance to future research focuses on
accelerate the diffusion of self‐secreted mediators and relevant subjects for pushing the practical application
even the formation of natural biofilm on the interior of MFCs.
space of anode, the freestanding carbon materials with
tailored porous structures are also developed as candi-
dates for commercial carbon electrodes.43,44 As a con- 2 | C A R B O N M A T E R I A L‐ BASED
sequence of these research studies on carbon material‐ AN ODES W ITH NATU RAL
based anodes, the MFCs show improvement in the BIOFILMS
performance by nearly an order of magnitude. However,
the EET efficiencies inside the natural biofilm formed on 2.1 | Pure carbon materials
these carbon material‐based anodes with a natural bio-
film are still unsatisfactory, because only the bacterial As mentioned above, MFC anode provides active sites for
cells nearby the carbon materials can transfer the elec- bacterial attachment and electron transfer. This function
trons effectively, whereas these bacterial cells, located far drives the anode materials to set high requirements
away from the material interfaces, inject electrons into concerning conductivity, biocompatibility, and antic-
anode through an inefficient path (adjacent non- orrosive ability. As the pure carbon materials can satisfy
conductive bacterial cells).45,46 Therefore, the concept of the aforementioned demands, they have been employed
hybrid biofilm has been employed, in which carbon as substrate materials for the growth of natural biofilms
materials and bacterial cells are previously mixed and in the bioanode of MFC. More importantly, the
then transferred to the substrate electrode for the for- morphologies and structures of pure carbon materials
mation of hybrid biofilms.47,48 In this case, the inserted play important roles in the bacteria‐hosting capability of
carbon materials in the hybrid biofilms can serve as anode and the EET efficiency between anode and natural
conductive electron transfer paths to enhance the EET biofilm. For example, pure carbon materials with mac-
efficiency. Moreover, the cell densities in these hybrid roporous structures (>2 μm) allow bacterial colonization
biofilms can be improved by changing the ratio between in the interior of anode, whereas microporous pure car-
carbon materials and bacterial cells or optimizing the bon materials can promote the diffusion of endogenous
transportation technologies. However, the simple mixing mediators (e.g., riboflavin) for improving the EET
mode between bacterial cells and carbon materials can- efficiency.55–57 Therefore, we summarize the part of pure
not ensure that every bacterial cell in the hybrid biofilms carbon materials based on their different dimensions, to
could make direct contact with the carbon materials. To understand the dependencies between MFC performance
further improve the EET efficiency, cell surface mod- and material structure.
ification has recently been employed to develop novel
hybrid biofilms. In this new mode, the carbon materials
are modified on the cell surface, and then the modified 2.1.1 | One‐dimensional (1D) carbon
bacterial cells are transferred to the substrate electrode materials
for the formation of hybrid biofilms, which integrate
every exoelectrogen with carbon materials to expand As one kind of famous 1D carbon materials, carbon na-
their contact interface for further optimizing the EET notubes (CNTs) emerge as substrate materials in MFC
and the performance.49–51 anode due to their large specific surface area, high
To date, the progresses on the different subfields mechanical strength, excellent conductivity as well as
of MFCs have been comprehensively summarized.52–54 specific fiber structure.58 Peng et al.59 investigated the
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452 | FAN ET AL.

voltammetric behavior and current generation capability With these efforts, we can further understand the influ-
of Shewanella oneidensis on CNT‐modified glassy carbon ence of slight distinction in anode materials with respect
electrode (GCE). The cyclic voltammetry curves showed to MFC performance, thus improving the level of fine-
a reduced oxidative/reductive peak separation with CNTs ness of the anode material designs.
modification, indicating that the good conductivity
of CNTs enhanced the kinetics of direct electron trans-
fer between outer membrane cytochrome c and 2.1.2 | Two‐dimensional carbon materials
CNT‐modified GCE electrode. As a result, the current
generation capability of this modified electrode exhibited Compared with 1D carbon materials, the plane structure
an 82‐fold increase as compared with that of bare GCE of two‐dimensional carbon materials can offer an en-
electrode in the Shewanella oneidensis‐involved electro- larged contacting area for bacterial attachment and
chemical cells. However, the performance of MFCs with EET.63,64 Thus, some of the two‐dimensional carbon
CNT‐modified GCE electrode has not been provided in materials have been put on the domain of MFC anode.
this study. To disclose the real application of CNT Among them, graphene is one most important re-
modification in MFC anode, a CNT‐modified CC elec- presentatives, which possesses good conductivity, stabi-
trode has been fabricated in a single‐chamber MFC.60 lity, and biocompatibility as well as high specific surface
The MFC displayed a maximum power density of area. In a typical example, graphene was used to
65 mW·m−2, whereas the maximum power density was modify the stainless‐steel mesh (SSM), which served as
only 26 mW·m−2 in the case of MFC with unmodified the anode for MFC with Escherichia coli as the
CC, confirming the positive function of CNT modifica- biocatalyst.65 As the modification of graphene can in-
tion toward MFC performance. Mohanakrishna et al.61 crease the surface area and thus the number of attached
also fabricated the multiwalled carbon nanotube bacteria, the modification of graphene on SSM has re-
(MWCNT)‐impregnated plain graphite anode by using sulted in an 18‐fold increase in the maximum power
conductive epoxy adhesive for MFC. They found that the density of MFC. It is noted that the potential toxicity of
microbial mediator‐involved charge transfer between materials should be taken into consideration for MFC
the anolyte and the modified anode was more effective anode, as it will affect bacterial growth. In most cases,
due to the facilitated surface area after the impregnation reduced graphene oxide (rGO) is obtained by the che-
of MWCNT. Therefore, we can conclude that the CNTs mical reduction of graphene oxide (GO), and the residual
modification can accelerate both the direct and indirect reducing agents (e.g., hydrazine monohydrate) possibly
electron transfer for optimizing the MFC output, which poison bacteria. To remove the potential toxic hazards,
may be attributed to their high conductivity, large surface the electrochemical reduction method was used to prepare
area, and the fiber structure that connects the anode and graphene for MFC anode. Similar to the chemically re-
cytochrome c on bacterial outer membrane. duced graphene, the electrochemically reduced graphene
Although the above research studies have deeply ex- could also improve the MFC performance.66 Another bio-
plored the effect of CNTs on anode performance, the compatible and sustainable approach is the bioreduction of
information of this material on long‐term stability is GO. Zhou et al.67 developed a biosynthesized graphene
rarely mentioned. In this case, Zhang et al.62 fabricated by using Eucalyptus leave extract as reducing agent
the CNT‐modified graphite felt (GF) through a (Figure 1A). When using the biosynthesized graphene as
dipping–drying process, and they evaluated the long‐ anode materials in MFC, they found that the maximum
term stability of the MFC with this CNT‐modified anode. power density was 70% higher than that of MFC with an-
Unlike the MFC with CF anode, which represented a ode modified with electrochemically reduced graphene.
declining performance, the MFC with CNT‐modified Such enhancement could be explained by the biomolecules
anode exhibited a constant performance during the coating‐induced surface hydrophilization and biocompati-
whole testing time (13 months). The author attributed bilization of biosynthesized graphene, which made the
this enhanced stability to the better growth of electro- anode surface less harmful and more available for bacterial
chemically active biofilms (EABs), the enhanced inter- attachment and growth.
action between anode and EABs, as well as the increased Although the graphene nanosheet possesses large
EET after the modification of CNTs. The 1D carbon surface area, the π–π stacking between graphene na-
materials include the CNTs, carbon nanowires, and car- nosheets will sacrifice this superiority. In this regard, the
bon nanofibers (CNFs); however, the latter two kinds of reduced graphene particles, which seem like crumpled
carbon materials have not been found to be used in paper balls (Figure 1B), have been developed as anodic
MFCs. It is encouraged to probe the performances of materials for the MFCs.68 Due to the aggregation‐
MFCs with these carbon materials as anode modifier. resistant property and open structure, the reduced
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FAN ET AL. | 453

F I G U R E 1 (A) Schematic of the fabrication process of biosynthesized graphene. Reproduced with permission: Copyright 2019,
Elsevier.67 (B) Scanning transmission microscope image of the rGO particles. (C) Polarization and power density curves of MFCs with
different anodes. Reproduced with permission: Copyright 2012, Elsevier.68 HDA, 1,6‐hexanediamine; MFC, microbial fuel cell; rGO, reduced
graphene oxide

graphene particles enhanced the surface area of anode, was also conducive to performance improvement. They
the electrochemical kinetics, as well as the mass transfer. also optimized the 3D structure from the aspects of
As a result of these enhancements, the reduced graphene length, packing densities, and surface conditions, and
particle‐modified anode delivered a maximum power concluded that the 3D anode with long and loosely
density of 3.6 W·m−3 in the MFC test, which signified a packed MWCNTs exhibited the highest performance in
1.3‐fold increase as compared with those of MFC MFC. The CVD method is available to fabricate the 3D
with reduced graphene nanosheet‐modified anode self‐standing materials for increasing the applicability of
(Figure 1C). The MWCNT‐derived graphene oxide na- MFCs. As a typical example, a 3D CNTs sponge has been
noribbons (GONRs) are another kind of two‐dimensional developed for MFC by using a three‐zone furnace cou-
carbon materials, which not only inherit conductive pled with a quartz tube (Figure 2A).70 The 3D CNTs
cellular pili‐like feature from MWCNTs, but also offer sponge showed a length of 10 cm without base materials
large electrochemical active surface area as graphene. (Figure 2B). Moreover, the scanning electron microscopy
Thus, the use of GONRs has been demonstrated to make (SEM) image revealed that the sponge possessed a high
the EET process on MFC anode more effective.63 porous structure (Figure 2C), which was ideal for mi-
crobial penetration and growth on the exposed surface.
Thus, the MFC with this 3D CNTs sponge produced a
2.1.3 | Three‐dimensional (3D) carbon maximum power density of 2150 W·m−3. Undoubtedly,
materials the CVD method is widely used for the fabrication of
various 3D materials; however, this method is expensive
The porous structures of 3D carbon materials can ac- and also complicated. In this context, the carbon
celerate the mass transfer of fuel and the diffusion of self‐ material‐doped chitosan hydrogel has become an attrac-
secreted mediator. Moreover, the penetration of bacterial tive choice for MFC anode. Liu et al.71 fabricated a CNT
cells into the interior surface of the anode is also per- hydrogel by electrochemical deposition of CP in a
mitted if the pore sizes or channel sizes are larger than CNT–chitosan solution at −3 V (Figure 2D,E). The re-
those of bacterial cells. On the basis of these advantages, sults demonstrated that the CNT hydrogel was a more
the 3D carbon materials have attracted much scientific effective MFC anode, compared with CP, which could be
interest in the field of MFC anode. By taking advantage attributed to the enhanced electrochemical surface area
of the chemical vapor deposition (CVD) method, Erbay and large content of functional groups on the surface.
et al.69 developed a novel 3D MFC anode, in which the Nevertheless, the pore size of this CNT hydrogel is about
MWCNTs were directly grown on the wires of SSMs in hundreds of nanometers; thus, bacterial penetration
the radial direction. Apart from the large 3D surface, the into the interior of CNT hydrogel is not feasible. To solve
minimal Ohmic loss between MWCNTs and substrate this issue, the ice segregation‐induced self‐assembly
electrode, caused by the use of direct growth strategy, technology was used to unidirectionally freeze the
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454 | FAN ET AL.

F I G U R E 2 (A) Schematic of the used chemical vapor deposition device for the fabrication of carbon nanotube (CNT) sponge. (B, C)
Photograph and scanning electron microscopy (SEM) image of CNT sponge. Reproduced with permission: Copyright 2015, Elsevier.70
(D) Schematic illustration of the preparation of CNT hydrogel on carbon paper (CP). (E) Photograph of CNT hydrogel on the CP.
Reproduced with permission: Copyright 2014, American Chemical Society.71 (F–H) SEM images of 3D multiwalled carbon nanotube
scaffold at different magnifications. Reproduced with permission: Copyright 2011, Royal Society of Chemistry72

MWCNT/chitosan dispersion.72 After freeze‐drying, a 3D The abovementioned methods are universal for the
MWCNT scaffold was obtained, which possessed a micro- fabrication of 3D CNT or graphene. Besides them, there
channeled structure with a channel size of about 16 μm existed some special strategies for CNTs or graphene,
(Figure 2F–H). Thus, this 3D MWCNT scaffold could per- due to their different structures and properties. For ex-
mit the interior bacterial colonization, which finally pro- ample, the fiber‐like structure of CNTs allows them to
duced a maximum volumetric power density as high as become a precursor for fabrics. Inspired by this, Delord
2.0 kW·m−3; however, the operation conditions of the used et al.73 used the wet‐spinning process to assemble
flow MFC configuration were not optimized. On the basis MWCNTs into long filaments, which could be manually
of the same method, the hierarchically porous chitosan/ woven to obtain a CNT fiber textile (CNTex). The CNTex
vacuum‐stripped graphene scaffold has also been success- showed similar macroscopic and microscopic scales as
fully obtained, which was an effective anode for MFC.43 CP (Figure 3A,B), but it possessed a much large
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FAN ET AL. | 455

macropore scale (200–700 μm) than that of CP (100 μm). of textile provided open 3D channels to guarantee the
As this large‐scale porosity and nanostructration pro- internal colonization of bacterial cells and efficient sub-
moted bacterial colonization, the CNTex anode was su- strate transport, whereas the microscale porous CNT
perior to CP anode in the maximal current density of layer strongly interacted with bacterial cells to accelerate
MFC. Similarly, GO nanosheets have been found to form the EET, which finally resulted in a 68% higher max-
graphene hydrogel during the hydrothermal treatment imum power density as compared with that of CC anode.
process. By freeze‐drying the hydrogel, a 3D porous On the basis of this study, the same group changed the
graphene aerogel with a pore size of some 10 μm 3D substrate from textile to sponge, and the as‐prepared
was fabricated (Figure 3C).74 Benefiting from these por- CNT sponge still retained the 3D porous structure
ous structures, a maximum power density of 5 mW·m−3 of the sponge with a pore size range of 300–500 μm
was realized when using it as an MFC anode. (Figure 3E,F).44 Compared with the previous CNT–textile
As some natural substrates possess 3D porous struc- anode, the CNT‐sponge anode exhibited better con-
tures, modifying carbon materials on their surfaces is a ductivity, stability, and continuous 3D CNT surface, re-
simple but an effective way to obtain 3D carbon sulting in a 48% increase in the maximum areal power
material‐based anodes for MFC. Xie et al.75 developed a density of MFCs. The graphene sponges have also been
two‐scale porous anode by conformally coating CNTs demonstrated as a high‐performance 3D anode for MFC,
on textile (Figure 3D). The macroscale porous structure further confirming the superiority of 3D sponge

F I G U R E 3 (A, B) Photograph and schema of carbon nanotube (CNT) fiber textile. Reproduced with permission: Copyright 2017,
Elsevier.73 (C) Scanning electron microscopy (SEM) image of three‐dimensional porous graphene aerogel. Reproduced with permission:
Copyright 2018, Elsevier.74 (D) SEM image of CNT–textile composite. Reproduced with permission: Copyright 2011, American Chemical
Society.75 (E) SEM image of CNT sponge. (F) Photograph of CNT‐sponge electrode. Reproduced with permission: Copyright 2012, Royal
Society of Chemistry.44 (G–J) SEM images of stainless steel fiber felts (G, H) and carboxyl graphene‐modified stainless steel fiber felts (I, K)
at different magnifications. Reproduced with permission: Copyright 2014, Elsevier76
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456 | FAN ET AL.

substrate.77 However, the nonconductivity of these two Benefiting from the N‐doping and bamboo‐like structure,
3D substrates may have some adverse effects on the MFC the bamboo‐like NCNTs provided better biocompatibility
performance to some extent. In this context, Hou et al.76 and enlarged active area for EET, ultimately leading to
employed the conductive stainless steel fiber felts (SSFFs) 1.6‐fold increase in the peak current density of MFC
with an open macroporous structure (Figure 3G,H) as when compared with CNT. By changing the external N
the substrate for the fabrication of 3D MFC anode. sources from ethylenediamine to the concentrated am-
The modification of graphene on the SSFFs made the monium hydroxide83 and N2,84 some other kinds of N‐
surface much rougher but preserved the macroporous doped carbon materials have also been developed, which
structure (Figure 3I,K), which further increased the were proven to largely improve the MFC anode. Never-
contact area between anode and bacterial cells. Thus, the theless, whether the type of N sources would affect the
MFC with graphene‐modified SSFFs anode delivered a performance of MFC is an undisclosed issue. To
remarkably increased maximum power density as com- make this clear, Iftimie and Dumitru82 utilized two
pared with that of MFC with SSFFs anode (2142 vs. procedures for the fabrication of two kinds of
0.8 mW·m−2). N‐doped CNTs and compared their application potentials
in MFC anode. The N‐doped CNT with 4‐nitroaniline
was indexed as CNT1, whereas the other one with
2.2 | Heteroatom‐doped carbon 4‐nitrobenzenediazonium tetrafluoroborate was indexed
materials as CNT2. As shown in Figure 4C, the peak intensities at
400 and 405.8 eV in the XPS pattern of CNT2 are much
The modification of pure carbon materials has been de- higher than those of CNT1, indicating higher contents
monstrated to be efficient for enhancing the performance of the nitro group of 4‐nitrophenyl layer and partially
of MFCs. However, the pure carbon materials possess a reduced nitro groups, such as –NH2 and –NH2OH. Such
hydrophobic nature theoretically, which will affect the high contents of these N‐contained groups can help to
biocompatibility for bacterial adhesion and biofilm for- improve the surface hydrophilicity and bacterial adhe-
mation on the anode.78,79 In general, the acid treatment sion, so the maximum power density of MFC with CNT2
can introduce some functional groups to make the pure as an electrode is higher than that of MFC with CNT1 as
carbon materials hydrophilic, but the electrical con- an electrode (Figure 4D).
ductivity will become poor at the same time.80 Thus, The carbon material doped by dual heteroatoms has
doping heteroatoms into carbon materials has been also been used as MFC anode.85 The in‐situ formation of
proposed as a useful strategy. On the one hand, het- N, S‐doped graphene on the graphite plates by using
eroatom doping can break the chemical inertness of pure electrolysis in (NH4)2SO4 solution has increased the
carbon materials to improve the hydrophilicity and bio- maximum power density of MFC from 0.39 ± 0.020 to
compatibility for bacterial adhesion. On the other hand, 0.67 ± 0.034 W·m−2. This result can be explained by the
the hydrophilic defects created by the doping of het- doping of heteroatoms, the improved electron transfer,
eroatoms are conducive to the EET between anode and and the microporous structure. Although the XPS char-
cytochrome c on outer membranes of bacterial cells. To acterizations have revealed the doping of S atom into
date, various heteroatom‐doped carbon materials have graphene, its effect on the MFC performance has not
been developed for MFC anode. In this part, we will been mentioned. Therefore, relevant investigations
classify them according to the use of exogenous or should be performed to confirm whether the doping of S
endogenous sources of heteroatoms. atom has a positive effect on the MFC performance in
future research studies.

2.2.1 | Exogenous sources of heteroatom

2.2.2 | Endogenous sources of heteroatoms
Among various heteroatoms, the most common case is
nitrogen (N‐) doped carbon materials for the MFC anode. The use of exogenous sources of heteroatoms for the
As a typical example, Ci et al.81 developed a kind of fabrication of heteroatom‐doped carbon materials will
special N‐doped CNT (bamboo‐like NCNTs) that dis- result in increased cost, inconvenient fabrication process,
played a bamboo‐like structure (Figure 4A) as modifying and additional toxic hazards. Thus, research studies on
material for MFC. The high‐resolution N 1s X‐ray pho- the fabrication of heteroatom‐doped carbon materials
toelectron spectra (XPS) of bamboo‐like NCNTs revealed have begun to flourish in the use of precursors that can
the presence of three types of N atoms, confirming the serve as carbon and heteroatom sources simultaneously.
successful doping of N into this material (Figure 4B). The first one is melamine, which can afford abundant N
 26379368, 2021, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cey2.113, Wiley Online Library on [19/02/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
FAN ET AL. | 457

F I G U R E 4 (A,B) Transmission electron microscopy image and N 1s X‐ray photoelectron spectra (XPS) of bamboo‐like NCNTs.
Reproduced with permission: Copyright 2012, Elsevier.81 (C) N 1s XPS of different N‐doped carbon nanotubes (CNTs). (D) Polarization and
power density curves of different microbial fuel cells (MFCs). MFC1, MFC2, and MFC3 were respectively fabricated with pure CNT, CNT1,
and CNT2. Reproduced with permission: Copyright 2019, Elsevier82

atoms for N doping due to the high N content (66.7%) in performance, some of N‐doped porous carbon materials
the molecular structure. By using porous melamine foam derived from candle soot,88 almond shell,56 and silver
as the precursor, You et al.86 developed a 3D macro- grass89 have also been created as anode materials for
porous N‐enriched graphitic carbon (NGC) scaffold for MFC. Although these anode materials possessed im-
MFC anode. The N content in this NGC scaffold is as proved MFC performance, the effects of pore types on the
high as 10.89%. Such high N content could accelerate the MFC performance are confusing. In this case, Zou et al.57
EET, as the density‐functional theory (DFT) calculations prepared the porous N‐doped CNF aerogel for MFC an-
revealed that the interactions between pyrrolic N struc- ode by the pyrolysis of freeze‐dried bacterial cellulose
ture and active center of cytochrome c on the outer pellicles. The porous structure of CNF aerogel can be
membrane of bacterial cells were enhanced. Moreover, tuned by the alteration of pyrolytic temperature. With the
the existing 3D macroporous structure maximized the increased pyrolytic temperature (600–1000°C), the mi-
space for bacterial attachment and facilitated mass cropores gradually disappeared, whereas the content of
transport. On the basis of these advantages, the MFC mesopores in the structure of CNF aerogel was found to
with this NGC anode delivered a maximum power den- be increased (Figure 5A). The mesopores not only be-
sity of 750 mW·m−2. haved as bags with a suitable size to trap and release
Natural biomass is another kind of the precursor in- flavin molecules, but they also offered curvature or kink
tegrating the functions of carbon and heteroatoms surfaces to increase the contacting opportunities toward
sources. For example, the biomass carbon with N doping electroactive sites for effective surface absorption and
derived from mango wood has been prepared as anode two‐electron transfer electrochemistry (Figure 5B). As a
material for MFC, which obtained a maximum power result, the CNF obtained at a pyrolysis temperature of
density of 589.8 mW·m−2.87 As the presence of porous 1000°C showed the highest content of mesopores and the
structure in the anode will upgrade the MFC best performance in MFC. In another work, the
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ET AL.
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FIGURE 5
| 458
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FAN ET AL. | 459

researchers have adjusted the pore sizes of the coffee process; thus, the MFC with the PPy@NMCF‐1000 anode
waste‐derived N‐doped activated carbons (CWACs) for achieved the best performances among all tested MFC with
optimizing the MFC performance.94 Unlike the meso- different NMCF anodes. Certainly, this high performance
pores converted from micropores in previous work, the also originated from the bacterial attachment in the 3D
mesopores here originated from macropores. However, macroporous structure of PPy@NMCF‐1000 anode.
the same conclusion was obtained, that is, the increase in The carbonization or pyrolysis of natural biomass not
the mesopores content of CWACs favored the perfor- only can produce the N‐doped carbon materials but also
mance of MFC. It is worth noting that the sizes of those generate carbon materials doped with other heteroatoms.
discussed pores are in the range of several to dozens of By taking the advantage of bread as the raw material, a
nanometers, allowing the access of mediators or sub- 3D macroporous carbon foam with high content of N, P,
strate. However, for the macropores that can serve as the and S (NPS‐CF) has been created as MFC anode.92 The
channels for bacterial penetration, their appearances in doping of N, P, and S has largely improved the bio-
the structures of biomass‐derived N‐doped carbon ma- compatibility of NPS‐CF for favoring the enrichment of
terials are still valuable for the performance improve- bacterial cells on the surface as compared with CC
ments of MFCs. Silk cocoon is an abundant natural (Figure 5G–J), ultimately leading to a 2.57‐fold maximum
material that possesses an intrinsically 3D nonwoven areal power density. Unfortunately, the individual func-
structure. By directly heating it at high temperatures tions of S‐ and P‐doping have also not been revealed in
(Figure 5C), Lu et al.90 obtained a N‐enriched 3D pseu- this study. Another example was the porous
dographitic anode with multiple layers and pores carbon–silica (PC/Si) composite, which was prepared by
(Figure 5D) as anode for MFC, which produced a 3.1‐fold the carbonization of the distiller's grains.93 The PC/Si
maximum power density compared with that of MFC exhibited a honeycomb‐like porous structure with
with CC anode. This result can be attributed to the fact abundant macropores and mesopores, which were in the
that the enriched N content and hierarchical 3D micro- size range of 2–15 μm and 3–4 nm, respectively
structure improve the biocompatibility and habitat for (Figure 5K). These porous structures can increase the
the formation of biofilm on anode. To further improve active area for bacterial adhesion and flavin‐mediated
the application potential of biomass‐derived 3D macro- electron transfer. More importantly, the presence of Si
porous N‐doped carbon materials in MFC anode, the N‐ was found to largely increase the number of bacterial
dopant states have been optimized by the integration of cells on the electrode surface (Figure 5L,M). These fac-
exogenous N sources biomass.91 As the N‐dopant states tors guaranteed that the maximum power density of
and their corresponding contents were highly associated MFC with PC/Si anode was 4.5‐fold higher than that of
with the added precursors, the polyaniline (PANI) and MFC with CC anode.
polypyrrole (PPy) were, respectively, added during the
pyrolysis of naturally abundant nitrogenous corncobs to
obtained 3D N‐doped macroporous carbon foams 2.3 | Carbon‐based composites
(NMCF) with different N‐dopant states (Figure 5E). The
primary N component was graphitic N for the NMCFs The carbon‐based composites can reinforce and enrich
prepared at 1000°C with the addition of PANI and the surface properties of the corresponding pure carbon
without an external N source (Figure 5F). In contrast, the materials or even adjust their space structure to further
pyrrolic N was the dominant N component in the structure increase the power density. Thus, various carbon‐based
of NMCF prepared at 1000°C with the addition of pyrrole binary composites have been widely developed as anode
(PPy@NMCF‐1000). The DFT calculations indicated that materials for MFC. On the basis of the types of introduced
the pyrrolic N was the key component to promote the EET components, these binary composites can be divided into

F I G U R E 5 (A) Pore size distribution of CNF aerogel based on DFT model versus different pyrolytic temperatures. (B) Proposed direct
electrochemistry of flavins on electrode with different structures. Reproduced with permission: Copyright 2016, Wiley.57 (C,D) Schematic
illustration of the fabrication process of carbonized silk cocoon and its SEM image. Reproduced with permission: Copyright 2017, Elsevier.90
(E) Schematic presentation of the preparation of NMCF samples with the addition of different exogenous N sources. (F) The content
of various N‐dopant states in the NMCF samples. Reproduced with permission: Copyright 2020, Elsevier.91 (G–J) SEM images of NPS‐CF (G,H)
and CC (I,J) bioanodes with the attachment of bacterial cells. Reproduced with permission: Copyright 2018, Elsevier.92 (K–M) SEM images of
PC/Si composite, bacterial cells grown on PC/Si anode before and after the HF treatment. Reproduced with permission: Copyright 2018, Royal
Society of Chemistry.93 CC, carbon cloth; CNF, carbon nanofiber; DFT, density‐functional theory; HF, hydrofluoric acid; NMCF, N‐doped
macroporous carbon foam; NPS‐CF, N, P, and S carbon foam; PANI, polyaniline; SEM, scanning electron microscopy
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460 | FAN ET AL.

three categories: carbon/carbon composites, carbon/metal improvement. The former one allowed the formation of
composites, and carbon/conducting polymer composites. 3D hierarchically porous structure for enriching the
The defined carbon/metal binary composites cover the bacterial biofilm, whereas the latter one provided an N‐
carbon/pure metal composites and carbon/inorganic metal doped surface to adsorb flavin for improving EET effi-
compounds. Considering the effectiveness of binary com- ciency. Besides rGO, the GONR has also been integrated
posites toward performance improvement of MFCs, the with N‐doped CNT. Liu et al.103 synthesized an N‐doped
carbon‐based ternary composites that exhibited more MWCNT@GONR composite with core/shell structure by
abundant surface properties and delicate structures have a microwave‐assisted unzipping process and used it as
also been created to improve the anode/bacteria interac- anode for MFC. The encapsulation of the MWCNT core
tions, EET efficiency, and bacterial adhesion. Thus, we re- with GONR improved the hydrophilicity and surface
view these carbon‐based composites in this section and area of MWCNT, enriching the bacterial adhesion. Thus,
highlight the enhancement strategies. the MFC with MWCNT@GONR anode delivered
higher power density than that of MFC with MWCNT
anode (970 vs. 3291 mW·m−2). The doping of N to
2.3.1 | Carbon/carbon binary composites MWCNT@GONR further enhanced the electrical
conductivity and surface roughness, resulting in an
As previously reported, the 1D fiber structure of CNT is not additional improvement in the power density of MFC
beneficial for bacterial adhesion,95 whereas the π–π stacking‐ with N‐doped MWCNT@GONR (3444 mW·m−2). Taken
induced aggregation of graphene nanosheets during the together, the synergistic effect between individual com-
reduction of graphite oxide will reduce the superiority of ponents can be coupled with the strategy of doping
graphene in the surface area.96 However, when we integrate heteroatom to further upgrade the MFC performance.
these two kinds of carbon materials together, the graphene
can retain its suitable plane structure for bacterial attach-
ment, and the CNT can be inserted between the graphene 2.3.2 | Carbon/metal binary composites
nanosheets to reduce the aggregation degree for extending
the electrochemical active sites.97 Therefore, graphene/CNT In general, the noble metal nanoparticles can be used to
composite has become a kind of classic carbon/carbon bin- fabricate carbon/metal binary composites for MFC an-
ary composite for MFC anode. In a typical example, Zou ode, because their good biocompatibility and the ex-
et al.98 created a hierarchically porous MWCNT@rGO cellent electrocatalytic activity favor the bacterial
composite (the input ratio of MWCNT to GO was 1:2) for attachment and enhance the EET efficiency between
MFC anode through a solvent‐processed method. As shown anode and bacterial cells. For example, the MFC with
in Figure 6A–F, the layered aggregation observed on the biogenic gold nanoparticles/MWCNT composite anode
SEM image of rGO sample has not occurred for exhibited a better performance as compared with that of
MWCNT@rGO, which displayed obvious porous network MWCNT anode,104 whereas the 3D graphene aerogel
architecture. This result implies that the insertion of anode produced a 1.8‐fold increase in the power density
MWCNTs effectively protects the rGO nanosheets from ag- of MFC after decorating with platinum nanoparticles.105
gregation and bridges the separated rGO nanosheets. The However, the high cost of these noble metal nano-
extended surface area enriched the bacterial cells on the particles will limit their application. In this context, the
anode, whereas the improved multidirectional connections inorganic metal compounds naturally become the can-
between rGO sheets ensured a high electron transfer rate, didates to construct carbon/metal binary composites.
therefore leading to a sixfold increase in the MFC Song et al.99 developed a graphene/Fe3O4 composite as
performance. anode material for MFC. They found that the presence of
N‐doped carbon/carbon binary composites, which not Fe3O4 component in this composite largely increased the
only preserve the advantages of carbon carbon/carbon bacteria‐hosting capability of anode (Figure 6G,H), due
binary composite but also possess the positive effects of to the high affinity between Fe3O4 nanoparticles and
N doping, are highly appealing to MFC anode. Wu Shewanella species. Thus, the maximum power output of
et al.102 fabricated a hierarchically porous N‐doped MFC with graphene/Fe3O4 composite anode was 2.8
CNTs/rGO composite by using PANI as an N source times that of graphene anode. The usage of SnO2 nano-
for MFC anode. The performance of MFC with particles to decorate CNT anode was also demonstrated
N‐doped CNTs/rGO anode was superior to those of to improve the MFC performance,106 and the research
MFCs with N‐CNTs, N‐rGO, and CNTs/rGO anodes, studies explained that the electrostatic binding between
confirming that both the fabrication of composites and SnO2 nanoparticles and cytochrome c on the outer
the doping of N were effective for the performance membrane of bacterial cells facilitated the EET.
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| 461

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FIGURE 6
ET AL.
FAN
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462 | FAN ET AL.

Compared with the abovementioned metal oxides, TiO2 conducting materials, PPy can exhibit outstanding con-
nanoparticles were more frequently used to prepare ductivity in neutral pH condition,111 which is more
various carbon/TiO2 composites anodes for improving compatible with the MFC. In this context, Zou et al.112
the MFC performance due to their good biocompatibility constructed a PPy‐coated CNTs composite anode for
and high resistance to corrosion.107,108 Subsequently, the MFC with E. coli as the biocatalyst. They found that the
researchers explored the preferred crystallinity of TiO2 MFC with this anode delivered a maximum power den-
nanoparticles for MFC performance, and they concluded sity of 228 mW·m−2. In another research, the power
that the presence of amorphous TiO2 instead of TiO2 density of MFC with PPy/rGO composites anode was
nanoparticles on the surface of rGO produced better evaluated to be 1068 mW·m−2.113 However, we cannot
performance in MFC anode due to the enhanced specific have direct knowledge of the PPy contribution from these
surface area for contacting with bacterial cells and ac- works, due to the lack of information about MFCs with
cepting electrons from self‐secreted mediators.55 CNT or rGO. To make it clear, a PPy/GO composite was
Besides metal oxides, the metal sulfide and metal car- uniformly coated on the CF anode for MFC anode
bide have also been integrated with carbon materials to through the in situ electropolymerization of Py with GO
develop efficient anodes for MFC. Wang et al.100 used FeS2 as the anionic dopant in the presence of substrate elec-
nanoparticles to decorate rGO for improving the applica- trode.114 The PPy/GO anode had a 37% higher cell vol-
tion potential of rGO in MFC anode. They disclosed that tage than GO anode. Moreover, the PPy/GO anode also
the FeS2/rGO anode had better interaction with microbial exhibited better stability during 120 cycles of lactate
film and enhanced EET efficiency as compared with those feeding. These results can be attributed to the improved
of rGO (Figure 6I–K), ultimately resulting in obvious im- electronic conductivity, the enhanced bacterial adhesion,
provements in the start‐up rate, voltage, and power of MFC. and the increased EET efficiency caused by the sy-
In another research, the decoration of rGO anode with nergistic effect between PPy and GO.
Mo2C nanoparticles was proven to increase the maximum PANI is another attractive choice to fabricate the
power density of MFC from 812 to 1697 mW·m−2.109 This carbon/conducting polymer anode in MFC, as its in-
result is due to the excellent electrocatalytic activity of trinsic positive charge can improve the adhesion of ne-
Mo2C nanoparticles toward the electron shuttle (riboflavin) gatively charged bacterial cell on the anode.115–117 As a
and several microbial fermentation metabolites (e.g., hy- typical research, Qiao et al.118 fabricated a CNT/PANI
drogen and formate), which are conducive to the accel- composite anode with a networked‐rod nanostructure for
eration in anodic bioelectrocatalysis reaction and electron MFC, which delivered a maximum power density of
transfer between biofilm and anode. Even replacing 42 mW·m−2. The integration of PANI with gra-
the rGO anode with CNT anode, the introduction of phene119,120 and graphene nanoribbons121 has also been
Mo2C nanoparticles still has a positive effect on MFC proven to improve the MFC performance with these
performance,110 strongly proving that the Mo2C is a good carbon material‐based anodes. Moreover, PANI has also
component to develop carbon‐based composites for further been extended to integrate with one 3D carbon material‐
optimizing MFC performance. based anode. Yong et al.101 developed a PANI‐decorated
graphene foam with 3D macroporous structure as an
anode for MFC. The PANI has been demonstrated to
2.3.3 | Carbon/conducting polymer binary have an important role in recruiting bacteria on elec-
composites trode, as the bacterial cells can densely adhere to the
external and interior surfaces of 3D graphene/PANI foam
Owning to the good conductivity and environmental instead of 3D graphene foam (Figure 6L–N). On the other
durability of conducting polymers, their application as level, the synergistic integration between PANI and 3D
the components to construct carbon/conducting polymer graphene promoted the direct EET between bacteria and
composites is appealing for MFC anode. Among various anode. Thus, the MFC with 3D graphene/PANI foam

F I G U R E 6 (A–J) Scanning electron microscopy (SEM) images and schematic diagrams of MWCNT@rGO composite (A,D), reduced
graphene oxide (rGO) (B,E), and multiwalled carbon nanotube (MWCNT) (C,F). Reproduced with permission: Copyright 2016, Elsevier.98
(G,H) SEM images of bacterial cells grown on graphene and graphene/Fe3O4 composite anode. Reproduced with permission: Copyright 2017,
Wiley.99 (I) SEM images of FeS2/rGO bioanode. (J,K) Cyclic voltammogram and differential pulse voltammogram of different bioanodes.
Reproduced with permission: Copyright 2018, Wiley.100 (L–N) SEM images of bacterial cells adhered to three‐dimensional graphene/polyaniline
foam at different magnifications. Reproduced with permission: Copyright 2012, American Chemical Society101
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FAN ET AL. | 463

produced a maximum power density of 768 mW·m−2, 3 | C A R B O N M A T E R I A L‐ BASED

whereas this value for MFC with graphene foam was A N O D E WI T H A RT I F I C I A L
only 12.8 mW·m−2. Besides the abovementioned PPy and BIOFILM
PANI, some other conducting polymers including poly-
dopamine and poly(diallyldimethylammonium chloride) 3.1 | Carbon material‐based hybrid
have also been used to combine with carbon material‐ biofilm
based MFC anode.122,123 These two kinds of conducting
polymers possess positive charge as PANI, thus enriching For the above investigations of MFC anodes, the carbon‐
the bacterial cells on the carbon material‐based anodes based materials were modified on the substrate electrode
for the performance improvement of MFCs. for the natural growth of biofilm. However, the electron
transfer inside these naturally formed biofilms is in-
efficient when the thicknesses of biofilm exceed a certain
2.3.4 | Carbon‐based ternary composites limit.129 Furthermore, even for the carbon‐based mate-
rials with macroporous structures, it is still difficult to
The more components in the composites, the more make full use of their interior surfaces, as the bacterial
properties can be integrated.124 In this case, some colonization will block the channels over time.47 In an early
carbon‐based ternary composites have been created for work, Liang et al.130 found that the simultaneous addition
MFC anode. The 3D graphene with macroporous struc- of CNT powders and bacterial cells into the anode chamber
ture allows bacterial penetration, and the presence of of MFC resulted in the formation of a composite biofilm on
MWCNTs can prevent graphene nanosheet from re- the anode, which increased the output voltage of MFC.
stacking and bridge the separated nanosheets. Moreover, Although this study initiated the application of hybrid
the high affinity between Fe3O4 nanoparticles and bac- biofilm in MFC anode, there was no significant increase in
terial cells can accelerate bacterial attachment. In this the biomass on anode. The improved performance of MFC
case, a 3D graphene/MWCNTs/Fe3O4 anode has been was only attributed to the fact that the inserted CNT re-
developed with the purpose of combining all above- duced the anodic resistance. In this regard, researchers
mentioned enhanced strategies.125 The graphene/ have fabricated the bacteria cell/CNT suspension and fil-
MWCNTs/Fe3O4 anode exhibited excellent bacteria‐ tered this suspension by a cellulose acetate filter for creating
hosting capability and high EET efficiency. Therefore, the bacteria/CNT composite films (Figure 7A).45 The SEM
the MFC with this anode delivered a maximum power images revealed a densely packed biofilm on the exterior
density of 882 W·m−3, which was obviously higher than surface of this composite film (Figure 7B). More im-
those of corresponding binary composites. However, the portantly, the CNT and bacteria interpenetrated throughout
poor conductivity of Fe3O4 nanoparticles has a negative the interior space of films (Figure 7C). In contrast, less cell
impact on the electron transfer to some extent. The same density was found on the exterior surface of CNT anode
group employed the core/satellite structured Fe3O4/Au with a natural biofilm growth manner, whereas no cell was
nanoparticles to replace the Fe3O4 nanoparticles in the observed on the interior surface of this control anode. Thus,
design.126 In the devised 3D macroporous graphene foam the application of hybrid biofilm can improve both the EET
decorated with Fe3O4/Au nanoparticles (Fe3O4/Au‐ and cell density on the bioanode of MFC, making it a better
3DGF), the electrons produced by bacterial cells could replacement for traditional bacteria‐colonized carbon
transfer through Au satellites instead of Fe3O4 core, material‐based anodes. Besides the pure CNT, the
further promoting the EET. Moreover, the advantages of CNT‐based nanocomposite was also used to fabricate hy-
3D macroporous graphene foam and Fe3O4 nanoparticles brid biofilm in MFC anode. Park et al.132 developed an
for the bacteria‐hosting ability were well preserved. Fe3O4/CNT/E. coli hybrid biofilm for MFC, which also
Consequently, the maximum power density of MFC with produced a better power density as compared with that of
Fe3O4/Au‐3DGF anode was 2980 mW·m−2, which was natural biofilm. Apart from the enhanced EET by inserting
much higher than the value obtained from the previous CNT into biofilm, the intrinsic magnetic property allowed
work using the graphene/MWCNTs/Fe3O4 anode. The the fixation of hybrid biofilm on the substrate electrode
N‐doping strategy was also used for carbon‐based ternary under an external magnetic field, which helped to form a
composites for further improving the MFC performance. multilayered biofilm and increase the cell density of the
The developed anode materials including N‐CNT/PANI/ anode. Obviously, this study provides a universal strategy to
MnO2 and S/N‐CNT/PANI/MnO2 displayed better MFC replace the traditional suction filter process for the fixation
performance, compared with the corresponding binary of hybrid biofilm to substrate electrode, which can elim-
counterparts, strongly confirming their better synergistic inate the possible metabolic activity loss or bacterial shed-
effects.127,128 ding, but the poor conductivity of Fe3O4 that can affect the
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464 | FAN ET AL.

F I G U R E 7 (A–C) Schematic presentation of the fabrication process of bacteria/CNT composite film and its SEM images at top and side
views. Reproduced with permission: Copyright 2018, Wiley.45 (D–F) Proposed bidirectional EET mechanism in the rGO/bacteria hybrid
biofilm and its SEM images at side and top views. Reproduced with permission: Copyright 2014, Wiley.131 (G) Schematic illustration of the
preparation of G‐CNT hybrid biofilm anode. (H) The current generation capabilities of anodes with different hybrid biofilms in an MFC
using an external resistor of 1000 Ω. Reproduced with permission: Copyright 2015, Wiley.129 CNT, carbon nanotube; EET, extracellular
electron transfer; MESy, microbial electrosynthesis system; G‐CNT, graphene–carbon nanotube; GO, graphene oxide; MFC, microbial fuel
cell; rGO, reduced graphene oxide
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FAN ET AL. | 465

EET should be considered for a further improvement in the has the space to be improved. Recently, cell surface
MFC performance. modification technology has received much attention,
Graphene is another good precursor for the fabrica- through which various function materials can be coated
tion of hybrid films, as its planar structure can provide on the surface of individual living systems.135–137 Thus,
the suitable habitat for bacterial attachment. Encouraged the cell surface modification technology has become an
by this, Yong et al.131 developed a 3D rGO/bacteria hy- effective strategy for further improving the EET between
brid biofilm by the self‐assembly of bacterial cells and the anode and bacterial cells, because it allows every bac-
GO. During the fabrication process, the water‐soluble GO terial cell in hybrid biofilm to intimately make contact
nanosheets behaved like fishing nets to capture the with nanomaterials.138,139
bacterial cells. Meanwhile, the GO nanosheets were re- The use of carbon materials as surface modifiers for
duced to rGO by the captured bacterial cells, which self‐ exoelectrogens is still in its infancy, and only carbon dots
assembled to form the hybrid biofilm due to the π–π (CDs) have yet been used as a surface modifier. Yang
stacking between nanosheets (Figure 7D). The SEM et al.140 have exploited CD‐fed bacterial cells for MFC. As
images confirmed that the rGO/bacteria hybrid biofilm shown in Figure 8A–D, unlike the rare bacterial cell with
delivered a 3D macroporous network with a large a smooth profile, the black spots that could be assigned to
amount of bacteria on the surface of graphene na- CDs were found on the surface of CD‐fed bacterial cell.
nosheets (Figure 7E,F), ensuring the high cell density in The TEM images from cryo‐electron tomography further
the MFC anode and unobstructed substrate transport. revealed that the CDs penetrated into the CD‐fed bac-
Moreover, the multiplexed conductive pathways could be terial cell and were found in the cytoplasm, periplasm,
formed (Figure 7D) due to the good conductivity of rGO and inner membrane of the bacterial cell (Figure 8E,F).
in this hybrid biofilm, accelerating the electron transfer These CDs not only favored the EET and cellular adhe-
between bacterial cells and substrate electrode. As a re- sion but also accelerated the metabolic rate, ultimately
sult, this hybrid biofilm outperformed the natural biofilm leading to an increased maximum current density of
in the MFC performance. On the basis of this study, the MFC. Apart from the good conductivity, CDs also possess
same group replaced the native bacterial cells with the good photoelectrical responsive capability. Inspired by
engineered bacterial cells, which displayed the enhanced this, the CDs have been used as a dual‐functional
flavin biosynthesis and transportation.133 In this case, the modifier to boost the performance of photo‐assisted
local concentration of flavins was increased, ultimately MFC.141 The bacterial cells modified with N,S‐doped CDs
enhancing the electron shuttle‐mediated EET rate in the were fabricated by an electrostatic attraction strategy, in
rGO/engineered bacteria hybrid biofilm and the MFC which the bacterial cells carried a negative charge,
performance. Moreover, the graphene‐based composite whereas the N,S‐doped CDs were previously modified
was also used to construct hybrid biofilm for further with amine‐terminated ionic liquid to show a positively
optimizing MFC performance. Zhao et al.129 integrated charged surface. The laser confocal scanning microscopy
CNT into 3D rGO/bacteria hybrid biofilm for improving images of functional bacterial cells showed a green
the EET and thus the MFC performance. The fabrication fluorescence from CDs, and the TEM images revealed
process of graphene–carbon nanotube (G‐CNT) hybrid that the CDs were coated on bacterial surfaces
biofilm was similar to that of 3D rGO/bacteria hybrid (Figure 8G–I). The differential pulse voltammetry spectra
biofilm, except for the use of a GO–CNT composite as a displayed that the oxidation and reduction peak poten-
substitute for GO (Figure 7G). The current density of tials of cytochrome c on the N,S‐doped CD‐modified
MFC with G‐CNT hybrid biofilm was higher than that of electrode in the dark condition were negatively and po-
rGO hybrid biofilm (Figure 7H), confirming the effec- sitively shifted, compared with those of unmodified
tiveness of inserting CNT into rGO hybrid biofilm. bacterial cells, respectively. Moreover, the shift degrees
were increased under light illumination (Figure 8J,K).
These results indicated that the good conductivity and
3.2 | Carbon material‐modified photoelectrical responsive capability together promoted
individual bacterial cell the EET efficiency. As a result, the MFC with functional
bacterial cells generated a maximum power density of
The abovementioned hybrid biofilms were developed by 1697.9 mW·m−2 under light illumination, which is
mixing the nanomaterials with the bacterial cells. During 2.6‐fold higher than that of the MFC with unmodified
this process, the bacterial cells may aggregate together, bacterial cells. These successes achieved by using
owing to which the bacterial cells inside the aggregations CD‐modified bacterial cells will encourage us to intensify
cannot make direct contact with the nanomaterials.134 In the investigation of carbon material‐modified bacterial
this regard, the EET efficiency in the hybrid biofilm still cells in MFCs.
26379368, 2021, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cey2.113, Wiley Online Library on [19/02/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
FAN

(See caption on next page)

FIGURE 8
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 26379368, 2021, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cey2.113, Wiley Online Library on [19/02/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
FAN ET AL. | 467

4 | CONCLUSIONS A ND a natural biofilm. Thus, the fabrication of novel

PERSPECTIVES carbon‐based hybrid biofilm is promising for MFC.
In the future, the enhancing strategies used in the
In this review, we focused on the carbon material‐based traditional anode with a natural biofilm can be fur-
anodes that have been used in MFCs for improving ther introduced for the fabrication of novel hybrid
performance. On the one hand, carbon materials have biofilms. For example, the doping of heteroatoms can
been used as anodic materials for bacterial habitat. In improve the performance of carbon material‐based
this type, the CNTs and graphene are the most com- anode with natural biofilms; however, the ques-
monly investigated carbon materials. Then, some en- tion whether it could provide a better performance in
hancement strategies, including the introduction of 3D the manner of hybrid biofilms and cell surface
porous structures, heteroatoms, and other kinds of na- modification still remains unanswered. Moreover,
nomaterials (metals, metal organic compounds, and the optimization of space structure has been de-
conducting materials), have been employed to enlargen monstrated to display positive effects on the perfor-
the surface area and enrich the surface properties of mance of carbon material‐based anode with natural
carbon materials for increasing their bacteria‐hosting biofilm, because it is conducive to the diffusion of
capabilities and the EET efficiencies. Moreover, these substrate and mediators. However, most of the cur-
enhancement strategies were also integrated together to rent hybrid biofilms are randomly formed. Thus, it is
develop novel carbon materials with better performance, believed that the regulation of spatial structure of
such as 3D macroporous heteroatom‐doped carbon ma- these hybrid biofilms would extend their application
terials, carbon‐based ternary composites. On the other potentials in MFCs.
hand, in view of the low cell density on anodic materials, (2) Exploring the new generation of carbon‐based an-
the concept of hybrid biofilm has been proposed as MFC odes to integrate MFCs with other energy‐related
anode. The hybrid biofilm involving CNT and graphene systems. Up to now, the carbon material‐based an-
and their composites was created, which improved EET odes have been demonstrated to obviously improve
efficiency expect for the higher cell density. Moreover, the MFC performance. However, the maximum
the single‐cell surface modification technology has been open‐circuit voltage of MFC cannot exceed 1.1 V in
used to ensure that each bacterial cell in the hybrid theory. Except for the cascading of multi‐anodes
biofilm can form good contact with the carbon material in series, the sole use of MFC still has its limitation.
for the best EET efficiency. In this case, developing dual‐functional anodes to
Although these sophisticated carbon materials and integrate MFC with some other energy systems
delicate hybrid biofilms have brought enormous strides seems to be a good choice. On the one hand, much
in the performance of MFCs, the research studies on more effort should be dedicated to endowing the
carbon‐based anode of MFC still have not dealt with a carbon‐based anodes of MFC with photoelectrically
number of aspects. In the future, the research studies can responsive ability. The chemical‐to‐electrical con-
focus more on the following aspects: version can be coupled with solar‐to‐electrical con-
version for improved electricity production. On the
(1) Intensifying the investigation on the carbon‐based other hand, the carbon‐based anodes of MFC can
hybrid biofilms for MFC. Unlike the extensive re- be offered capacitive property, which can also realize
search studies on the development of novel carbon the higher output. Certainly, it is worth to input
materials as anode materials for MFC, only several strong effort in probing into the combinational use of
groups have paid their attention to the carbon‐based these three technologies or the integration of MFC
hybrid biofilms. However, these reported works with other kinds of energy‐related systems.
strongly proved that these carbon‐based hybrid bio- (3) Revealing the relationships between carbon material‐
films outperform the same carbon materials but with based anode and the long‐time stability of MFC. After

F I G U R E 8 (A–D) Transmission electron microscopy (TEM) images of carbon dot (CD)‐fed bacterial cells (A,B) and pristine
bacterial cells (C,D) at different magnifications. (E,F) TEM images constructed by cryo‐electron tomography for CD‐fed bacterial cells.
Reproduced with permission: Copyright 2020, Springer Nature.140 (G,H) Bright and fluorescence field images of the functioned bacterial
cells. (I) High‐resolution TEM images of the functioned bacterial cells. (J,K) Differential pulse voltammogram of cytochrome c on the
unmodified electrode and CD‐modified electrode in the dark or light conditions. (L) Polarization and power density curves of MFC with
pristine and functional bacterial cells under dark or light conditions. Reproduced with permission: Copyright 2019, Elsevier141
 26379368, 2021, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cey2.113, Wiley Online Library on [19/02/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
468 | FAN ET AL.

the output of MFC reaches a new elevated level, the 10. Liu H, Ramnarayanan R, Logan BE. Production of electricity
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472 | FAN ET AL.

128. Wang Y, Zheng H, Chen Y, Wen Q, Wu J. Macroporous

Rong‐Bin Song at Zhengzhou University. His
composite capacitive bioanode applied in microbial fuel cells.
Chin Chem Lett. 2020;31:205‐209. research interests focus on single‐cell surface
129. Zhao C, Wu J, Ding Y, et al. Hybrid conducting biofilm with modifications and their applications in microbial
built‐in bacteria for high‐performance microbial fuel cells. fuel cells.
ChemElectroChem. 2015;2:654‐658.
130. Liang P, Wang H, Xia X, et al. Carbon nanotube powders as
Rong‐Bin Song received his PhD degree
electrode modifier to enhance the activity of anodic biofilm in
microbial fuel cells. Biosens Bioelectron. 2011;26:3000‐3004.
from the School of Chemistry and
131. Yong YC, Yu YY, Zhang X, Song H. Highly active bidirec- Chemical Engineering at Nanjing Uni-
tional electron transfer by a self‐assembled electroactive versity in 2017. He continued his post-
reduced‐graphene‐oxide‐hybridized biofilm. Angew Chem Int doctoral research at Nanjing University
Ed. 2014;53:4480‐4483. from 2017 to 2020. Currently, he joined
132. Park IH, Christy M, Kim P, Nahm KS. Enhanced electrical Zhengzhou University as an associate professor. His
contact of microbes using Fe3O4/CNT nanocomposite anode
recent research interests focus on the novel electrode
in mediator‐less microbial fuel cell. Biosens Bioelectron. 2014;
materials for microbial fuel cell, single‐cell surface
58:75‐80.
133. Lin T, Ding W, Sun L, Wang L, Liu C‐G, Song H. Engineered modification, and biofuel cell‐based self‐powered
Shewanella oneidensis‐rGO biohybrid with enhanced bio- biosensor.
synthesis and transport of flavins enabled a highest bioelec-
tricity output in microbial fuel cells. Nano Energy. 2018;50: Zhaohui Li received his PhD degree
639‐648.
from the State Key Laboratory of
134. Song RB, Wu Y, Lin ZQ, et al. Living and conducting: coating
individual bacterial cells with in situ formed polypyrrole.
Chemo/Biosensing and Chemometrics
Angew Chem Int Ed. 2017;56:10516‐10520. at Hunan University in 2007. He did
135. Xiong W, Zhao X, Zhu G, et al. Silicification‐induced cell ag- his postdoctoral training in Walt
gregation for the sustainable production of H2 under aerobic Group at Tufts University from 2007
conditions. Angew Chem Int Ed. 2015;54:11961‐11965. to 2009 and in Pacific Northwest National Labora-
136. Yang SH, Lee K‐B, Kong B, Kim J‐H, Kim H‐S, Choi IS. tory from 2009 to 2011. At present, he is a full
Biomimetic encapsulation of individual cells with silica.
professor at Zhengzhou University. His research
Angew Chem Int Ed. 2009;48:9160‐9163.
interests mainly focus on nanomaterial prepara-
137. Li P, Jiang Y, Song R‐B, Zhang J‐R, Zhu J‐J. Layer‐by‐layer
assembly of Au and CdS nanoparticles on the surface of tion and its applications in chemo/biosensing.
bacterial cells for photo‐assisted bioanodes in microbial fuel
cells. J Mater Chem B. 2021;9:1638‐1646. Qichun Zhang is a professor at City
138. Liu SR, Cai LF, Wang LY, et al. Polydopamine coating on University of Hong Kong. His research
individual cells for enhanced extracellular electron transfer.
interests include carbon‐rich conju-
Chem Commun. 2019;55:10535‐10538.
139. Yu YY, Wang YZ, Fang Z, et al. Single cell electron collectors
gated materials and their applications
for highly efficient wiring‐up electronic abiotic/biotic inter- in optoelectronic and semiconductor
faces. Nat Commun. 2020;11:4087. devices as well as microbial fuel cells.
140. Yang C, Aslan H, Zhang P, et al. Carbon dots‐fed Shewanella Dr. Zhang is a fellow of the Royal Society of
oneidensis MR‐1 for bioelectricity enhancement. Nat Chemistry. He has published more than 400
Commun. 2020;11:1379. papers, with >21,800 total citations and an
141. Guo D, Wei H‐F, Song R‐B, et al. N,S‐doped carbon dots as
H‐index of 81. From 2018 to 2020, he is a highly
dual‐functional modifiers to boost bio‐electricity generation
cited researcher in cross‐field (top 1%) on Clarivate
of individually‐modified bacterial cells. Nano Energy. 2019;
63:103875. Analytics's lists.

AUTH OR BI OGRAPH IES

Xiaoqi Fan received his BS degree How to cite this article: Fan X, Zhou Y, Jin X,
from the College of Chemical Engi- Song R‐B, Li Z, Zhang Q. Carbon material‐based
neering at Zhengzhou University in anodes in the microbial fuel cells. Carbon Energy.
2020. Currently, he is a master's 2021;3:449‐472. https://doi.org/10.1002/cey2.113
candidate under the supervision of full
Prof. Zhaohui Li and associate Prof.