Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
S Kalathil, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia
SA Patil, Technische Universität Braunschweig, Braunschweig, Germany
D Pant, Flemish Institute for Technological Research (VITO), Boeretang, Belgium
© 2018 Elsevier Inc. All rights reserved.
Glossary
Bioanode The electrode where bacteria transfer metabolically produced electrons after substrate oxidation reactions and form
a biofilm.
Biocathode or biotic cathode The electrode from which bacteria accept electrons to reduce electron acceptors such as oxygen.
Electrochemically active bacteria or biofilm Certain microbes (e.g., Shewanella sp. and Geobacter sp.) are electrically active and
can directly use the anode as a terminal electron acceptor for achieving their respiration. These bacteria referred to as
electrochemically active bacteria can colonize on the MFC anode and form biofilmsewidely referred to as electrochemically
active biofilms.
Extracellular electron transfer A process in which electrochemically active bacteria transport their metabolically generated
electrons outside of the cells to insoluble materials such as anode or metal oxides through a series of protein networks.
Microbial fuel cell It is a bioelectrochemical system or device that generates electricity through microbially driven oxidation of
biodegradable substrates at the anode and abiotic or microbially catalyzed oxygen reduction reaction at the cathode.
Abbreviations
3D Three dimensional
BES Bioelectrochemical system
CaS Calcium sulfide
COD Chemical oxygen demand
Cu-MF Copper-melamine foam
EAB Electrochemically active bacteria/biofilm
EET Extracellular electron transfer
ET Electron transfer
Fe3O4 Magnetite
309
310 Microbial Fuel Cells: Electrode Materials
Current Status
During the last decade, several scientific and engineering developments due to trans-disciplinary research efforts concerning funda-
mental electron transfer mechanisms, reactor configurations, and materials have led to considerable increase in power generation
and wastewater treatment efficiencies of MFCs.4 In addition to wastewater treatment and energy recovery, the application areas for
MFCs have also been expanded to resource recovery of nutrients (e.g., nitrogen and phosphorous)5 and critical metals,6 bio-
sensing7,8 and desalination.9 Some large-scale practical demonstrations of MFC-based technologies are currently under trial. Exam-
ples include the energy-efficient wastewater treatment systemdElectrogenic BioReactor system (www.emefcy.com), the BioVoltTM
reactors for wastewater treatment and energy recovery (http://cambrianinnovation.com/), and the plant-MFCs powering LEDs
(light-emitting diodes) (www.plant-e.com). Lately, the interlinking possibilities of MFCs with other technologies for the generation
of two or more energies and wastewater treatment have also attracted considerable attention.10–12 Despite its sustainable nature and
specific application niche, this technology concept still has a long way to go before its full potential is realized. This is because of
scientific and technological challenges such as increasing the power outputs to higher levels and a considerable decrease in the unit
costs since it has to compete in the low-value market.
Fig. 2 Electron transfer mechanisms from microorganisms to the anode in microbial fuel cells. (A) Indirect electron transfer via redox mediators
and primary metabolites such as H2, and (B) direct electron transfer via outer-membrane cytochromes, proteins or enzymes, and conductive pili such
as nanowires.
312 Microbial Fuel Cells: Electrode Materials
The key component of an MFC is the bioanode where microorganisms grow as a biofilm that functions as “living biocatalysts.” The
MFC performance largely depends on this living biofilm, and hence a robust electrochemically active biofilm (EAB) should be
developed at the anode. A prior understanding of microbe–electrode interactions is critical to optimize the anode architectures.
There are several factors affecting the interactions of microbes with the anode such as surface roughness, surface chemistry, material
type, porosity, and hydrophilicity.19 To be a suitable bioanode, the material should meet several criteria as depicted in Fig. 3.
Carbon-based electrodes
Carbon-based electrodes are commonly employed in MFCs due to their biocompatibility, long durability, good conductivity, and
low cost.22 The interesting feature of the carbon material is that it can exhibit various morphologies and structures for designing
attractive and efficient electrodes.22 Carbon-based anodes promote efficient attachment of bacteria by accelerating EAB formation
and provide a conductive pathway for the EET.
Graphite
Graphite is a crystalline form of carbon with the sp2 hybridization structure. Due to high stability and conductivity, graphite is
a promising material as bioelectrodes in MFCs.20 Different forms of graphite electrodes such as rods, felts, foams, and brushes
have been employed as bioanodes in MFCs. For instance, Chaudhuri and Lovley used graphite bioanodes in a glucose-fed MFC
using Rhodoferax ferrireducens as an inoculum.23 The authors observed that the graphite felt bioanode produced higher power
density as compared to the graphite rod. The high surface area of graphite felt led to dense biofilm growth at the bioanode, which
allowed high glucose oxidation. Logan et al. developed graphite brush bioanodes for cubic and bottle air cathode MFCs24
(Fig. 4). The graphite brush electrode significantly reduced internal resistance of the cubic MFC by producing a power density
of 2400 mW/m2. Graphite sheet-based bioanode outperformed graphite felt in an E. coli-inoculated MFC by producing twofold
higher power density.25 Doping of graphite with metals has been proved to be an effective strategy to improve the bioanode
performance. For example, doping of graphite with calcium sulfide (CaS) enhanced bacterial affinity toward the electrode surface
Fig. 3 Pert diagram showing the criteria for suitable bioanodes. Reproduced from Xie, X.; Criddle, C.; Cui, Y. Design and Fabrication of Bio-
electrodes for Microbial Bioelectrochemical Systems. Energ. Environ. Sci. 2015, 8, 3418–3441 with permission from Royal Society of Chemistry.
Microbial Fuel Cells: Electrode Materials 313
Fig. 4 Graphite fiber brush anode electrode used in (A)-Cubic-MFC (C-MFC) and (B)- Bottle-MFCs (B-MFC), and photographs of the reactors con-
taining the brush electrodes: (C)- C-MFC shown with the brush anode, and (D)- B-MFC with brush anode and side port cathode. Reproduced from
Logan, B.; Cheng, S.; Watson, V.; Estadt, G. Graphite Fiber Brush Anodes for Increased Power Production in Air-Cathode Microbial Fuel Cells.
Environ. Sci. Technol. 2007, 41, 3341–3346 with permission from American Chemical Society.
and lowered the electric potential for the EET process.26 Also, it was noticed that CaS was better dopant over iron-containing
compounds, Fe3O4 and FeS.
Fig. 5 (A), (B), and (C) Scanning electron microscopic (SEM) images of reticulated carbon foam-pomelo peel (RCF-PP) at different magnifications;
the inset of A is a digital image of a peeled Pomelo. (D) Energy dispersive X-ray spectrum of RCF-PP. Reproduced from Chen, S.; Liu, Q.; He, G.
et al. Reticulated Carbon Foam Derived From a Sponge-Like Natural Product as a High Performance Anode in Microbial Fuel Cells. J. Mat. Chem.
2012, 22, 18609–18613 with permission from Royal Society of Chemistry.
Stainless steel
Stainless steel (SS) is an excellent metal-based material alternative to carbon-based materials as the MFC bioanode due to its
outstanding mechanical properties, electrical conductivity, and corrosion resistance (e.g., of high grade SS materials).36 It is easy
to scale-up and offers stability for long-term operation of MFCs. Recently, several studies have reported SS as efficient bioanodes
for producing stable current densities. A plain SS bioanode outperformed flat graphite electrode by producing higher current under
identical experimental conditions.36 However, the plain SS is not good enough to develop thick and robust biofilm, which may
prevent to produce high current from the MFC. To tackle this issue, Ketep et al. proposed a three-dimensional (3D) SS foam
with appropriate porosity as the bioanode for MFCs.37 The 3D SS foam produced higher current than plain SS (four times) and
carbon cloth (two times). Surface modification of the SS is also proved to be an effective strategy to improve the performance of
SS-based bioanodes.38 Liang et al. modified the surface of SS by heat treatment, carbon coating, hydrophilization, and polyaniline
coating.38 All the surface modifications of SS showed better performance over unmodified plain SS bioanodes that are usually less
biocompatible.
Advanced electrodes
In addition to the use of the traditional materials, researchers have also tried purposely built 3D materials and surface modification
strategies to fabricate anodes for MFCs.
the inner layers and clumping of the fibers were the major issues identified with these carbon brush electrodes. The polyaniline
precursor-based electrospun carbon fiber mats possessed high porosity that allowed efficient mass transfer within the electrode
material but had a low mechanical strength.39
The natural precursor materials utilized for purposely built electrodes include loofah,40 kenaf stem (Hibiscus cannabinus),41
coconut shells,42 cardboard,43 mushroom and corn stem,44 and pomelo peel.44 They generally possess macroscale pores that allow
good mass transfer and high specific surface area for biofilm formation. Most of them resulted in achieving higher current densities
(for instance, the multilayered carbonized cardboard anode produced up to 7 mA/cm2) but possessed low mechanical strength and
relatively low conductivity thus limiting their scalability in BESs. Despite several favorable properties of above-mentioned materials
for use as anodes in BESs, some critical limitations such as low conductivity and fragile structures have hindered their large-scale
applications. The lower conductivity of carbon materials, in particular, of the porous electrodes, leads to higher specific electrical
resistivity.
Ceramic electrodes
Ceramic-based bioanodes seem to be promising electrode materials for practical applications of MFCs.47 There are many studies
available on ceramic MFCs with outstanding power outputs.47 The ceramics provide a conducive environment for bacterial attach-
ment and exhibit excellent stability under harsh wastewater conditions. For example, ice-templated titanium-based ceramics (ITTC)
bioanode produced a current density of 128.7 A/m2 in a Geobacter sulfurreducens-based MFC, the highest current density produced
(normalized to the electrode surface area) to date.48 The ITTC provided highly porous 3D architectures and macrochannels for effi-
cient mass transfer and biofilm formation (Fig. 6).
Fig. 6 (A) 3D TiO2 porous scaffold, precursor of ITTC electrodes, (B) SEM image of the internal architecture of the TiO2 scaffold, and (C) ITTC elec-
trode obtained by reduction of TiO2 porous scaffolds. Arrows indicate the freezing direction. Reproduced from Massazza, D.; Parra, R.; Busalmen, J.
P.; Romeo, H. E. New Ceramic Electrodes Allow Reaching the Target Current Density in Bioelectrochemical Systems. Energ. Environ. Sci. 2015, 8,
2707–2712 with permission from Royal Society of Chemistry.
316 Microbial Fuel Cells: Electrode Materials
Cathode Materials
Similar to the bioanode, the cathode is also an integral part of MFCs. Usually, sluggish substrate reduction reactions (mainly oxygen
reduction reaction) at the cathode due to poor catalytic activities of materials mainly limit the performance of MFCs. Hence, the
development of high-performing cathodes has immense priority to improve the performance of MFCs. Most of the electrode mate-
rials used as bioanodes have also been employed for the cathode development. Generally, cathodes are classified as abiotic and
biotic cathodes as summarized below.
Abiotic cathodes
Abiotic cathodes usually reduce oxygen to produce water, which is thermodynamically highly favorable in the presence of a catalyst.
Platinized carbon electrodes are commonly employed as oxygen-reducing cathodes in MFCs.49 However, high cost and catalyst
poisoning prevent the practical applications of Pt-based cathodes. The high-cost Pt has been replaced by other nonprecious elec-
trodes like Mn2O3, Fe2O3, and heteroatom doped carbon.49,50 The catalyst at the cathode is not needed if ferricyanide is used as
catholyte.51 However, the use of ferricyanide is not sustainable for long-term operation of MFCs.
Electrodes constitute a major component for MFCs and besides the biocatalyst the most extensively researched area in this field.
Carbon-based materials are most frequently used as electrodes, both anode and cathode. For the anode, the main developments
have been toward the surface treatment to improve the bacterial attachment and biofilm formation. Considerable efforts have
also been directed toward enhancing the specific surface area of the materials for achieving higher anodic biofilm densities. At
the cathode side, oxygen reduction has been the reaction of choice as the electron accepting mechanism, and the efforts here
have been to develop electrodes with non-platinum group metals as catalysts. Over the years, several alternatives have been
proposed as mentioned above for both submerged and gas diffusion air cathodes, which are low-cost and highly performing.58
There is still room for further development of the MFC electrodes as the material science is highly advanced. Highly porous and
conductive materials such as 3D graphene scaffolds are available, which can be employed as both anode and cathode in MFCs.
Fig. 7 SEM images of the biotic cathodes showing nanowire-like structures. Reproduced from Jang, J. K.; Kan, J.; Bretschger, O.; Gorby, Y. A.;
Hsu, L.; Kim, B. H.; Nealson, K. H. Electricity Generation by Microbial Fuel Cell Using Microorganisms as Catalyst in Cathode. J. Microb. Biotechnol.
2013, 23, 1765–1773 with permission from The Korean Society for Microbiology and Biotechnology.
Microbial Fuel Cells: Electrode Materials 317
Electrode materials should be highly stable in harsh wastewater conditions for long-term MFC operation. In particular, 3D electrode
materials should possess optimum pore size to avoid clogging related issues in wastewater treatment applications. Currently, the
high cost of the materials and surface modification strategies mainly hinders the MFC scale-up for practical applications. Hence,
cheaper and stable materials as well as efficient strategies for making composite metal- or carbon-based electrodes should be devel-
oped to extend the application of MFCs at large-scale levels. Future efforts need to be directed toward testing upscaling of the effi-
cient electrodes for MFCs as well as making clever combinations of anode and membrane or cathode and membrane to develop an
ideal membrane electrode assembly.
See also: Enzymatic Electrodes: Characteristics, Fabrication Methods, and Applications; Enzymatic Phosphorylation of Peptides and Proteins;
Implantable Enzyme-Based Biofuel Cells.
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Further Reading
Beyenel, H.; Babauta, J. T. Biofilms in Bioelectrochemical Systems: From Laboratory Practice to Data Interpretation, Wiley & Sons, 2015. ISBN 978-1-118-41349-4.
Guo, K.; Prévoteau, A.; Patil, S. A.; Rabaey, K. Engineering Electrodes for Microbial Electrocatalysis. Curr. Opin. Biotechnol. 2015, 33, 149–156.
Kumar, A.; Hsu, L. H.-H.; Kavanagh, P.; Barrière, F.; Lens, P. N. L.; Lapinsonnière, L.; Lienhard, V.; Schröder, U.; Jiang, S.; Leech, D. The ins and Outs of Microorganism-Electrode
Electron Transfer Reactions. Nat. Rev. Chem. 2017, 1, 1–13.
Logan, B. E. Microbial Fuel Cells, John Wiley & Sons: Hoboken, 2008.
Logan, B. E.; Rabaey, K. Conversion of Wastes Into Bioelectricity and Chemicals by Using Microbial Electrochemical Technologies. Science 2012, 337, 686–690.
Logan, B. E.; Hamelers, B.; Rozendal, R.; Schröder, U.; Keller, J.; Freguia, S.; Aelterman, P.; Verstraete, W.; Rabaey, K. Microbial Fuel Cells: Methodology and Technology. Environ.
Sci. Technol. 2006, 40, 5181–5192.
Relevant Websites
https://www.is-met.org/.
http://www.bioelectrochemical-soc.org/.
http://www.engr.psu.edu/ce/enve/logan/bioenergy/research_mfc.htm.
http://www.geobacter.org/Microbial_Fuel_Cells.
https://www.linkedin.com/groups/1903929.
https://www.mudwatt.com/.