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Renewable Energy xxx (2016) 1e18

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

An overview on emerging bioelectrochemical systems (BESs):


Technology for sustainable electricity, waste remediation, resource
recovery, chemical production and beyond
Suman Bajracharya a, b, 1, Mohita Sharma a, c, 1, Gunda Mohanakrishna a,
Xochitl Dominguez Benneton a, David P.B.T.B. Strik b, Priyangshu M. Sarma c,
Deepak Pant a, *
a
Separation & Conversion Technologies, VITO e Flemish Institute for Technological Research, Boeretang 200, 2400, Mol, Belgium
b
Sub-Department of Environmental Technology, Bornse Weilanden 9, P.O. Box 17, 6700 AA, Wageningen, The Netherlands
c
Environmental and Industrial Biotechnology Division, The Energy and Resource Institute (TERI), Darbari Seth Block, Habitat Place, Lodhi Road, New Delhi,
110003, India

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

Article history: Bioelectrochemical systems (BESs) are unique systems capable of converting chemical energy into
Received 12 January 2016 electrical energy (and vice-versa) while employing microbes as catalysts. Such organic wastes including
Received in revised form low-strength wastewaters and lignocellulosic biomass were converted into electricity with microbial fuel
23 February 2016
cells (MFCs). Likewise, electrical energy was used to produce hydrogen in microbial electrolysis cells
Accepted 2 March 2016
Available online xxx
(MECs) or other products including caustic and peroxide. BES were also designed to recover nutrients,
metals or removal of recalcitrant compounds. Moreover, photosynthetic micro-organisms as well as
higher plants were implemented to use solar energy for electricity generation. The diversity on microbial
Keywords:
Recalcitrant removal
and enzymatic catalysts offered by nature allows a plurality of potential applications. As compared to
Microbial electrocatalysis conventional fuel cells, BESs operate under relatively mild conditions and do not use expensive precious
CO2 sequestration metals as catalysts. The recently discovered microbial electrosynthesis (MES) of high-value chemicals has
Biosensors greatly expanded the horizon for BES. Newer concepts in application as well as development of alter-
Value-added chemicals production native materials for electrodes, separators, catalysts along with innovative designs have made BES very
promising technology. This article discusses the recent developments that have been made in BESs so far,
with the emphasis on their various applications beyond electricity generation and resulting perfor-
mances as well as existing limitations.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction this context, the development of renewable energy sources has


become crucial for a sustainable landscape, especially by
There is a growing demand for new energy sources due to the decreasing the dependency on energy import and by diversifying
limited accessibility and pollution caused by the use of fossil fuels. energy production sources [147]. Bioelectrochemical systems
At present, the annual energy demand is approximately 13 (BESs) have considerably boomed over the past decade for their
terrawatts (TW) worldwide and it is estimated to reach around contribution as an emerging sustainable technology for concurrent
23 TW by the year 2050 [15]. Meanwhile, intensive resource utili- electricity production and wastewater treatment [122]. In addition,
zation in municipal, industrial and agricultural activities will BESs also offer unique possibilities for clean and efficient produc-
continue the process of environmental degradation creating envi- tion of fuels and high-value chemicals using microorganisms [48].
ronmental threats of global warming and related consequences. In As the BES functions in a completely multi-disciplinary approach, a
large quantum of research have been conducted worldwide in the
fields of microbiology, electrochemistry, bioelectrochemistry,
biotechnology, environmental science, materials science, etc. In
* Corresponding author.
E-mail addresses: deepak.pant@vito.be, pantonline@gmail.com (D. Pant).
these electrochemical systems, the redox potentials of an oxidation
1
Equal contribution. reaction at the anode and a reduction reaction at the cathode create

http://dx.doi.org/10.1016/j.renene.2016.03.002
0960-1481/© 2016 Elsevier Ltd. All rights reserved.

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
2 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

a potential difference which is the driving force for electrons to flow identified as the electron-transferring microbes and as such well-
from a low potential to high potential, spontaneously [137]. This studied. However, stable and higher currents have been recorded
flow of electrons through an external circuit is measured as electric more often in MFCs with mixed cultures in bioanodes, rather than
current. Whenever, microbes or enzymes are involved in the with pure cultures. The presence of Geobacteraceae in the bioanode
oxidation or reduction or both reactions, the system is termed as a community often showed high power densities registered in MFCs
microbial electrochemical system (MXC) or in a broader term BES [86,101]. The highest current density reported so far in MFC was
[64]. If microbes catalyze the anodic reaction, they are applied as 390 A m2 obtained using mixed culture at the layered-corrugated
bioanode and if microbes catalyze the cathodic reactions, they are carbon anode with high surface area [19]. The nature of substrate,
applied as biocathode. Microbial fuel cells (MFCs) are a type of MXC anode potential and electrolyte chemistry affect the microbial ac-
that generate electricity from the degradation of organic matter in tivity and electron transfer [52,134]. Higher electrolyte conductivity
anode chamber. A low redox potential for the oxidation of organic ascertains the better performance of microbial electrochemical
matter at the anode and a high redox potential for the oxygen systems but the electrolyte conductivity should not go beyond the
reduction reaction (ORR) at the cathode, typically results into tolerance level of bacteria [168]. However, it was identified that the
bioelectricity generation. In the case of microbial electrolysis cells application of halophilic bacteria in BESs have reported to produce
(MECs), an external voltage is applied to subject the cathode po- the current densities up to 85 A m2 with bioanodes formed from a
tentials driving the production of valuable chemicals [169]. The BES salt-marsh inoculum and cultivated in a 1.5 times more saline
in which CO2 or organic molecules are cathodically reduced to electrolyte than seawater [151]. Significant current densities and
higher value organic molecules is called microbial electrosynthesis power densities obtained from MFCs, as reported in various studies,
(MES) [144]. In addition, BESs have also emerged with other ap- are listed in Tables 1 and 2 respectively. The performance of MFCs
plications such as microbial desalination cells (MDCs) for the also relies on the electrode material used and its structure. Graphite
desalination of water, and sediment or plant microbial fuel electrodes with a roughened surface have shown to produce higher
cellsdwherein microbes are intermingled with plant roots for the power densities than flat graphite electrodes [189]. Likewise,
electricity generation [12,27,47]. Moreover, BESs are also identified increasing the surface area of MFC anodes using porous materials
as efficient bioreactors for the treatment of recalcitrant pollutants such as graphite brush, carbon felt and carbon nanotubes, have
and toxic wastewaters; the process is termed as bioelectrochemical shown considerable increase in current density [20,53,123]. Higher
treatment (BET) or microbial electroremediation [124]. surface area of electrodes provides a larger surface for bacterial
In this direction, the present review provides the overview of (i) adhesion and electron transfer between the bacteria and electrode,
all types of BESs and their applications, (ii) the basic working thereby demonstrating noteworthy improvement in current den-
principles involved, (iii) substrate utilization, (iv) synthesis of tar- sities. Direct electron transfer phenomenon of microbes with metal
geted chemicals and (v) the recent concepts and developments electrodes has also been demonstrated including dimensionally
made in BES. This review emphasizes the recent advances in BES stable anodes (DSA, titanium over iridium and tantalum oxide),
that were developed beyond electricity generation. This review also stainless steel and platinum electrodes [44,139]. Current densities
helps to attract the young researchers from the allied disciplines of obtained with porous carbon anodes are typically higher than those
BES to advance the technology with multiple applications. reported with metals except for platinum [217]. A switch from
planar electrodes to three-dimensional electrodesdhaving opti-
2. Types of bioelectrochemical systems mized microstructuresdwas correlated to a considerable increase
on bioelectrode performance [167]. Macrostructure modification in
Based on the desired end objectives, BESs can be broadly clas- anode, with multi-layered corrugated carbon configuration evi-
sified into electrogenesis systems, electrohydrogenesis systems, denced a huge rise in current densities [19]. Especially once mass
microbial desalination systems, microbial electrosynthesis systems transport limitations are tackled by flow-through electrodes,
and bioelectrochemical treatment systems. Each type of BES with higher current and power densities can be achieved as a result of
specific names as shown in Fig. 1 are discussed in the following low internal resistances [170]. The relevance of cathode materials in
sections. the power densities obtained from MFCs is demonstrated in Table 2
based on the MFC studies reporting similar anode materials. Cata-
2.1. Microbial fuel cells (MFCs) lysts e.g. MnO2 coated air cathodes and membrane and cloth
electrode assemblies as cathode in MFCs reported higher power
MFCs harness electrical current from the microbial oxidation of densities. Materials used for MFC construction, design and config-
organic matter using a solid electrode as an electron acceptor [143]. uration influence the internal resistance, which in turn govern the
The anode surface of MFCs facilitates microbial attachment and total performance of the system.
oxidation of organics, thereby generating electrons which are then
simultaneously transferred to the cathode compartment via an 2.2. Microbial electrolysis cells (MECs)
external circuit containing an external load. Electroneutrality is
warranted by ions transport through an ion-permeable medium or MECs utilize the property of bacteria to convert chemical energy
a membrane while electricity is produced in the process. The first of to electrical energy and allow electrolysis of water [194]. External
such systems was demonstrated by M.C. Potter in 1911, which power applied onto the electrical circuit of BES drives electrons
achieved a maximum voltage of 0.3e0.5 V [140]. Electroactive from anode to the cathode and also supports the hydrogen gener-
bacterial biofilms developed on the anode of BES function as the ation at the cathode [78]. Contrary to the MFCs, the cathode of
electrocatalytic unit for electricity generation. Production of MECs operates under anaerobic conditions that facilitate hydrogen
bioelectricity in MFC is directly dependent on the capacity of production. However the anoxic environment in MECs, along with
exoelectrogens (microbes generating electricity) present on the high concentrations of hydrogen production, can also promote
anode, which facilitate the transfer of electrons from the reduced methane production once CO2 and methanogens are available. A
substrate to the anode. Oxidation of complex organic matter in few of the methods to mitigate methane production includes the
wastewater requires diverse microbial communities. Dozens of aeration of the cathode chamber between batches, lowering of the
bacterial species have been found of being able to produce electric pH, operation at short retention times and giving a heat shock to
current. The Shewanella and Geobacter species were earlier the inoculum, or adding chemicals that inhibit the growth of

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18 3

Fig. 1. Schematic overview of various types of bioelectrochemical systems (BESs).

methanogens [23]. Hydrogen production in MECs, according to cathode. Cathodic biocatalysts (with attached cathodic biofilms)
their configurations and the substrates treated, are listed in Table 3. reduce the available terminal electron acceptor to produce value
Higher electric currents are typically observed in MECs, when added products [112,125,144]. The bioelectrosynthesis process can
compared to MFCs, which is due to the additional applied voltage be highly specific, depending on the biocatalyst catalyzing the
that helps overcoming the cathode limitations in MEC [170]. The redox reaction and the terminal electron acceptor involved in the
energy required for MEC operation can also be provided by another process, along with the electrochemically active redox mediators or
separate MFC as a power source [198]. This study reported a suitable reducing equivalents. Biocathodes are the key components
hydrogen production rate of 0.24 m3-H2 m3d1 and energy re- of microbial electrosynthesis, where the electrode oxidizing mi-
covery of 23% using a fermentation effluent as substrate. However, croorganisms are involved in the formation of reduced value-added
for the supply of a stipulated voltage that allows for maximal product such as acetate, ethanol, butyrate [6]. MES refers to the
hydrogen production in MEC, efficiently connected multiple MFCs production of chemical compounds in an electrochemical cell by
are required [198]. In a MEC with bioanode and biocathode, electricity-driven CO2 reduction as well as reduction/oxidation of
expensive metals like platinum are not required as catalyst and other organic feedstocks using microbes as biocatalyst [144]. As a
preferably, the enrichment of microbes on the carbon cathode de- proof of concept [130] presented MES as a microbial catalysis of CO2
creases the start-up time and produces comparable current den- reduction to multi-carbon organic compounds using electrical
sities to those of bioanode [78]. Furthermore, the hydrogen current at the cathode. As such, MES is also prospected as an
synthesized in MECs can also drive the biochemical production of alternative strategy to capture electrical energy in covalent chem-
other chemicals [144]. Most common examples of reduction re- ical bonds of organic products. Several studies have reviewed and
actions at the cathode are proton reduction to hydrogen, oxygen highlighted different aspects of MES including microbiology,
reduction to H2O2 and CO2 reduction to methane (CH4) and acetate technology and economics, as well as deep understanding on the
[23,26,158]. These recently developed BESs for the production of metabolic routes involved, electron transfer mechanisms and
valuable chemicals and biofuels such as organic acids, or alcohols practical considerations [41,143,144].
from low value compounds or CO2 [125,130,166] are deliberated in
the next section.
2.4. Enzymatic fuel cells (EFCs)

2.3. Microbial electrosynthesis (MES) Enzymatic fuel cells (EFCs) make use of specific enzymes on the
electrode surface (or in electrolyte suspension) that facilitate the
MES, also known as bioelectrosynthesis, is a new-fangled catalytic oxidation of fuel and drive specific reactions desired for
perspective of BES which utilizes the reducing power generated various applications. Davis & Yabrough [37] demonstrated the use
from the anodic oxidation to produce value added products at the of microbes and enzymes in biofuel cells using glucose oxidase.

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
4 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

Table 1
Overview of current densities reported in MFCs in connection to the type of microbial culture used and anode material.

Source inoculum Type of MFC and anode material/specifications Current density (A m2) Reference

Geobacter spp. Two chamber/graphite sticks 0.065 [10]


Geobacter spp. Two chamber/graphite anodes at 0.2 V/AgAgCl 0.16e1.14 [10]
Anaerobic culture of Escherichia coli K12 Two-chambered MFC/platinum paddle electrodes (5 cm2) 5 [150]
and ethanol as substrate
Anaerobic culture of Escherichia coli K12 Two-chambered MFC/platinum paddle electrodes (5 cm2) 50 [150]
and formate as substrate
Pre-acclimated bacteria from MFC Cube shaped single-chamber MFC/graphite fiber brush 8 [100]
anode (7170 m2 m3 brush volume)
Mixed culture 2.5 ml anode chamber, bicarbonate buffer/Double cloth 9.9 [51]
electrode assemblies (CEAs); (2  7 cm2 projected electrode area),
Klebsiella pneumonie L17 Two chamber/Carbon felt 1.2 [216]
Rhodopseudomonas palustris DX-1 Single chamber/graphite brush 9.9 [206]
Geobacter sulfurreducens Single chamber/DSA at 0.2 V/AgAgCl 5 [44]
Geobacter sulfurreducens Single chamber/solid graphite at 0.2 V/AgAgCl 8 [44]
Geobacter sulfurreducens Single chamber/multiple stainless steel anode at þ0.2 V/AgAgCl 2.4 [45]
Mixed culture Single chamber/Graphite plates projected surface area of 70 cm2 0.27 to 0.35 [124]
Mixed culture 3D carbon fiber anode prepared by gas assisted electrospining; 30 [20]
anode polarised at 0.2 V/AgAgCl
Mixed culture Half-cell semi batch reactor/Layered corrugated Carbon 70e400 [19]
anode/polarised at 0.2 V/AgAgCl
Mixed culture from air cathode MFC 30 ml anode chamber/Double cloth electrode assemblies 16.4 [50]
(CEAs); (2  100 cm2 projected area);
Geoalkalibacter subterraneus Planar graphite electrode poised at 0.2 V/SCE; Saline 4.68 ± 0.54 [14]
electrolyte 3.5% NaCl
Mixed culture 3D scaffold-NanoWeb reticulated vitreous carbon 68 ± 30 [54]
electrode at 0 V/AgAgCl
Garden compost Carbon cloth, 0.2 V/SCE 33.5 [85]
Garden compost Stainless steel foam at 0 V/SCE 100 [85]
Geobacteraceae dominated secondary Ag sheet anode at 0.2 V/AgAgCl 11 [9]
mixed culture from wastewater
Geobacteraceae dominated secondary Cu sheet anode at 0.2 V/AgAgCl 15 [9]
mixed culture from wastewater
Geobacter sulfurreducens Ice-templated titanium based ceramic anode, 88% porosity 128.7 [115]
Mixed culture Carbonized corn stem 31.2 [84]

DSA: Dimensionally stable anode.


SCE: Standard calomel electrode.

Glucose oxidase has been widely used in pacemakers, indicator mushrooms, have been evaluated as cathodes, showing a high
lights, small actuators, micro pumps, and other glucose electro- turnover rate, good stability and high selectivity [83,211]. Multi-
oxidizing anode-based systems, because of its thermostability enzyme based EFCs are generally preferred over single enzyme
and high selectivity [75]. Several enzymes are used on anode and systems so as to increase the substrate conversion and the perfor-
cathodes, based on their specific redox function. If highly selective mance of the system as a whole [118]. Many studies are now
enzymes are used at the anode and cathode, this eliminates the focusing on cascade of enzymes in FECs to facilitate complex
need of any membrane between the anode and cathode compart- mechanisms and 3-D electrode configurations to provide ample
ments. However, enzymatic catalysts are usually reported to surface area for enzymatic reactions. However, due to the utiliza-
oxidize the fuel partially and heat generation occurs as a result of tion of purified enzymes with catalytic capacity, the cost for EFCs
side reactions, which might be detrimental to the enzymatic ac- are still high.
tivity [118,132]. The shelf life of these enzyme-based systems has
been extended through encapsulation in micelle polymers that 2.5. Microbial solar cells (MSCs)
provide a buffering capacity for pH control and a hydrophobic niche
to prevent enzymatic degradation [118]. The flavin adenine Microbial solar cells (MSCs) make use of photoautotrophic
dinucleotide-dependent glucose dehydrogenases (FADGDH)/ microbes or higher plants to entrap solar energy which is further
Osmium (Os)-polymer-based electrodes showed high sensitivity utilized by electroactive bacteria to perform electrode-driven
towards glucose and also reported higher current densities, which reactions. These reactions include generation of electric current
made them suitable for use as bioanodes in glucose based EFCs or compounds like hydrogen, methane, ethanol, hydrogen
[211]. The Pyrroquinolinequinone-dependent alcohol dehydroge- peroxide etc. Primarily photosynthesis leads to the generation of
nase (PQQ-ADH), enzyme originating from acetic acid bacteria, has organic compounds, which are subsequently fed into the anode
been reported for the development of EFCs and biosensors, as it can compartment where they are oxidized by electroactive microbes
undergo quasi-reversible electrochemistry at an exposed carbon to produce electrons. These electrons are then transferred to the
surface [59,207]). This enzyme was reported to be capable of using cathodic side where reduction of oxygen leads to the formation of
different redox mediators and also has a good electron transfer water [46]. The phototrophic biofilms developed on the anode
kinetics [207]. Higher energy densities in combination with lower contain species of cyanophyta including Synechocystis, chlor-
power outputs make EFCs suitable for independently powering the ophyta and other electroactive microbes [182]. A system for
wireless sensor applications such as video monitoring and also for treatment of algal blooms in lakes has been reported based on
the development of other portable power devices [7,59]. The use of MSC principles, where algal biomass provided by Microcystis
FAD-dependent fructose dehydrogenase, obtained from Glucono- aeruginosa and Chlorella vulgaris was fed as a substrate in MFCs
bacter, as an anodic catalyst, and copper containing laccase from along with lake water, for concomitant power production and

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18 5

Table 2
An overview of power densities reported in MFCs in connection to cathode material.

MFC design Anode Cathode Maximum power Reference


density (mW m2
projected cathode)

MFCs with carbon paper, carbon cloth and similar anodes


Single chamber Toray carbon paper (without MEA with Pt catalyst; PEM-carbon 262 ± 10 [94]
wet proofing; E-TEK) clothes assemblies
Dual chamber Plain carbon paper Aqueous air-cathode; Carbon paper 33 (anode area based) [102]
with platinum catalyst
Single chamber Carbon cloth (type A, E-TEK) Air-cathode; Carbon clothes, PTFE 766 [24]
(diffusion layer)
Single chamber air-cathode Carbon cloth Double Cloth Electrode 4300 [50]
Assemblies (CEA)
3
Miniatured tubular MFCs Untreated carbon veil Air cathode; untreated carbon veil; 9.8 W m [203]
MFCs with granular graphite and similar anodes
3
Open air biocathode with granular graphite Sludge biocathode; graphite 83 ± 11 W m [29]
tubular MFC configuration felt with MnO2 total electrolyte
Dual chamber Graphite granules Aqueous air cathode without catalyst; 5.88 (nominal cathode [56]
granular graphite with nano pores surface area based)
Dual chamber Graphite granules Sludge biocathode; graphie fiber brush 68.4 W m3 anolyte [210]
Tubular air-chamber MFC Graphite felt and graphite granules MEA; Canvas cloth with Ni and 86.03 [221]
MnO2 coating
Tubular air-chamber MFC Graphite felt and graphite granules MEA/Canvas cloth with graphite 24.67 [221]
and MnO2 coating
Tubular air-chamber MFC Graphite felt and graphite granules b-MnO2 catalyzed air cathode 172 ± 7 [215]
Two chambered MFC Carbon granules anode; acetate Activated nitrogen-doped 1377 ± 46 [208]
fed mixed culture carbon fiber cathode
MFCs with carbon and graphite brush anodes
Tubular cathode in single Plain graphite fiber brush MEA/ultrafiltration membrane; 18 W m3 [222]
chamber configuration graphite coating with CoTMPP catalyst total electrolyte
Single chamber MFC Graphite fiber brush MEA; Ion exchange membrane-graphite 449 ± 35 [223]
coating and CoTMPP catalyst; AEM
Single chamber Graphite fiber brush treated Air cathode; stainless steel mesh 1610 ± 56 [213]
with ammonia gas and Nafion binder with diffusion layer
3
Two chamber MFC Carbon brush anode Crumpled graphene cathode 3.3 W m [205]
Single chamber MFC carbon fiber brush anode Goretex diffusion layered carbon 1330 ± 30 [108]
cloth cathode
Single chamber MFC carbon fiber brush anode; PTFE diffusion layered carbon 1390 ± 70 [108]
acetate fed mixed culture cloth cathode
MFCs with carbon felt anodes
Two chamber upflow MFC Carbon felt Aqueous air cathode; activated 315 (cross-sectional [40]
carbon fiber felt area of separator)
Tubular air-cathode MFC Graphite felt A tubular air-cathode; non-Pt; 175.7 [220]
continuous MFC stack with
swine wastewater
Single chamber MFC carbon felt anode Manganese dioxideegraphene nano 2083 [201]
sheet (MnO2/GNS) air cathode
MFCs with graphene coated anodes
Two chamber MFC Crumpled graphene anode Carbon brush cathode; 3.6 W m3 [205]
Two-chamber MFC Graphene coated stainless with Carbon cloth cathode with 2143 [70]
steel fiber felt anode; Acetate ferricyanide catholyte
fed mixed culture
Two-chamber MFC Graphene coated carbon cloth Carbon cloth cathode with 1018 [70]
anode (acetate fed mixed culture) ferricyanide catholyte

CoTMPP: Cobalt tetramethylphenylporphyrin.


MEA: Membrane electrode assembly.

water treatment [200]. The algal biomass from photo- electricity [109].
bioreactordafter the treatment in an anaerobic digester, can be
used as a feed for the fuel cell [38]. A MSC with a photobioreactor 2.6. Plant microbial fuel cells (PMFCs)
using Chlorella at the anode, reached a light to electricity con-
version efficiency of 0.04% resulting in 14 mW m2 of average Plant microbial fuel cells (PMFCs) incorporate the living
power density [182]. Without mediator or carbon source in the plant's root system into the MFC anode so that the organic
anolyte, Synechocystis PCC6803 was reported to produce products, called as rhizodeposits, released to the soil by the roots,
539 mA m2, under higher light intensity (10,000 lux) and can be used as substrate for electricity production by electro-
resulted on effective CO2 sequestration (625 mmol CO2 m3) active microbes [180]. Hence, in a broader sense, PMFCs harness
[109]. Improvement of performance is possible by photo- solar radiation by transforming it into green electricity in a clean
bioreactor optimization, improved chemical energy transfer from and efficient manner. The rhizodeposits from the roots mainly
algae to bioanode, higher surface electrode area and enriched comprise exudates (sugars, organic acids), secretions (polymeric
electroactive biofilm [181]. The advantages of this system lie on carbohydrates and enzymes), lysates (dead cell materials) and
simultaneous CO2 sequestration and direct conversion of light to gases [180]. The choice of a plant for PMFC is crucial, as it directly

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
6 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

Table 3
An overview of experimental conditions and performances of hydrogen producing MEC with mixed culture biocatalyst.

BES specifications and anode/cathode Hydrogen Current Electric Efficiencies and Reference
material production rate density energy input recovery in %
(m3 H2 m3 d1) (A m2) (kWh m3 H2)

A) Bioanode and abiotic cathode


Two chamber; Graphite felt anode; 0.1 0.447 NA 53 ± 3.5% overall efficiency [154]
TiePt cathode; 0.5 V applied voltage
Single chamber; Graphite brush anode; 3.12 11.6 NA 78% overall efficiency [11]
carbon cloth with Pt coating cathode;
0.8 V applied voltage
Two chamber; graphite felt forced flow 5.6 16.4 NA 43% overall, 71% [172]
through anode; PteTi mesh cathode; cathodic H2 recovery
1 V applied voltage
Cloth separator; carbon felt anode; 6.3 4.7 NA 90% COD recovery [188]
carbon cloth cathode with Pt coating;
1 V applied voltage
Two chamber; graphite felt; nickel foam; 50 22.8 2.62 90% cathodic H2 recovery [80]
1 V applied voltage
Single chambered cube MEC; Graphite 7.9 ± 0.3 33.28 4.7 ± 0.5 40 ± 1% overall efficiency [128]
brush anode at 0.2 V/AgAgCl; Pt coated
carbon cloth cathode
Single chambered cube MEC; graphite 6.9 ± 0.8 26.08 2.9 ± 0.4 54 ± 5% overall efficiency [128]
brush anode at 0 V/AgAgCl
Single chambered cube MEC;graphite brush 3.6 ± 0.6 14.6 2.3 ± 0.3 58 ± 6% overall efficiency [128]
anode at 0.2 V/AgAgCl
Single chamber; graphite fiber brush anode; 17. 8 26.14 NA ~80% overall efficiency, [25]
Pt coated carbon cloth; 1 V applied voltage 93% cathodic H2 recovery
Two chamber MEC with AEM; Carbon NA 10.2 2.62 90% cathodic H2 recovery [171]
felt anode; 1 V applied voltage
Wastewater feed 100 L reactor with 6 0.006 NA NA 48.7% energy recovery; [67]
MEC cassettes; 2 carbon felt anodes in 41.2% CE
each cassette; stainless steel wool cathode;
1.1 V applied voltage
Glycerol, milk and starch feed single chamber MEC; 0.94 150 A m3 NA 91% cathodic H2 recovery [126]
graphite fiber brush anode; Pt coated graphite
fiber cloth cathode; 0.8 V applied voltage;
enriched anaerobic sludge inoculum
H-type reactor; Spent yeast and ethanol fed MEC;; 2.18 ± 0.66 222 ± 31.3 NA 87 ± 2% COD recovery, [173]
Graphite fiber brush anode at 0.3 V/AgAgCl; A m3 71 ± 4% CE
Stainless steel mesh cathode;pig manure inoculum
B) Biocathodes and abiotic anodes
Continuous mode double chamber reactor; 0.63 1.2 NA 49% H2 recovery [157]
graphite felt cathode at 0.7 V/SHE
Continuous mode double chamber reactor; 2.2 2.7 50% H2 recovery [79]
graphite felt cathode at 0.7 V/SHE
Double chamber reactor; graphite granules 2.5 NA NA 2.5% H2 recovery [114]
cathode at 0.59 V/SHE; autotrophic biocathode
Double chamber reactor; plain carbon cloth 376.5 mmol 1.28 NA 70% H2 recovery [57]
cathode at 0.8 V/SHE; autotrophic m2 d1
thermophilic biocathode
Double chamber reactor; graphite plate cathode; 9.2 L m2 d1 1.88 NA 39.4% electron recovery as H2 [82]
autotrophic biocathode at 0.75 V/SHE
Single chamber PANI/MWCNT modified carbon 0.67 205 A m3 NA 81% energy efficiency, [21]
cloth biocathode; 0.9 V applied voltage 42% H2 recovery, 72% CE

NA: Information not available; PANI: Polyaniline; MWCNT: Multi-walled carbon nanotube; CE: Coulombic efficiency; COD: Chemical oxygen demand.

controls the amount of rhizodeposits for bioelectricity genera- 2.7. Microbial desalination cells (MDCs)
tion. Reed manna grass [180], rice plants [39] and Spartina anglica
[69] have been utilized in separate studies. PMFCs from Microbial desalination cells (MDCs) utilize the electric potential
Pennisetum setaceum have been reported to be the most sus- difference developed across the anode and the cathode via MFC
tainable in terms of power production so far, with a maximum technology to operate in situ desalination. Cao et al. [12] reported
power generation of 163 mW m2 [27]. S. anglica PMFCs with the first water desalination system in combination with MFC
integrated oxygen reducing biocathodes reached the highest technology. MDCs comprise an additional middle compartment in
long-term (2 weeks) power output of 240 mW m2 [202]. PMFCs between the anode and cathode compartments, for water desali-
along with MSCs having phototrophic biofilms are considered a nation. The middle compartment is partitioned by an anion ex-
promising and novel energy harvesting systems. It was also change membrane (AEM) towards the anode and a cation exchange
identified that the total amount of rhizodeposits available for membrane (CEM) towards the cathode. Bacteria on the anode
oxidation at anode is directly proportional to bioelectricity gen- oxidize biodegradable substrates and generate electrons and pro-
eration, rather than the photosynthesis process occurring in the tons; the electrons are externally transferred to cathode whereas

plant [191]. the anions (e.g., SO24 , Cl ) in the desalination compartment
migrate to the anode and the cations (e.g., Kþ, Naþ) are transferred

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to the cathode to maintain charge neutrality, thereby, desalination that could be generated in anaerobic digestion.
of the middle chamber solution occurs [12,106,107]. In MDC, the A prediction of the economic gain from the scaled up MFCs
migration of ions from the saline water in the middle chamber treating wastewater concluded that although electricity generation
towards the anode and cathode increases the conductivity of the will not rationalize the MFC operation, the organic waste removal is
anolyte and catholyte. Thus, electrical power production in MDC more attractive with this more sustainable technology [55]. In this
has been improved due to higher conductivity and mass transfer. context, it is more realistic to utilize wastewaters as the source of
However, the increased salinity of water could adversely affect the energy and materials for valuable chemical production in-situ in
anodic/cathodic bacteria as well as the effluent water quality from MEC/MESs [103]. Production of hydrogen or hydrogen peroxide in
MDC [107]. The MDC can be operated for simultaneous organic and MECs with wastewaters as the source of electrons is energetically
salt removal with power production or can be combined to the beneficial as compared to the production via conventional elec-
conventional reverse osmosis (RO) process as a pretreatment for trolysis or other means, because the energy contained in waste-
lowering the salinity of feed solution, and to decrease energy water is further used in the production of chemicals [103]. But as an
consumption. Studies have estimated that an MDC can generate up exception, in a comparative experimental study between MFC and
to 58% of the electrical energy needed by downstream RO systems MEC, Cusick et al. [34] showed that the treatment efficiency in
[76]. Jacobson et al. [76] compared RO systems that use 2.2 kWh terms of chemical oxygen demand (COD) removal and the energy
energy to desalinate 1 m3 of seawater with MDCs, that can produce recoveries in terms of kWh kg1-COD were higher for MFCs than
1.8 kWh of electric energy, with a net benefit of 4 kWh by treating MECs with winery and domestic wastewaters. Eventually, utiliza-
1 m3 of seawater. When an MDC is operated in electrolysis mode for tion of BES technology for the treatment and recovery of energy and
hydrogen production at the cathode, 180e231% surplus energy chemicals from lower value wastes may become environmentally
than the input electricity can be recovered as H2, with the added and economically beneficial. An estimate of hydrogen production
advantage of water desalination [106,117]. cost of $4.51/kg-H2 from winery wastewater and $3.01/kg-H2 from
domestic wastewater was reported when both wastewaters were
3. Wastewater treatment in BES treated in MEC; these costs of hydrogen production were less than
the estimated market value of hydrogen ($6 kg1-H2) [34].
Bioelectricity generation has been the primary outcome from
the MFC technology. Apart from this, several other advantages are 4. Recalcitrant pollutants degradation in BES
associated with BES technology. Wastewater treatment is one of the
most important applications of BES. Current processes for biolog- 4.1. Dye decolorization and removal
ical treatment of low concentrated wastewaters are based on the
energy intensive conventional technologies which are not envi- Azo dyes, most of which are xenobiotics, contain one or more
ronmentally friendly. New approaches of wastewater treatment azo groups (-N]N-), and are the most widely used synthetic dyes
enabling substantial energy recovery are the most effective way to in textile, leather, cosmetics, plastics and food industries. Industrial
compensate the huge amount of energy consumed in conventional wastewaters containing dyes creates environmental problems due
wastewater treatments. BES associates the benefit of wastewater to their persistent colors which spoil the aesthetic values and
treatment from diverse origin and energy and resource recovery causality to toxic effects [127,193]). The contamination of azo dyes
through the production of bioelectricity or other valuable products in surface water hampers light penetration and decreases the
[133]. Conventional activated sludge process in domestic waste- amounts of dissolved oxygen, thereby threatening the aquatic life.
water treatment needs 0.3 kWh m3 for aeration and about twice of Studies have shown that azo dyes are toxic and mutagenic
this amount of energy for the pumping and other purposes [116]. [164,192]. Dyes are designed to be chemically and photolytically
Energy can be recovered from domestic wastewaters via anaerobic stable and are also not easily degradable to natural microbial action.
conversion of organic components to methane. But only a portion Due to their complex chemical structures, the decolorization of
of the potentially available energy is recovered through the com- these wastes is a challenging task. A range of physicochemical
bined anaerobic digestion and conventional aerobic wastewater treatments exists to decolorize effluents containing dyes. Namely,
treatment. The energy contained in the dissolved organic fraction is (i) chemical treatments like ozonation [31], alkalinisation etc.; (ii)
lost in the aerobic oxidation processes. If anaerobic digestion is physical treatments like adsorption, flocculation-coagulation etc.;
used in place of an aerobic process (activated sludge treatment), (iii) photo degradation; (iv) membrane processes [111] and (v) a
energy recovery as methane is possible but still the requirement of few biological treatments [89] can effectively decolorize the in-
concentrated waste stream >3 kg m3 organic load and the main- dustrial wastewaters. But these techniques are generally very
tenance of warmer temperatures >20  C are the main limitations expensive because they require large amounts of chemicals and
[103]. Also very large digesters are required to make the process additionally produce considerable amounts of sludge.
economical. Due to these reasons anaerobic digestion is applied Bioelectrochemical systems are successfully proven to decol-
only to treat the sludge from wastewater and high strength orize the dyes [33,127,186]. The range of the half-cell potentials for
wastewaters, but not low strength wastewater. When BESs are used the reduction of azo dyes to their constituent aromatic amines was
for treating the wastewater, only small amounts of solids (sludge) reported to be between 530 and 180 mV versus the standard
are produced. Therefore, there is no need of additional sludge hydrogen electrode (vs SHE) [193]. Sun et al. [186] carried out the
management and treatment strategies. Direct electricity generation decolorization of active brilliant red X-3B (ABRX3) utilizing the
from wastewaters in MFC can attain high energy efficiencies due to electrons generated from the biodegradation of readily biode-
the absence of carnot cycle limitations in power generation unlike gradable organic matter at the anode of air-cathode single-chamber
in combustion processes [103]. However, the energy recovery from MFC with concurrent bioelectricity generation. Glucose and con-
BES still remains low. Power densities produced in MFCs using only fectionery wastewaters were found to be suitable co-substrates for
domestic wastewater has attained up to 12 W m3 [65] which is ABRX3 decolorization. ABRX3 decolorization was significantly
equivalent to 0.07 kWh m3 produced over 6 h (6 h is typical improved in MFCs as compared to conventional anaerobic treat-
activated sludge treatment time). However, this energy recovery is ment. Mu et al. [127] used BES to decolorize acid orange 7 (AO7)
still low as the organic waste in domestic wastewater can poten- abiotically in the cathode, using acetate as the electron donor at the
tially produce up to around 2 kWh m3 based on the methane gas bioanode. AO7 decolorization rates up to 2.64 ± 0.03 mol m3 d1

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electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
8 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

Fig. 2. Possible mechanism of Acid Orange 7 reduction in bioelectrochemical systems. “Adapted with permission from (Mu et al. [127] Copyright (2009). American Chemical
Society.”

were achieved with simultaneous power generation, whereas the recalcitrant organochlorines. Improper handling and disposal of
decolorization rate was enhanced five times when power was industrial solvents and degreasing agents such as per-
supplied to the BES maintaining the cathode potential at 400 mV chloroethene (PCE) and trichloroethene (TCE) contaminate the
(vs SHE). The identification of decolorization products suggests the soil and groundwater. The physico-chemical technologies to treat
cathodic reaction mechanism depicted in Fig. 2. these subsurface pollutants are normally very expensive. Natu-
Alizarin yellow R (AYR) was decolorized in a dual-chamber BES rally existing anaerobic microorganisms can decay and detoxify
with a biocathode of enriched autotrophic biodegrading inoculum the chlorinated pollutants via in situ bioremediation processes
[33]. Within 48 h of operation under the optimized condition of pH and restore the contaminated soil and groundwater effectively
5.2, and 0.5 V of supplied voltage, the decolorization efficiency was and inexpensively [105]. A brief list of the removal of organo-
as high as 99.2% (from initial concentration of 100 mg L1), which chlorines through different types of BES, is overviewed in Table 4.
was higher than the efficiency obtained from abiotic and mixed Anaerobic bacteria can dechlorinate chlorinated aliphatic hydro-
sludge-inoculated biocathode operations. carbons (CAHs) in groundwater, by using them as terminal elec-
tron acceptor for microbial respiration [165]. Incomplete
4.2. Organochlorine removal dechlorination of PCE and TCE to the interemediate cis-
dichloroethene (cis-DCE) and then to vinyl chloride (VC) gener-
Organochlorines are organic compounds containing at least ally occurs in halorespiration. VC is a singly chlorinated ethene
one covalently bonded chlorine atom. Many derivatives of or- and a known carcinogen. Chlorinated compounds (PCE, TCE and
ganochlorines persist in the environment and have been found cis-DCE) reducing microorganisms compete for electrons in ace-
toxic to plants and animals, including humans. Industrial chlori- tate and hydrogen intermediates with sulfate, iron (III), and CO2
nated solvents, bleaching and preservative agents and chlorine- reducers [165]. Generally hydrogen (H2) is considered as ultimate
containing pesticides are the main anthropogenic source of electron donor for reductive dechlorination by Desulfitobacterium

Table 4
BESs for dechlorination of trichloroethene and other chlorinated compounds.

Compound BES Electrode Operating mode Removal rate Reference


(mol m3d1)

Trichloroethene Mediator- Methyl Viologen Glassy carbon cathode, Batch fed 0.001 [2]
platinum disk anode
1
Trichloroethene Direct graphite electrodes Batch 25 mmol d [184]
Trichloroethene Direct Carbon paper [1]
Trichloroethene Undetectable mediator Glassy carbon cathode, Batch fed 0.002e0.004 [3]
platinum disk anode
Trichloroethene Direct Graphite cathode 64 ± 2 mmol L1 d1 [4]
4-chlorophenol MFC; acetate in anode, Carbon fiber anode Batch fed 0.3 [61]
4-chlorophenol in and cathode
abiotic cathode
1,2-dichloroethane MFC; Dichloroethane in anode Graphite plate Recirculated 0.061e0.068 [138]
Ferricyanide in cathode anode and graphite anode and batch
granule cathode fed cathode
2-chlorophenol MEC acetate in anode, Graphite granule anode Batch fed 0.04 [183]
2-chlorophenol in biocathode and cathode

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S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18 9

spp and Dehalococcoides spp. [43,96,209]. But acetate and H2, parallel, power can be generated [62,145]. As per the reactions
solely or in combination, were identified as key electron donors mentioned in Eqs. (1) and (2) and also according to Fig. 3, sulfate
to stimulate anaerobic microbial dechlorination of chloroethenes was biologically reduced to sulfide which was then catalytically
to ethene at the chloroethene-contaminated site [66]. When ac- oxidized to sulfate using different anodes such as a metal
etate or H2 alone was the electron donor, syntrophic acetate- hydroxide-modified graphite [62], charcoal [32], graphite foil, car-
oxidizing species or H2/CO2 acetogens respectively were present bon fiber veil and activated carbon cloth [219]. In these studies,
as the co-culture. Certain dechlorinating bacteria were discovered oxygen was reduced at the air-cathode to maintain the electron
to be able to accept electrons directly from polarized graphite flow through the external circuit.
electrodes to sustain the dechlorination process [1,184]. These
findings have led to the development of BESs for groundwater D:desulfuricans Anode
Sulfate ƒƒƒƒƒƒƒƒƒƒƒƒ! Sulfide ƒƒƒƒƒƒƒƒƒƒƒƒ! Sulfate
remediation. TCE-dechlorinating bacteria can directly gain the Biocatalytical reaction Electrochemical reaction
required electrons from a negatively polarized carbon paper (1)
electrode [1]. Aulenta et al. [4] investigated the performance of
TCE dechlorination in bioelectrochemical reactor operating for Paracoccus spp Paracoccus sppþanode
about 570 days at different cathode potentials ranging ƒ! Sulfide ƒƒƒƒƒƒƒƒƒƒ! Sulfur
Sulfate ƒƒƒƒƒƒ (2)
from 250 mV to 750 mV vs SHE. At a cathode potential Rabaey et al. [145] reported sulfide and sulfate removal from the
of 250 mV vs SHE, methanogenesis was almost suppressed and wastewater, as solid sulfur accumulation on the granular graphite
94.7% of available electrons were accounted for dechlorination, anode of the MFC, with the ferricyanide redox couple for the
whereas at the cathode potential below 450 mV vs SHE, a cathodic reaction. The biocatalysts identified in this anaerobic
higher TCE dechlorination rate up to 64 ± 2 mmol L1d1 was oxidation of sulfide were Paracoccus species. In this process, sulfide
achieveddbut simultaneous methanogenesis was reported was shuttling the electrons between the bacteria and anode, un-
consuming about 60% of electric current [4]. BES for dechlorina- dergoing an oxidation to insoluble elemental sulfur. In the tubular
tion has shown stable and reproducible performance even in the MFC with air-cathode, at most 514 mg sulfide L1 day1 (unit
absence of organic carbon sources confirming long-term direct normalized to net anodic compartment volume, NAC) was removed
exocellular electron transfer [1,4]. Studies have also been carried via biocatalytical oxidation to elemental sulfur that resulted elec-
out to demonstrate the dechlorination of other chlorinated tricity generation which accounted maximum power outputs of
compounds in the BES including the dechlorination of chlor- 101 mW L1 NAC [145]. Activated carbon cloth was identified as a
ophenols and 1,2edichloroethane [74]. superior anode material for sulfide oxidation to sulfate, when
compared to graphite foil and carbon fiber, and it enabled to extract
4.3. Sulfide removal higher electric power density (0.51 mW cm2) in the batch mode
operation of a single-chambered, air-cathode MFCs, using sulfate-
Organic wastes and wastewaters generated from many pro- rich solutions [219]. Oxidation of solid sulfur to sulfate requires a
cesses ubiquitously contain sulfur compounds. Biological conver- high positive overpotential, whereas sulfide can be oxidized to
sion of sulfur compounds in the wastewaters by sulfate reducing elemental sulfur when the anode potential is controlled at or
bacterial releases sulfides, which are toxic, odorous and corrosive. above 0.27 V (vs SHE) in aqueous solutions at neutral pH (Fig. 3).
Sulfate reducing bacteria like Desulfovibrio desulfuricans are In the sulfide removing MFCs, elemental sulfur and/or soluble
commonly found in the wastewaters containing high organic load. polysulfide species were the dominant sulfide oxidation products
Treatment of sulfate-rich wastewaters with biological sulfate in the anode chamber [219].
reduction processes is a well-known effective method but the
treatment process is limited due to the generation of sulfides and
other sulfur-based gases which inhibit the bacterial metabolism 4.4. Chromium removal
and even cause the failure of the process, associated to the corrosive
and toxic nature of the sulfides [219]. MFCs can be used to remove Reduction of hexavalent chromium Cr(VI) at the cathode of
sulfides by oxidizing them electrochemically at the anode and, in MFCs has high utility in the bioremediation of Cr(VI) contaminated

Fig. 3. Pathways of sulfide/sulfate removal in MFCs. Reactions 1 is biological metabolism in sulfur reducing bacteria (SRB); Reactions 2 and 3 are chemical in nature.

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electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
10 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

sites, as the technology has low cost of operation, self-regenerating produced a surplus energy of 3.46 kJ gN1 which was more than the
ability and also provides a sustainable power supply [74]. Cr(VI) can required energy for the ammonium recovery by stripping [90].
be electrochemically or biocatalytically reduced to less toxic, less
soluble and less mobile trivalent chromium Cr(III). Acidic envi-
6. Production of chemicals in BES
ronment is required at the cathode for the electrochemical Cr(VI)
reduction in abiotic condition [199]. Several bacterial species of
6.1. Hydrogen
Bacilli and Clostridia as well as a number of proteobacter species
such as Pseudomonas dechromaticans, Escherichia coli, Desulfovibrio
Wastewaters from industrial, agricultural and municipal sources
vulgaris, Shewanella oneidensis, Aeronomas dechromatica and
contain large amounts of dissolved organic matter that are a po-
Enterobacter cloacae were reported to catalyze Cr(VI) reduction
tential resource for chemical and fuel production [155]. Biological
whenever a suitable carbon source like acetate was available to the
treatment technologies are known for the production of energy
biocatalysts [18,187]. The reduction of Cr(VI) was also attained in an
from wastewaters. Methanogenic anaerobic digestion has already
air-bubbling-cathode MFC in which the electrochemical reduction
been used worldwide for the production of biogas (a mixture of
of oxygen to H2O2 strongly favored the reduction of Cr(VI) [95].
methane and CO2). Hydrogen production from wastewaters by
Improvement to the biocathode for Cr (VI) reduction and electricity
acetogenic fermentation is another method of utilization of
generation was reported by [73] using tubular MFCs in which the
wastewaters [120,121]. However, low yields and thermodynamic
cathode to anode surface area ratio of 3:1 was maintained. Specific
limitations in microbial metabolism exist in the fermentation
rates of Cr(VI) reduction between 12.4 and 20.6 mg g1 volatile
process. BESs offer an alternative technology to upgrade the
suspended solid (VSS) h1 were achieved with power generation
hydrogen yield at a relatively low electric energy input when
from 6.8 to 15 W m3 using a graphite-fiber as cathode support for
compared to conventional water electrolysis; more specifically,
the biocatalyst. The graphite fiber biocathode showed better per-
MEC mode of operation has shown promising rates of hydrogen
formance for chromium reduction when compared to graphite felt
production. This technology is also termed as bio-
or graphite granules [73]. The rate of Cr(VI) reduction and elec-
electrohydrogenesis [97,136,152,156]. Hydrogen is extensively
tricity generation in MFCs were affected by various physicochem-
used both as chemical and fuel, in various industrial processes such
ical and biological conditions, like pH, redox mediators and the
as upgrading fossil fuels and saturating fats, hence H2 has unique
bacterial electrochemical activity. In addition, the anode potential,
values compared to methane. On COD basis, H2 production from
electrode materials and reactor configurations also influenced the
wastewater is 7 times more valuable than methane produced from
efficiency of the Cr(VI) reducing biocathode [74].
the same amount of wastewater [155]. H2 production in MEC can be
done from various organic sources, including waste materials as
5. Metal and nutrient recovery in BES
well as non-fermentable substrates [98]. Principally, bacteria
oxidize organic compounds typically, acetate and generate CO2,
Application of MFCs has not been limited only to the wastewater
electrons and protons at the anode of an MEC. The electrochemical
treatment and electricity generation, it has also expanded to
interaction of bacteria transfers the electrons to the solid anode.
electricity-driven production of number of value-added compounds
With an external voltage, the electrons flow to the cathode where
such as H2, acetate, etc. at the cathode [63]. MFCs have also been
they combine with protons to form hydrogen gas (Eqs. (3) and (4))
applied for the removal and recovery of metals from leachates and
[99]. For charge neutrality, the protons migrate from anode to
effluents from mining and metallurgical processes that would pref-
cathode in the solution. In practice, an applied voltage of >0.2 V is
erably result in the recovery of metals especially copper for (re-)use in
required for H2 production in MEC, which is less than the typical
industries [63]. A subsequent study by Ter Heijne et al. [68] demon-
voltage (>1.6 V) required for water electrolysis [98,99]. A mem-
strated the electrochemical reduction of copper at cathode, using
brane separates the anode and cathode chamber to avoid the
bioelectrochemical acetate oxidation at the anode. In this bio-
mixing of the substrate and product. The reactions that occur in a
electrochemical process, a bipolar membrane (BPM) was used for
MEC with acetate as substrate are as below.
simultaneous bioelectricity generation along with copper reduction/
removal at the cathode. The reduced copper was plated onto a flat
At anode : CH3 COO þ 4H2 O/2HCO 
3 þ 8e þ 9H
þ
(3)
plate graphite electrode at a current density of 3.2 A m2. Further
studies accomplished higher current densities in the range of 0.9e7
A m2 along with copper removal by using a larger anode surface than At cathode : 8Hþ þ 8e /4H2 or 8H2 O þ 8e /4H2

the cathode surface [119,212]. Zhang et al. [214] validated the recovery þ 8OH
of vanadium (V) and chromium (Cr) in dual chambered MFCs by
(4)
employing vanadium and chromium-containing wastewater as the
cathodic electron acceptor with simultaneous bioelectricity genera- Theoretically, hydrogen formation at the cathode occurs after
tion. The maximum power density of these MFCs was 970 mW m2 overcoming the endothermic barrier of 0.414 V vs SHE by
and showed enhanced electrode reduction efficiency by using the two applying only a small external voltage difference of 0.14 V to the
electron acceptors V5þ and Cr6þ together [214]. MEC, the oxidation reaction carried out by the anodic bacteria can
Apart from metals, nutrient recovery was also observed with supply the remaining overpotential (0.279 V) [98,154]. Concom-
MFCs. Particularly, successful ammonium (NHþ 4 ) recovery from itant wastewater treatment and H2 production in MEC is an effi-
urine was demonstrated by Kuntke et al. [90]. The electrons required cient approach to generate clean energy. The utilization of a wide
for the migration of NHþ 4 from anode to cathode are generated by the range of organic compounds by exoelectrogens in MECs makes it
anodic bacteria from the oxidation of organic matter. At the cathode, sustainable and economically advantageous. However, the
diffusion of ammonia (NH3) promotes the total ammonium trans- hydrogen evolution reaction (HER) occurs very slowly on carbon
ported to the cathode. Due to the localized high pH prevailing in the cathodes of MEC and need to overcome a high endothermic po-
cathode, NH3 stripping occurs and thus improves the transport of tential barrier (overpotential). To reduce the overpotentials, plat-
ammonium. The ammonium recovery rate and current density were inum (Pt) has been used as the catalyst. Electrodes with different
registered as 3.29 g-N d1 m2 (vs membrane surface area) and 0.50 amounts of platinum loadings are commercially available and also
A m2 (vs membrane surface area), respectively and the process prepared in laboratory. Titanium with platinum coating is used as

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electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18 11

cathode to avoid the overpotentials. However, platinum based reduction reaction. In addition, the cathodic or applied potential
electrodes are very expensive. Cathodes made from cheap non- that breaks the thermodynamic barrier of a biological reaction
noble metals like stainless steel, nickel (Ni) or nickel alloys have should be applied for a successful reduction reaction in MES.
also been tested for H2 production in MEC [71,110,162,163]. Nickel Homoacetogenic bacteria can efficiently convert CO2 to acetate,
and Nickel Molybdenum (NiMo) electrocatalysts have shown good which is a major intermediate molecule for the production of bio-
results with only a slightly larger overpotential than platinum chemicals [8]. Thermodynamically, the conversion of CO2 to acetate
[72,156]. By increasing the specific surface area of the Ni cathodes, requires 280 mV vs SHE cathodic potential. However, under
the cathode overpotential was lowered and high hydrogen pro- practical conditions a much lower potential is required to overcome
duction over 50 m3 m3 MEC d1 was attained [80]. the potential losses due to the microbial energy uptake and mass
It has been shown that bacteria can also catalyze the HER at and charge transfer resistances involved in bioelectrochemical
biocathodes [78,157]. Studies have focused on the upscaling and system. Apart from the above factors, several other underlying
improvement of H2 production in MEC by finding good performing factors such as electrode materials, reactor design, mediators in
cathodes materials. A bench scale 4 L MEC reactor using stainless electron transfer influence the overall process efficiency [41]. At
steel as cathode produced 0.9 m3 H2 m3-MEC d1 which had present the MES technology is at its infancy, therefore current
graphite felt as anode to treat acetate-containing saline wastewater studies are mainly focused on fabricating new proofs of concept.
[13]. An overview of the performances of H2 producing MECs along
with their operating conditions is presented in Table 3. Although 6.3. Methane
the applied voltage controls the electric current, the current den-
sities reported in MECs increased with the specific surface area of Methane generation from anaerobic digestion of organic sub-
electrodes. Higher current densities are reported with larger spe- strates has long been in practice and it is considered as a renewable
cific surface anodes like carbon felt and graphite brush anodes process. Still, to improve the sustainability of the methane gener-
(Table 3). Likewise, the production at the cathode of MEC is also ation process, recycling of the CO2 generated from various biolog-
enhanced by increasing the cathode surface area. Generally, metal ical processes can be integrated to produce more methane through
catalysts, like Pt and Ni are used for higher hydrogen production. microbial electrosynthesis. Microbial electrosynthesis of methane,
also known as electromethanogenesis, can proceed at lower tem-
6.2. Acetate peratures than anaerobic digestion. The specialty of electro-
methanogenesis through MEC is that the organic matter present in
MES took another approach to fix CO2 in multi-carbon com- wastewater can be treated and at the same time methane pro-
pounds such as liquid fuels or chemicals by electricity-driven duction is achieved. This process provides more advantages than
reduction reactions. This application is considered as a technol- traditional methanogenesis in terms of higher methane yield and
ogy for the storage of electrical energy in the CarboneCarbon bond utilization of the effluents issued from anaerobic digestion pro-
of value-added chemicals [130]. demonstrated the first proof of cesses [30,197].
microbial electrosynthesis using the acetogen Sporomusa ovata that Clauwaert and Verstraete [30] showed bioelectrochemical
could use electrons directly derived from a graphite cathode for the methane production using a single chamber configuration in MEC
reduction of CO2 to produce acetate and small quantities of 2- mode, using plain graphite as electrode. An applied potential
oxobutyrate [130]. Electron recovery in these products was more of 0.8 V (vs SHE) was employed, reporting a maximum methane
than 85% of the electrons transferred at the cathodes. Subsequent production rate of 0.75 ± 0.12 L L1-MEC d1 from 4.13 kg m3-
studies demonstrated the process of CO2 reduction using MES with MEC d1 COD loading with 86 ± 14% of acetate to methane con-
a wider range of microorganisms [129]. These studies showed the version, whereas without voltage application only 0.17 ± 0.06 L L1-
ability of other acetogenic bacteria, including Sporomusa silvacetica, MEC d1 of methane were generated at a COD feeding of
Sporomusa sphaeroides, Clostridium ljungdahlii, Clostridium aceticum 1.38 kg m3-MEC d1 with 47 ± 17% of acetate to methane con-
and Moorella thermoacetica to reduce CO2 to acetate, 2-oxobutyrate version. Treatment of anaerobic digestion effluents in a single
and formate. Electron recoveries in acetate and 2-oxobutyrate were chamber MEC with methane production was prospected as a viable
accounted for 84%, 48 ± 6%, 82 ± 10% and 53 ± 4% in S. silvacetica, technology for efficient waste treatment [30]. Sasaki et al. [161]
S. sphaeroides, C. ljungdahlii and C. aceticum respectively. Gong et al. focused on the use of a membrane-less configuration under a
[60] showed that sulfide can be used as electron donor at the anode working potential of 0.395 or 0.595 V (vs SHE) at neutral pH and
for microbial electrosynthesis. The study used a sulfur oxidizer, demonstrated efficient methane production. It was observed that
Desulfobulbus propionicus, at anode as a biocatalyst to oxidize the dominating methanogens on the cathode were different from
elemental sulfur to sulfate. The electrons generated in biotic anode those grown in control reactors with no electrochemical reactions
were used for CO2 reduction to acetate growing S. ovata on a [161].
graphite cathode. Marshall et al. [113] showed the improvements in In the scalability studies on MEC with multi-electrode configu-
rate of acetate production by CO2 reduction using mixed microbial rations for H2 production using acetate as substrate Rader et al.
communities termed as microbiomes. Jiang et al. [81] used a biotic [146], reported that the methanogenesis rates increased gradually
cathode of mixed culture of that accepts electrons from the anode with time. After 16 days of operation, the system showed little H2
and produced H2 abiotically to fix CO2 into methane and acetate. production but a subsequent CH4 production with good substrate
Bioelectrochemical CO2 reduction with electron capture efficiency conversion efficiency, showing that electromethanogenesis became
of 97% was reported controlling the cathode potential the predominant process at the biocathode, when operated with
below 950 mV vs NHE [81]. Marshall et al. [114] demonstrated effluents from dark fermentation and anaerobic digestion processes
improved performance of microbial electrosynthesis for acetate [146].
production at the highest rate of 1 g L1 d1 by autotrophic A biocathode dominated by Methanobacterium palustre was
microbiomes when operated for long term. Furthermore, the long shown to successfully reduce CO2 to methane, in combination with
term adaptation resulted into a stable and resilient biocathode. an abiotic graphite anode through a mediator-less mechanism
The conditions of the MES process must be created to allow the (kind of direct electron transfer) [26]. The thermodynamic con-
optimal metabolism of biocatalyst present at the biocathode. A straints of methane production from CO2 reduction, predict a
suitable terminal electron acceptor should be available for the cathodic potential requirement of 0.244 V vs SHE at standard

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
12 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

biological conditions. Practically, a wide range of applied cathode be highly cost-effective in comparison with the conventional sen-
potentials (i.e. between 0.5 and 1.0 V vs SHE) have been re- sors, as it can be built on low cost carbon-based materials. In MFC
ported for electromethanogenesis [22,26,196]. Cheng et al. [26] based biosensors, oxidation of organic matter in the inflow feed
demonstrated electromethanogenesis in combination with abiotic was catalyzed by the bacteria growing on the anode and produce
and biotic anodes and also with dual chamber and single chamber electrons giving an electrical signal. The electrical signal generated
combinations. Methane production with 80% overall efficiency by the MFC is associated with the rate of metabolic activity of the
(electrical energy þ substrate enthalpy) at 0.8 V vs SHE cathode in biofilm at the anode [42]. Any disturbance in the bacterial activity is
a single-chamber MEC was reported, with an anodic biofilm interpreted into a change in the electric current. When toxic
growing on acetate. In a double-chamber BES with an abiotic anode compounds are present in the feed water, the bacterial activities
[26] achieved 4.5 L m2 d1 of methane production with 96% en- will be affected, which can be detected in the variation in electrical
ergy/coulombic efficiency, controlling the cathode at 0.8 V vs SHE. signal. This extent of change in electric current was shown to be
Compared to conventional methanogenesis, the advantage of bio- directly associated to the specific disturbance imposed to the bio-
electrosynthesis is the physical separation of the oxidation of anode when other operational parameters of MFC such as pH,
organic waste from methane production, which protects the temperature and conductivity of the feeding solution were kept
methanogenic consortia from the inhibitory compounds that can constant [185]. MFCs were highly sensitive with regards to many
be present in the waste stream, and CO2 can be recycled for compounds present in the feed water. Hence, it can be used as an
methane production. Villano et al. [195,196] used mixed meth- early warning signal. In MFC based biosensors, transducers were
anogenic cultures as cathodic biocatalysts in dual chamber not required to translate the signal to a readable one as the bacterial
configuration to produce methane from CO2 at several applied growth on the anode directly produce measureable electrical signal
cathode potentials between -0.65 V to -1.0 V (vs SHE). from the sensing element. The application of MFC as biosensor for
BOD and toxic contaminants in water has been separately discussed
6.4. Other chemicals as in the following sections.

In recent studies on BESs, the production of value-added 7.1. BOD sensors


chemicals and fuels other than acetate, methane and hydrogen
has been highlighted [103,144]. Valuable products such as BOD has been used as a basic parameter to quantify the extent of
hydrogen peroxide and caustic soda were produced at the metallic organic contamination in the water systems. The electronic charge
cathode of MEC by applying external electric potential and at the generated from a mediator-less MFC is in good positive correlation
concomitantly achieved improved performance efficiency for to the concentration of organic matters. So, MFCs have been
wastewater treatment [25,142,158]. Electrosynthesis of fuels such investigated as BOD sensors [16,17,87]. Chang et al. [16] continu-
as methanol has long been reported from the electrochemical ously monitored the BOD of sample water on-line using an MFC, by
reduction of CO2 using metal catalysts like copper [5] but the measuring the electric current in amperometric mode. BOD values
process is energy intensive and not sustainable. In this context, of up to 100 mg L1 were in good linear fit with the electric current
microbial electrosynthesis could be a less energy intensive and generated. An extrapolation of the fitted model can be used to
sustainable solution for electricity-driven fuel and chemical pro- measure higher BOD values [16,17]. MFC as a BOD sensor can
duction. In recent studies, small amounts of ethanol and butyrate operate with stable performance for over 5 years with minimum
production have been reported as secondary products in MES, from maintenance service [16]. A performance overview of MFC-based
CO2 reduction using lithoautotrophs [6] whereas the heterotrophic BOD sensors is presented in Table 5, along with the operational
production of ethanol from acetate as substrate has been demon- characteristics of the MFCs. In all of the literature mentioned in
strated at the cathode of BES [179]. Most of the MES studies on CO2 Table 5, inoculation of the anode with mixed bacterial cultures is-
reduction reported H2 evolution at the cathode as a mediator for sued from wastewater was carried out to widen the variety of us-
the microbial CO2 reduction [6,81,114]. As an alternative to H2- able substrates and also for long-term performance stability. The
driven MES for CO2 fixation, an innovative strategy has been sug- quickest response time of MFC-based BOD sensors was 2.8 min for a
gested that uses formic acid (HCOOH) as an energy carrier [175]. scaled-down single chamber MFC and the response-time varied
Formic acid production from CO2 and water by bioelectrochemical with the reactor design [42]. Table 5 shows that the most recent
reactions, and its further conversion to isobutanol by engineered studies have improved the BOD detection range and response time
Ralstonia eutropha was demonstrated [91]. The R. eutropha strain of MFC based sensors.
was engineered to divert the usual poly-hydroxybutyrate synthesis
pathway to produce liquid fuel and also made it able to withstand 7.2. Toxicity sensors
electric current. The metabolically engineered strain was also used
for the conversion of CO2 to ethanol [131]. Xafenias et al. [204] MFC-based toxicity sensors was first demonstrated by [88]
showed increased 1,3-propanediol titers using a mixed-culture as which showed the variation in the electrical current in response
biocatalyst, with glycerol as a substrate. Along with the all the to the presence of contaminants such as heavy metals, like Pb and
above discussed products, few reports are available on the pro- Hg, organophosphorus pesticides (e.g. Diazinon) and poly-
duction of butanol, acetone and succinate through MES processes chlorinated biphenyls (PCBs) in the water samples. Principally, the
[58,166]. substrate consumption rate and the microbial activity in MFC bio-
sensors are directly linked to the electric current generated. A
7. BES based biosensors decrement in electric current under the exposure to a toxin, when
all of the operational conditions remain same, is an indication of
MFC technology can be applied for the easy and fast testing of toxic inhibition. An effect of toxic components on the
the water quality. MFC based biosensors have been proposed in electrochemically-active bacteria has been shown by a shift in the
recent studies for the detection of toxic compounds and for the polarization curves, specifically a doseeresponse relationship for
measurement of biochemical oxygen demand (BOD) of water nickel was visualized in the polarization curves [178]. A higher
samples. MFCs have the potential advantage for on-site and real- concentration of contaminant leads to a lower current at all over-
time monitoring of water quality [16,17]. MFC technology can also potentials [177,178]. MFC-based biosensors studied for the

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18 13

Table 5
Overview of performance, design and functional characteristics of MFCs used as BOD sensors.

Source of inoculum Anode Configuration Detection range Saturation signal Response time References
(BOD5, mg L1)

Enriched consortium (waste water) Graphite felt Two chamber 2.58e206 1.1 mA 0.5e10 h [87]
(based on charge)
Consortium (activated sludge) Graphite felt Two chamber 23e100 6 mA 1h [16]
Consortium (primary clarifier) Carbon paper Two chamber 10e250 233 mA m2 40 min [218]
Consortium (from an active MFC) Carbon cloth Single chamber 3e164 35 mA 2.8e8.7 min [42]
(air breathing cathode)

Table 6
Overview of the reactor, performance and functional characteristics of MFCs used as toxicant sensors.

Source of inoculum Anode material Toxicant-detection range (mg L1) Baseline signal Response time References

Mixed culture (Activated sludge) Graphite felt Diazinon:1e10 0.04 mA 20 mine2 h [88]
Pb: 1e10
Hg: 1e10
PCBs: 1e10
Mixed culture (active MFC) Graphite plate Cu2þ: 85 1.37 A m2 50e100 min [176]
Geobacter sulfurreducensn Ti/Ni/Au tri-layer Formaldehyde 0.1%e4% 4 mA cm2 <5 min [36]
Mixed culture (active MFC) Graphite plate Ni: 10 2.25 mA 30 min [177]
Mixed culture (waste-water) Carbon cloth Cr6þ: 1e8 0.10e0.12 V 5 min [92]
Fe3þ: 1, 8, 48
NO3 : 1, 8, 48
Mixed culture (active MFC) Carbon cloth Cd2þ 0.1e100 mg L1 32.2 mA 12 min [42]

detection of toxic components in water which are summarized in and difficult to identify.
Table 6. Table 6 shows that the lowest detection limit of the MFC The above stated limitations were generally established for
biosensors was 1 mg L1 for heavy metals like Pb, Hg, Cr and even MFC technologies in which only one biological component is
100 mg L1 for Cd, while the upper limits of detection were not present, whereas in the case of biocathodes, plenty of limitations
assessed within the short range of concentrations employed. are typically associated beyond the anodes. Reduction of over-
It has been established that MFC based sensors could be sen- potentials and high coulombic efficiencies often remain the main
sitive to the target compounds with the detection limits lower technological challenges of BES to solve in future applications.
than 1 ppm, and can be operated for long time with stable per- Upscaling the production at industrial scale is also found as the
formance. However, a few key constraints of MFC-based bio- major limiting step for BES technologies. Stacking up the number
sensors have to be addressed for full scale installation of this of MFCs and integration of number of electrodes in a single sys-
technology. These constraints are low selectivity, lower detection tem have been reported in literature. Even though the research so
limit, risk of other microbial infections and mass-transfer limita- far provided promising results, the upscaling of BES still need to
tions concerning substrates and products [35]. Recent advances address the overpotentials and other associated design aspects.
made in MFC-based biosensors have broadened the perspective Reproducibility of bench scale performances in the large scale
for simple, on-site and cost-effective water quality monitoring. systems will certainly make the process economically and
The use of highly acid/base tolerant and halo-tolerant microbes in environmentally feasible. Studies have also proposed the possible
MFC biosensors will be highly attractive for industrial wastewater way to incorporate the BES technology in existing wastewater
monitoring [35]. treatment plants. It has been projected more technically feasible
to incorporate MEC for simultaneous waste treatment and
8. Future prospects and conclusions hydrogen production than running MFC for electricity generation
from wastewater. The possible and appropriate scheme to incor-
BESs are versatile systems designed for converting chemical porate MEC to produce hydrogen gas in existing wastewater
energy into electrical energy (and vice-versa) while employing treatment plant as proposed by Escapa et al. [49] is shown in
microbes as catalysts. MES is the most recent application of BESs Fig. 4.
utilized for the electricity-driven chemical and fuel production. In anodic mechanism of MFCs, mixed cultures are considered
However, the understanding of the multi-disciplinary aspects to be as effective biocatalysts with wastewaters as substrate. In
involved in MES processes is still on its infancy. Compared to MES, less is known about the behavior of cathodic biofilms,
conventional industrial microbiology, MES requires more expertise planktonic cells and electron transfer mechanism involved. It is
from other disciplines such as electrochemistry, bio- also necessary to understand the interface of both biofilms and
electrochemistry and materials sciences. Generally, the perfor- planktonic cells. Conceptually, mixed as well as pure homo-
mance of any biological system is dependent on the substrate acetogenic bacterial cultures could effectively carry out CO2
conversion, biocatalyst activity, specificity of the enzymes involved reduction. The electron transfer efficiency and involved mecha-
in the conversion process and redox conditions. In the case of nism, biofilms sustainability in electrochemical system and
electrochemical processes it also depends on the conductivity of biochemistry of the microorganisms command the selection of
the electrolyte (either anolyte or catholyte), mediators involved, type of biocatalyst to be chosen. Selection of biocatalyst is also
anode and cathode potentials, overpotentials (voltage losses), mass influenced by the terminal electron acceptor to be used for
and charge transfer etc. Since MES result from a combination of reduction process. To take full advantage of MES, it is very
these two processes, the overall limitations are especially complex important to understand which intracellular and extracellular

Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002
14 S. Bajracharya et al. / Renewable Energy xxx (2016) 1e18

Fig. 4. Possible scheme to incorporate BES in wastewater treatment plant. Flowchart shows the processes in an existing wastewater treatment plant (top) and the proposed plant
(bottom) incorporating the Microbial Electrolysis Cell for wastewater treatment and hydrogen production. “Adapted from Escapa et al. [49] Copyright (2012), with permission from
Elsevier”.

factors influence the metabolic rate. reductive dechlorination of trichloroethene to ethene with electrodes
serving as electron donors without the external addition of redox mediators,
The combination of BES technology with the fermentation
Biotechnol. Bioeng. 103 (2009) 85e91.
technology termed as Electro-fermentation (EF) has added a new [2] F. Aulenta, A. Catervi, M. Majone, S. Panero, P. Reale, S. Rossetti, Electron
future prospect of versatile BES application. The concept is to use transfer from a solid-state electrode assisted by methyl viologen sustains
electrical energy as source of reducing power for microbial efficient microbial reductive dechlorination of TCE, Environ. Sci. Technol. 41
(2007) 2554e2559.
fermentation and also to provide the required electrons for gen- [3] F. Aulenta, P. Reale, A. Canosa, S. Rossetti, S. Panero, M. Majone, Character-
eration of the product of interest. Researchers from the BES and ization of an electro-active biocathode capable of dechlorinating tri-
fermentation disciplines are focusing on EF. EF is foreseen as po- chloroethene and cis-dichloroethene to ethene, Biosens. Bioelectron. 25
(2010) 1796e1802, http://dx.doi.org/10.1016/j.bios.2009.12.033.
tential application to overcome many biological, electrochemical, [4] F. Aulenta, L. Tocca, R. Verdini, P. Reale, M. Majone, Dechlorination of Tri-
logistical and economic challenges incorporated in the production chloroethene in a continuous-flow bioelectrochemical reactor: effect of
of value-added products in BES. cathode potential on rate, selectivity, and electron transfer mechanisms,
Environ. Sci. Technol. 45 (2011) 8444e8451.
[5] M. Azuma, M. Watanabe, Electrochemical reduction of carbon dioxide on
Acknowledgments various metal electrodes in low-temperature aqueous KHCO3 media,
J. Electrochem. Soc. 137 (1990) 1772e1778.
[6] S. Bajracharya, A. ter Heijne, X.D. Benetton, K. Vanbroekhoven, C.J. Buisman,
Suman Bajracharya is supported by a PhD grant from VITO's D.P. Strik, D. Pant, Carbon dioxide reduction by mixed and pure cultures in
strategic research fund (1310225). Mohita Sharma acknowledges microbial electrosynthesis using an assembly of graphite felt and stainless
Indo-Belgian scholarship from the Flemish Government (Vlaamse steel as a cathode, Bioresour. Technol. 195 (2015) 14e24.
[7] S.C. Barton, J. Gallaway, P. Atanassov, S. Calabrese Barton, J. Gallaway,
Gemeenschap-1F2B8G/JDW/2012-2013/12-BTL-IND-02) for sup-
P. Atanassov, S.C. Barton, Enzymatic biofuel cells for implantable and
porting her stay at VITO. G. Mohanakrishna gratefully acknowl- microscale devices, Chem. Rev. 104 (2004) 4867e4886, http://dx.doi.org/
edges the Marie-Curie Intra-European Fellowship (IEF) supported 10.1021/cr020719k.
[8] P. Batlle-Vilanova, S. Puig, R. Gonzalez-Olmos, M.D. Balaguer, J. Colprim,
project BIO-ELECTRO-ETHYLENE (Grant No: 626959) from the Eu-
Continuous acetate production through microbial electrosynthesis from CO2
ropean Commission. with microbial mixed culture, J. Chem. Technol. Biotechnol. (2015), http://
dx.doi.org/10.1002/jctb.4657.
[9] A. Baudler, I. Schmidt, M. Langner, A. Greiner, U. Schroder, Does it have to be
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electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
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Please cite this article in press as: S. Bajracharya, et al., An overview on emerging bioelectrochemical systems (BESs): Technology for sustainable
electricity, waste remediation, resource recovery, chemical production and beyond, Renewable Energy (2016), http://dx.doi.org/10.1016/
j.renene.2016.03.002

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