Science of the Total Environment 824 (2022) 153923

Contents lists available at ScienceDirect

Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Integration of microbial electrochemical systems and photocatalysis for

sustainable treatment of organic recalcitrant wastewaters:
Main mechanisms, recent advances, and present prospects
⁎
Razieh Rafieenia a, , Mira Sulonen a, Mohamed Mahmoud b, Fatma El-Gohary b, Claudio Avignone Rossa a
a
Department of Microbial Sciences, University of Surrey, Guildford GU2 7XH, United Kingdom
b
Water Pollution Research Department, National Research Centre, 33 El-Buhouth St., Dokki, Cairo 12311, Egypt

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Comprehensive revision of the literature

on coupling of photocatalysis and biodeg-
radation in MESs
• Photo-enhanced extracellular electron
transfer and electrode-biofilm interac-
tions resulted in enhanced removal of re-
calcitrant pollutants.
• Novel photocatalysts, and composite elec-
trodes have shown great potential to ac-
celerate the degradation.
• Light distribution inside the reactors and
the cost of production for photobioreactors
are the main challenges for the scale-up.

A R T I C L E I N F O A B S T R A C T

Article history: In recent years, microbial electrochemical systems (MESs) have demonstrated to be an environmentally friendly tech-
Received 3 December 2021 nology for wastewater treatment and simultaneous production of value-added products or energy. However, practical
Received in revised form 20 January 2022 applications of MESs for the treatment of recalcitrant wastewater are limited by their low power output and slow rates
Accepted 12 February 2022
of pollutant biodegradation. As a novel technology, hybrid MESs integrating biodegradation and photocatalysis have
Available online 17 February 2022
shown great potential to accelerate the degradation of bio-recalcitrant pollutants and increase the system output. In
Editor: Yifeng Zhang this review, we summarize recent advances of photo-assisted MESs for enhanced removal of recalcitrant pollutants,
and present further discussion about the synergistic effect of biodegradation and photocatalysis. In addition, we ana-
Keywords: lyse in detail different set-up configurations, discuss mechanisms of photo-enhanced extracellular electron transfer,
Microbial electrochemical systems and briefly present ongoing research cases. Finally, we highlight the current limitations and corresponding research
Recalcitrant pollutants gaps, and propose insights for future research.
Photocatalysis
Biodegradation
Biofilm
Electrodes

Abbreviations: CB, Conduction band; EET, Extracellular electron transfer; EAB, Electrochemically-active bacteria; ICPB, Intimate coupling photocatalysis and biodegradation; MESs, Microbial
Electrochemical Systems; MFC, Microbial fuel cell; MWCNTs, Multiwalled carbon nanotubes; •OH, Hydroxyl radicals; PEC, Photoelectrochemical cells; ROS, Reactive oxidative species; 3D, Three-
dimensional; TiO2, Titanium dioxide; UV, Ultraviolet; VB, Valence band; VL, Visible light.
⁎ Corresponding author.
E-mail address: r.rafieenia@surrey.ac.uk (R. Rafieenia).

http://dx.doi.org/10.1016/j.scitotenv.2022.153923
0048-9697/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
R. Rafieenia et al. Science of the Total Environment 824 (2022) 153923

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Integration of photocatalysis and biodegradation in MESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Mechanism of photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3. Configurations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.1. Bioanode-photocathode MESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.3.2. Photoanode-biocathode MESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.3. MESs with biophotoanode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3.4. Sequential photoelectrochemical cells (PEC) – MESs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Biocatalysts and biofilms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1. Microbial communities in MESs treating recalcitrant wastewaters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2. Photoelectrode-microbe interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Relieving toxicity of recalcitrant compounds on microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.1. Substrate and by-product inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2. Alternative electron acceptors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.3. Co-metabolism strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Summary, challenges, and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction
Recalcitrant pollutants are a diverse group of contaminants, including
endocrine disruptors, antibiotics, dyes, chlorinated compounds, polycyclic
aromatic hydrocarbons, pharmaceutical and personal care products, and
pesticides (Huang et al., 2011), which are resistant to conventional waste-
water treatment technologies, and remain biologically active even at trace
concentrations. Owing to their harmful effects on humans, animals, and
plants, the treatment of organic recalcitrant pollutants attracts great atten-
tion. The hazards associated with those pollutants include mutagenicity,
carcinogenicity and ecotoxicity, development of antibiotic-resistant bacte-
ria, abnormal growth in children, increased risk of cancer, alteration of
the immune system, and changes in reproductive function (Gupta and
Thakur, 2017; Roccuzzo et al., 2021). For instance, the release of pharma-
ceuticals into the environment has seen a sustained increase worldwide be-
cause of their intensive use for the treatment of human and animal diseases.
The occurrence of some groups of recalcitrant pollutants including pharma-
ceuticals, phenolic substances, disinfectants, and detergents in aquatic envi-
ronments could be originated in industries, animal farms, hospital effluents,
and households (al Qarni et al., 2016). Many other types of recalcitrant pol-
lutants, including polycyclic aromatic hydrocarbons, dyes, and chlorinated
compounds, are discharged to water bodies from coal-fired power plants,
petroleum refining, municipal solid waste incineration, and chemical in-
dustries (Gupta and Thakur, 2017).
Conventional wastewater treatment plants are generally designed to re-
move suspended solids and biodegradable organic matter but are unable to
efficiently eliminate recalcitrant pollutants since most of them are not bio-
degradable and/or cause inhibition of bacterial growth (Huang et al., 2011;
Verlicchi et al., 2012; Zhang et al., 2015). Thus, further treatment is re-
quired to eliminate their associated risks. Although physical and chemical
wastewater treatment technologies, such as ozonation, photocatalysis,
Fenton reaction, electrochemical processes, adsorption, chemical precipita-
tion, and membrane technology, seem to be promising at removing non-
biodegradable pollutants (Deng and Zhao, 2015; Gomes et al., 2020; Kurt
et al., 2017), they present major drawbacks, such as their relatively high
costs and production of secondary pollutants (i.e. sludge production and/
or air pollution) (Palanisamy et al., 2019; Rajasulochana and Preethy,
2016).
In recent years, microbial electrochemical systems (MESs) have
emerged as a sustainable technology for the production of valuable prod-
ucts and/or renewable energy from different waste streams (Gude, 2016;
Jayashree et al., 2015). The hallmark of MESs is to exploit the capability
of electrochemically-active bacteria (EAB) to catalyze bioelectrochemical
reactions and exchange the resulting electrons with either an electron
donor (i.e. cathode) or an electron acceptor (i.e. anode), resulting in
converting organic (and inorganic) pollutants into valuable products (i.e.
electricity, methane, hydrogen peroxide, hydrogen gas, or other value-
added products) (Kundu et al., 2013; Pant et al., 2013). In the last few
years, considerable efforts have been made on MESs concerning the devel-
opment of improved electrode materials (Divya Priya et al., 2020; Guo
et al., 2015; Li et al., 2016; Wei et al., 2011; Zhang et al., 2013); the identi-
fication of electroactive microorganisms in microbial communities (Croese
et al., 2011; Liu et al., 2020b; Logan and Regan, 2006; Paitier et al., 2017;
Xu et al., 2018a); the optimization of operational conditions (Gadkari
et al., 2020; Goswami and Mishra, 2017; Martin et al., 2010; Patil et al.,
2010; Tremouli et al., 2017); and overcoming the existing challenges in
MESs applications (Kim et al., 2007; Pandey et al., 2016; Trapero et al.,
2017).
In typical MESs, biodegradation is combined with electrochemical pro-
cesses in one device, enabling high removal of organic matter, including re-
calcitrant wastewater. More importantly, this integration overcomes the
majority of the limitations of individual processes, such as high operation
and maintenance costs, energy consumption and/or sludge production
(Palanisamy et al., 2019). However, the major challenges for sustainable
treatment of recalcitrant wastewaters are the low removal processes as a re-
sult of the poor biodegradability of recalcitrant compounds and their toxic-
ity towards EAB and other microbial guilds in MESs. In order to circumvent
these challenges, the combination of MESs and photocatalytic processes in
one system could accelerate the degradation of refractory compounds and
enhance removal efficiencies, resulting in a much higher recovery of
value-added products (Fischer, 2018). The use of MESs for wastewater
treatment has been revised thoroughly (Goswami and Mishra, 2017;
Gude, 2016; Kadier et al., 2020; Keong Ngaw et al., 2015; Palanisamy
et al., 2019; Pandey et al., 2016; Slate et al., 2019; Zheng et al., 2020). How-
ever, to the best of our knowledge, there is no comprehensive review ad-
dressing in detail the removal of recalcitrant compounds using MESs
combined with photocatalysis. In this review, we aim at summarizing re-
cent developments in this nascent technology for the elimination of recalci-
trant pollutants with simultaneous energy and resource recovery.
As mentioned above, MESs is a hybrid technology that combines elec-
trochemical processes and biodegradation in one device, with EAB being
the catalysts attached to bioelectrodes. In those systems, treatment

2
R. Rafieenia et al.
efficiency is generally higher than conventional electrochemical systems
since lower overpotentials are needed to drive the electrochemical reac-
tions (Huang et al., 2011). Due to the continuous discharge of electrons
generated by oxidation of organic substrates, MESs support enhanced pol-
lutant removal efficiencies compared to conventional biodegradation
(Palanisamy et al., 2019). Therefore, MESs has been highlighted as a prom-
ising technology for the removal of a wide range of recalcitrant pollutants,
as it requires a much lower energy supply than standard electrochemical re-
duction, resulting in lower operational costs (Kadier et al., 2020). In addi-
tion, MESs presents the advantage of less sludge production compared to
biological treatment (Munoz-Cupa et al., 2021). The degradation of some
recalcitrant compounds using MESs has been studied, including nitroben-
zene (Wang et al., 2012), 4-chlorophenol (Wen et al., 2013; Zhou et al.,
2017), Congo red (Huang et al., 2018), black liquor (Chen et al., 2019),
2-chloro-4-nitrophenol (Yu et al., 2020b), erythromycin (Hua et al.,
2019), xenobiotics (Fernando et al., 2018), carbamazepine (Tahir et al.,
2019), and 2-mercaptobenzothiazole (San-Martín et al., 2020). The syn-
ergy of biological degradation and electrochemical processes may over-
come some of the limitations of individual processes; however, energy
input is required to accelerate the removal process and avoid reduced sys-
tem efficiencies (Dewan et al., 2008; Escapa et al., 2016). Coupling MESs
with photocatalysis could increase the process efficiency, by capturing
the solar energy and supplying the energy demands for the biodegradation
of recalcitrant pollutants (Vinayak et al., 2021). Moreover, additional
energy provided by photocatalysis, would be utilized to degrade toxic com-
pounds which are not degradable by microorganisms, resulting in en-
hanced performances (Zhu et al., 2021). Mechanistic aspects of molecular
photocatalysis have been previously reviewed and discussed in detail by
several papers (Banerjee et al., 2014; Sobczyński et al., 2004; Zhu and
Zhou, 2019) and is not covered here as it is not in the scope of his review.
2. Integration of photocatalysis and biodegradation in MESs
As mentioned above, the toxicity of recalcitrant compounds present in
real wastewater for EAB reduces MES efficiency due to poor biofilm
Fig. 1. Configurations of photo-assisted MESs: a) photoanode-biocathode; b) bioanode-photocathode; c) intimately coupling of photocatalysis and biodegradation; and
d) sequential PEC and MES.
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formation and low biodegradation (Mahmoud et al., 2014). An innovative
option is the use of integrated systems using photocatalysis technology and
MES, in which a photocatalyst non-selectively transforms bio-recalcitrant
pollutants into less toxic, readily available compounds that can be easily de-
graded by the biofilm microorganisms. Different configurations of MESs in-
tegrated with photocatalysis are shown in Fig. 1, and some of the factors
affecting photocatalysis and biodegradation in integrated MESs are summa-
rized in Fig. 2.
2.1. Mechanism of photocatalysis
Photocatalytic degradation of pollutants relies on the generation of elec-
tron/hole (h+) pairs as a result of the transfer of electrons from the valence
band (VB) to the conduction band (CB) of the photocatalyst, caused by light
irradiation:
Photocatalyst þ hv ! hþ þ e− (1)
Holes can react with H2O molecules adsorbed on the photocatalyst sur-
face generating hydroxyl radicals (•OH). These highly reactive •OH attack
the pollutants non-selectively and degrade them to less toxic, more biode-
gradable compounds (Antolini, 2019).
Despite the high efficiency of light-to-energy conversion, there are
still challenges in the application of photocatalytic processes for the re-
moval of recalcitrant pollutants. The main reasons are: 1) Photocatalytic
reactions are fast and therefore, it is difficult to control the intermediate
products. The inherent tendency of electron/hole pairs to recombine re-
duces electron transfer and consequently, the efficiency of the process
(Lianos, 2017); 2) Efficient photocatalysts, such as TiO2, are only highly
reactive under high-energy UV light (Dong et al., 2015; Yu et al.,
2020a); 3) Mass transfer limitations, caused by either a small surface
area of the electrode or by poor adsorption of pollutants on the electrode
that may reduce the system efficiency, or a combination of both (Dong
et al., 2015; Zhao et al., 2017).
R. Rafieenia et al.
Fig. 2. Factors affecting photocatalytic and microbial degradation in photo-assisted MESs.
2.2. Photocatalysts
During photocatalysis, the reactions between electrons generated
through light excitation and pollutants occur on the surface of the
photocatalysts. Therefore, the capacity of the photocatalyst for harvesting
light represents a key factor for the transportation of electrons from VB to
CB and the generation of electron/hole pairs (Wangab et al., 2016). In ad-
dition, an efficient photocatalyst should be cost-effective, chemically stable,
and non-toxic (Antolini, 2019), and for systems integrating photocatalysis
and biodegradation, the photocatalysts need to be bio-compatible (Yu
et al., 2020a).
Based on their band gap energy, photocatalysts can be induced by either
visible light (VL) or ultraviolet light (UV). Photocatalysts with a large band
gap can only absorb a small fraction (<5%) of irradiated solar light (Dong
et al., 2015). For instance, TiO2-based photocatalysts are the most studied pho-
tocatalytic materials for refractory pollutant removal in MES systems. How-
ever, it can only absorb UV light due to its large band gap (i.e., 3.0–3.2 eV)
(Nakata and Fujishima, 2012). In addition, using UV-induced photocatalysis
in systems combining photocatalysis and biodegradation is discouraged for
two main reasons: 1) the high operational costs associated with the light
source, and 2) the deleterious effect of UV light on the microorganisms in
the biofilm.
To increase the photocatalytic activity of photocatalysts under VL, dif-
ferent methods have been proposed to reduce their band gap energy. The
first method is the incorporation of a noble metal, such as Au (Oros-Ruiz
et al., 2013), Pt (Guayaquil-Sosa et al., 2017), and Ag (Xiong et al., 2017),
into TiO2. Photogenerated electrons could be attracted by the noble metals,
which have a lower Fermi level (a thermodynamic quantity defined as the
work required to add one electron to a solid material) than TiO2, while
photogenerated holes would remain in TiO2 (Ni et al., 2007). Although
noble metals could efficiently increase the photocatalytic activity of
photocatalysts, their high costs limit their industrial applications.
The second method to enhance the VL activity of photocatalysts is by
the incorporation of non-metal dopants. Non-metal doping seems to be a
more cost-effective method compared to noble metal doping, and therefore
more promising for industrial applications (Wangab et al., 2016). Non-
metals can substitute for oxygen lattice sites of photocatalyst, reducing
the band gap (Yu et al., 2020b) . So far, non-metals such as N (Ansari
et al., 2016; Liu et al., 2021), C (He et al., 2017), F (Yu et al., 2012), B
(Liu et al., 2008), P (Lin et al., 2005; Ren et al., 2020), S (Boningari et al.,
2018) and I (Tojo et al., 2008), have been used for TiO2 doping. Among
those, N is the most extensively studied dopant in photocatalytic MESs
(Zhou et al., 2017, 2018).
In addition to noble metals or non-metals, transition metals could be
also used as dopants to expand the range of photocatalyst induction to
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Science of the Total Environment 824 (2022) 153923
light (Litter, 1999). Among the transition metals, Fe (Man et al., 2019),
Co (Man et al., 2019), Ni (Man et al., 2019; Shen et al., 2019), Mo (Man
et al., 2019; Xing et al., 2019), Cr (Chang et al., 2014), and Mn (Anju
Chanu et al., 2019) have been used as dopants to enhance photocatalytic
activity. An advantage of transition metals compared to the other dopants
is the inhibition of electron-hole recombination due to their efficient elec-
tron trapping characteristics. In general, doping with metals/non-metals
is considered a complex process that needs to be performed at high temper-
atures (Dong et al., 2015). Surface modification of photocatalyst with or-
ganics under mild conditions is another method to increase the VL
activity of photocatalyst. Organic ligands such as dyes are adsorbed on
the photocatalyst surface, allowing high absorption of the VL. The organic
molecule in the excited state can transfer electrons to the CB of the
photocatalyst. For all the methods mentioned, stability, non-toxicity on mi-
croorganisms, and cost-effectiveness are the factors that need to be consid-
ered for industrial applications (Dong et al., 2015; Peiris et al., 2021;
Reginato et al., 2020).
2.3. Configurations
As mentioned earlier, there are different reactor configurations in
which MESs are integrated with photocatalysis. In this section, we present
a detailed description and discussion of the different configurations
shown in Fig. 1.
2.3.1. Bioanode-photocathode MESs
This type of photo-MES consists of a bioanode connected to a photocath-
ode via an external circuit. The difference of potential between anode and
cathode leads to the migration of bio-generated electrons from the anode
to the cathode, which are subsequently combined with photo-generated
holes. Irradiation of the photocathode accelerates the redox reaction, since
the photo-generated holes combine with bio-generated electrons, leaving
the photo-generated electrons for cathodic reduction (Wang et al., 2019c).
In contrast to standard MESs, pollutants in bioanode-photocathode MESs
are not degraded by oxidation at the anode; they are reduced at the cathode
by accepting the electrons migrating from the anode (Antolini, 2019).
Bioanode-photocathode MESs have been used for degradation of refrac-
tory compounds, including azo dyes (Ding et al., 2010; Han et al., 2017;
Hou et al., 2017b; Long et al., 2019) and pharmaceuticals (Wang et al.,
2019b; Xu et al., 2020b). A degradation efficiency of 82% for active bril-
liant red X3, an azo dye was reported for a photo-MFC system consisting
of a bioanode and blue titanium nanotube arrays as the photocathode,
with a current output of 138.66 mA.m−2 (Long et al., 2019). Interestingly,
the rate constant of decolorization (k) with illumination was twice of that
for dark conditions, demonstrating an enhanced removal efficiency, most
R. Rafieenia et al.
likely caused by the photo-generated electrons. A photo-MES with a TiO2-
coated photocathode was developed for methyl orange degradation and
concurrent H2 production under UV irradiation (Hou et al., 2017b). With
an initial methyl orange concentration of 50 mg/L, they obtained a high
decolorization efficiency of 96% within 8 h. In another study, a bio-
photoelectrochemical system, equipped with a bioanode and a BiVO4/
RGO (B/G) composites photocathode, was used for 2,4-dichlorophenol re-
moval (Tu et al., 2020). Under illumination, the MES exhibited high current
generation and 2,4-dichlorophenol degradation, which were 50% and 63%
higher than under dark conditions, respectively, suggesting the significance
of photocatalytic process on current output and pollutant degradation. Re-
cently, a removal efficiency of 75.94% for ibuprofen, with a current density
of 0.75 A/m2, was reported for a novel photo-MFC consisting of a CuInS2
photocathode. In addition, the integrated system showed good long-term
stability for ibuprofen removal (73.75% after five times reuse) (Xu et al.,
2020b).
2.3.2. Photoanode-biocathode MESs
Photoanode-biocathode MESs are another type of photo-assisted MESs
that have been designed and used to achieve higher removal of recalcitrant
compounds and energy generation. Currently, platinum-based catalysts are
the most extensively used materials for cathodic oxygen reduction reactions
in MESs. However, high cost, short service life, and kinetic limitations are
the major drawbacks for their industrial application (Antolini, 2019). Micro-
bial catalysts are promising alternatives to metal-based cathodes, having the
advantages of cost-effectiveness and long-term stability. In a biocathode, mi-
croorganisms adhere to the cathode surface and perform the cathodic reac-
tions using the electrons transferred from the anode. The consumption of
photo-generated electrons by cathodic microorganisms facilitates the sepa-
ration of photo-induced electron/hole pairs from the anode; thus, improving
pollutant degradation. (Su et al., 2020). Examples of electron acceptors used
in biocathodes are O2, Fe3+, NO− 2−
3 , and SO4 .
Very few studies have reported the use of photoanode-biocathode MESs
for the removal of recalcitrant pollutants. The first study on the removal of
refractory pollutants using biocathode-based MESs was reported by Du
et al. (2014b). They presented an MFC consisting of a TiO2-based photocat-
alytic anode and a biocathode to degrade methyl orange with accompany-
ing generation of electricity. Although the performance of the biocathodes
in terms of pollutant removal and power output, was comparable to Pt-
based cathodes, the O2 affinity of the electrode surface should be carefully
studied since it is an important factor affecting MESs performance (Wang
et al., 2016). More recently, Sui et al. successfully used an MFC consisting
of an Ag-doped TiO2 photoanode and a biocathode for electricity genera-
tion and rhodamine B degradation, achieving a pollutant degradation effi-
ciency of 99.5% with a current output of 1.26 mA m−2 (Sui et al., 2017).
In addition, the biocathode could provide a stable oxygen-reducing
cathodic reaction without kinetic limitations. Recently, a novel photoanode-
biocathode system was fabricated by Su et al. and evaluated for the simulta-
neous removal of nitrate and methyl orange, using TiO2/g-C3N4 nanosheet/
graphene as a photoanode and a biocathode pre-cultured with denitrifying
bacteria (Su et al., 2020). The removal performance of methyl orange was
about 90% after 21 h and nitrate was effectively reduced to N2 by the
biocathode.
2.3.3. MESs with biophotoanode
A biophotoanode is a two-sided electrode where one side is illuminated,
and the other side is colonized with EAB (Fischer, 2018). The synergistic ef-
fect of a biophotoanode could be related to enhanced extracellular electron
transfer (EET) resulting from the production of biodegradable intermedi-
ates by photocatalysis. In addition, EAB accelerate the electron migration
from VB to CB, resulting in an increase in the photocatalysis rate (Long
et al., 2020). The synergistic degradation of pollutants includes three
steps: pollutant adsorption on the electrode; photocatalysis on the light-
side of the electrode; and biodegradation of intermediates by biofilm
bacteria. In fact, the electron transfer between photocatalysts and microor-
ganisms has a key role in enhancing the efficiency of the combined processes.
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Science of the Total Environment 824 (2022) 153923
For instance, it has been reported that the permeability of bacterial cell mem-
branes could be improved when mild photocatalysis with appropriate dura-
tion and intensity is applied, resulting in improved EET (Zhang et al., 2021a).
Qian et al. were the first to fabricate a biophotoanode by interfacing a
hematite (α-Fe2O3) nanowire photoanode and Shewanella oneidensis MR-1,
an EAB (Qian et al., 2014). They observed a 150% higher photocurrent gen-
eration than the corresponding abiotic photoelectrode. Li et al. investigated
the photo-induced EET from Geobacter sulfurreducens to hematite under VL
irradiation (Li et al., 2014). They observed a 40% increase in microbial res-
piration after illumination of the hematite surface, which was correlated
with photocurrent production. In another study, Feng et al. constructed a
composite biophotoanode by combining a hematite photocatalyst and car-
bon materials (Feng et al., 2016). Besides achieving higher current outputs,
they reported that the biophotoanode promoted faster biofilm formation
and shorter start-up time (1.1 days) compared to the dark system (2.5 days).
Only a few studies have applied biophotoanodes for recalcitrant com-
pound removal. Long et al. used a composite biophotoanode fabricated
from a combination of WO3/TiO2 and carbon felt for aniline degradation
(Long et al., 2020). Current generation under illumination by the hybrid elec-
trode increased by 28% compared to the dark conditions (38.8 and 27.7 mA.
m−2 respectively). In addition, the biophotoanode showed a higher pollutant
degradation rate (96%) compared to the abiotic photoanode (89%) and
bioanode (38%). Further electrochemical and microbial community analysis
confirmed that higher efficiencies of biophotoanode were due to the in-
creased EET and higher enrichment of EAB in the microbial community. Re-
cently, Liu et al. constructed a biophotoanode by integrating nano-Ag3PO4
and Shewanella oneidensis MR-1 which was applied for the degradation of p-
chlorophenol (Liu et al., 2020a). In the absence of light, no significant p-
chlorophenol degradation was recorded, while a degradation efficiency of
21% was observed in the photo-induced system. Their study suggested that
bio-generated electrons produced by microbial respiration could be trans-
ferred to the nano-Ag3PO4 photocatalyst and attracted by photogenerated
holes. Thus, photogenerated electrons use p-chlorophenol as an electron ac-
ceptor, contributing to its degradation.
Intimate coupling photocatalysis and biodegradation (ICPB) is a novel
technology, which combines biodegradation and photocatalysis in the
same reactor to increase the potential of refractory compounds removal
(Li et al., 2012).The concept of ICPB was first suggested by Marsolek
et al. and applied to remove 2,4,5-trichlorophenol in a photocatalytic
circulating-bed biofilm reactor (Marsolek et al., 2008). ICPB has been suc-
cessfully used to enhance the biodegradation of recalcitrant compounds in
various reactor types. Some of these works include tetracycline hydrochlo-
ride (Xiong et al., 2017), 4, 5-trichlorophenol (Marsolek et al., 2014), 2,4,5
trichlorophenol (Li et al., 2012), phenanthrene (Cai et al., 2019), nitroben-
zene (Yang et al., 2015), and oxytetracycline (Ding et al., 2018), and atra-
zine (Zhang et al., 2021c). It is well understood now that the intimate
coupling photocatalysis and biodegradation approach not only optimizes
the removal of recalcitrant compounds, but also lowers the operational
costs (Yu et al., 2020a).
Generally, an ICPB substratum is made of a porous carrier coated with a
semiconductor photocatalyst. Illumination of the photocatalyst generates
various reactive oxidative species (ROS), including •OH and •O− 2 and h ,
+
which attack refractory compounds and transform them into biodegradable
substances (Fischer, 2018). The products of photocatalysis then diffuse into
the porous carrier and are degraded by the microorganisms in the biofilm.
The mechanism involved in ICPBs is similar to biophotoanodes; however,
biofilm formation inside the porous carrier (instead of the exposed surface
of the anode) prevents direct contact between the photocatalyst and bio-
film, and protects bacteria from damage by shear forces and ROSs. More-
over, bacteria are protected in the interior of the porous carrier and thus
remain active under UV light (Yu et al., 2020a; Zhang et al., 2012).
The next level application of ICPB technology would be its integration
with MESs for electricity generation from bio-recalcitrant compounds.
This emerging field combines the advantages of ICPB electrodes and
MESs for the sustainable treatment of refractory compounds. To date,
very limited research exists on recalcitrant pollutants removal in MESs
R. Rafieenia et al. Science of the Total Environment 824 (2022) 153923

with ICPB electrodes. The first study on the application of ICPB electrodes
in MESs for treatment of recalcitrant pollutants was reported by Zhou
et al., who applied a VL-induced ICPB anode in an MES for 4-
chlorophenol degradation (Zhou et al., 2017). The ICPB anode was made
of a macroporous carbon foam coated with an N-doped TiO2 photocatalyst.
The MES with ICPB anode promoted higher degradation efficiency (41%)
compared to MESs with bioanode only (28%) or with an abiotic
photoanode (10%). Further studies using the same MES confirmed that
EAB were able to transfer the electrons generated by photocatalysis to the
ICPB anode (Zhou et al., 2018). A recent study reported a high degradation
of 2,4,6-trichlorophenol in an ICPB-MFC made of fibrous carbon felt anode
coated with VL-induced photocatalyst mpg-C3N4 (79.3%) within 10 h, a
value ~1.2–1.4-fold higher than the unilluminated MFC and the
photocatalytic-only process (Wang et al., 2019d). The current output using
an ICPB anode was 5.34 A/m2, almost twice the current produced by a
bioanode (2.80 A/m2). A summary of studies on recalcitrant pollutants re-
moval by photo-assisted MESs is shown in Table 1.
Despite these promising results, the use of ICPB electrodes in MESs is
still considered as a new research field and is still in its infancy. Fundamen-
tal understanding of the possible mechanisms involved in ICPB, the interac-
tion between biofilm microorganisms and photocatalysts, the impact of
operational parameters on degradation efficiency, and the development
of novel photocatalysts are among the research fields to be studied.
2.3.4. Sequential photoelectrochemical cells (PEC) – MESs
It is possible to combine photocatalytic or photoelectrochemical cells
(PEC) with MES as separate reactors in a sequential hybrid system to en-
hance the removal efficiency of recalcitrant pollutants (Yuan et al., 2010).
Electricity produced by organic biodegradation in MES would provide the
required external electric output to drive self-powered, sustainable PECs,
in terms of renewable energy production (e.g. H2) and photocatalytic or-
ganic matter degradation (Du et al., 2017). A typical PEC is composed of
an n/p-type semiconductor anode and a metal or p-type semiconductor
cathode. In a hybrid PEC-MES, photo-generated holes in PEC combine
with bio-generated electrons released in the biodegradation of organic
compounds in MES, leaving the photo-generated electrons for cathodic re-
duction. Thus, higher cathode potentials could be achieved that facilitate
the microbial degradation in the bioanode and consequently enhance the
overall performance (Zhang et al., 2019). Due to the synergy between the
photocatalytic oxidation in PEC and the microbial degradation in MES,
the hybrid system has the potential to be applied for the treatment of recal-
citrant wastewaters rich in low-biodegradable pollutants.
Yuan et al. used the energy derived from biodegradation of organic mat-
ter in an MES to accelerate the photocatalytic oxidation of p-nitrophenol by
PEC (Yuan et al., 2010). Their hybrid system showed higher treatment effi-
ciencies and accelerated p-nitrophenol degradation in comparison with
MES and PEC alone. Du et al. used a sequential PEC-MES for methyl orange
degradation (Du et al., 2017). The methyl orange decoloration rate with
PEC alone was not significant, with a kinetic constant k = 0.052 h−1, 10-
fold lower than that obtained by the hybrid system (k = 0.490 h−1). In ad-
dition, the power density of the hybrid system was significantly enhanced
compared to the MES alone (1650 and 990 mW·m−2, respectively). Zeng
et al. studied levofloxacin removal using a sequential MES-PEC hybrid sys-
tem, achieving complete mineralization of levofloxacin in <85 min (Zeng
et al., 2019). The MES provided bio-generated electrons for the efficient
pollutant degradation in PEC. Those studies suggest that the sequential con-
nection of MESs and PECs represents a promising system integrating
photocatalysis and bio-electrochemical degradation for the treatment of re-
calcitrant wastewaters and power generation.
3. Biocatalysts and biofilms
3.1. Microbial communities in MESs treating recalcitrant wastewaters
Biofilms have a pivotal role in pollutant degradation and concomitant
energy or chemical production in MESs. A biofilm is formed by the attach-
ment of microorganisms on a solid surface (typically electrodes in MESs)
(Rittmann, 2018). Electroactive bacteria in the biofilm can perform EET
to and from the electrode surface. In this section, we explore anodic and ca-
thodic biofilms and their interactions with electrodes.

Table 1
A summary of recalcitrant pollutants treated by photo-assisted MESs.
Type of hybrid system Recalcitrant Aeration Electrolyte Photocatalyst Light Removal Current Reference
compound source efficiency (%) generation

Dual chamber Metronidazole Not Na2SO4 (MoW) Visible 94.5 1.0 A/m2 (Wang et al., 2019b)
Bioanode-photocathode
Dual chamber Methyl orange Not Na2SO4 TiO2 nanotube arrays UV–Visible 88.3 3.25 A/m2 (Du et al., 2014b)
photoanode-biocathode
2
Dual chamber Methyl orange Not Na2SO4 Pd-SiNW Visible 84.5 0.8 A/m (Han et al., 2017)
Bioanode-photocathode
Dual chamber Active brilliant red X3 Not Na2SO4 TiO2 nanotube arrays UV–Visible 82.0 6.24 mA (Long et al., 2019)
Bioanode-photocathode
Single chamber Methyl orange Not KCl TiO2/g-C3N4 UV–Visible 90.0 0.84 mA (Su et al., 2020)
photoanode-biocathode nanosheet/graphene
3
Single chamber Bioanode-photocathode 2,4-dichlorophenol Not None BiVO4/RGO UV–Visible 68.5 60.31 A/m (Tu et al., 2020)
Single chamber Nitrofurazone Not Na2SO4 g-C3N4/CdS Solar 83.1 9 mA (Hou et al., 2020)
Bioanode-photocathode
Single chamber Methyl orange Not PBS TiO2 UV 96.0 – (Hou et al., 2017b)
Bioanode-photocathode
Single chamber Methyl orange Not PBS g-C3N4/BiOBr UV–Visible 97.8 – (Hou et al., 2017a)
Bioanode-photocathode
2
Dual chamber Ibuprofen Yes KCl CuInS2 Visible 75.9 0.75 A/m (Xu et al., 2020b)
Bioanode-photocathode
−3
Dual chamber Oxytetracycline Not None BiOCl/reduced Visible 98.9 24.63 A m (Zhang et al., 2021b)
Bioanode-photocathode graphene oxide aerogel
(BGA)
Dual chamber Rhodamine B Yes Na2SO4 Ag/TiO2 UV 99.5 0.0012 A/m2 (Sui et al., 2017)
photoanode-biocathode
Dual chamber with ICPB anode 4-Chlorophenol Not NaHCO3 N-TiO2 Visible 41.0 0.4 A/m2 (Zhou et al., 2017)
Single chamber with ICPB anode 2,4,6-Trichlorophenol Yes None mpg-C3N4 Visible 79.3 5.34 A/m2 (Wang et al., 2019d)
Dual chamber with biophotoanode Aniline Not None WO3/TiO2 UV–Visible 85.0 3.5 mA (Long et al., 2020)
Dual chamber Ofloxacin Not Na2SO4 LiNbO3/CF UV 86.5 2.3 A/m2 (Xu et al., 2020a)
Bioanode-photocathode
Single chamber MFC with photobiocathode 2,4,6-trichlorophenol Yes None N-TiO2 Visible 100% 0.38 A/m2 (Zhu et al., 2021)

6
R. Rafieenia et al.
As mentioned above, anodic EAB in the biofilm accept electrons from
electron-donating substrates and transfer the obtained electrons to the
anode. The efficiency of a biofilm depends on the EET performance of its
functional microbial groups (Rittmann, 2018). Among EAB, Geobacter
sulfurreducens and Shewanella oneidensis are the most studied species (Nimje
et al., 2012; Palanisamy et al., 2019). However, other electroactive bacteria,
including species from Citrobacter, Klebsiella, Arcobacter, Propionibacterium,
Clostridium, Enterobacter, and Aeromonas genera have been detected in MESs
(Anh Pham et al., 2003; Fedorovich et al., 2009; Kadier et al., 2016; Kim
et al., 2019).
Although Shewanella and Geobacter have both outer-membrane cyto-
chromes and conductive nanowires, power production in single-species cul-
tures is generally lower than in mixed cultures. That is mainly due to the
synergistic interactions between different members of a microbial commu-
nity (Ishii et al., 2008; Watson and Logan, 2010). Monitoring microbial
communities and the metabolic interactions between different species is es-
sential to optimize the degradation efficiency in MESs. The microbial pop-
ulations evolved in MESs vary from one system to another, depending on
the operational and biological parameters as well as on the nature of the re-
calcitrant pollutants to be treated (Logan and Regan, 2006). In addition, the
structure of the microbial community in MESs might change during its op-
eration. A study performed by Hodgson et al. on an MFC cascade, revealed
that the abundance of genera in the anodic biofilm shifted between the first
and last reactors of the cascade (Hodgson et al., 2016). Another study per-
formed by Paitier et al. showed that microbial evolution in an MFC contin-
ued after 20 days of operation, and even after the voltage was stabilized
(Paitier et al., 2017).
The use of microorganisms in the cathode instead of abiotic catalysts
has been suggested as a cost-effective and environmentally friendly ap-
proach to increase MESs performance (Rozendal et al., 2008). To optimize
the biocathodes, understanding the functional species in cathodic biofilms
as well as elucidation of the mechanisms by which they facilitate the ca-
thodic reduction are crucial factors (Kim et al., 2015). Sui et al. performed
microbial community analysis to determine the cathodic microbial popula-
tions in an MES treating rhodamine B (Sui et al., 2017). Their MFC
consisted of a TiO2-based photoanode and a biocathode for oxygen reduc-
tion. The phylogenetic profile of the cathodic biofilm showed that the dom-
inant phyla belonged to Proteobacteria (75.38%), Bacteroidetes (19.05%),
and Nitrospirae (3.51%). It is well known that numerous EAB belong to
Proteobacteria (Rittmann, 2018). At the genus level, the cathodic biofilm
was dominated by electroactive genera such as Acinetobacter sp. (41.5%)
and Shewanella sp. (4.51%), indicating the key role played by these species
in the cathodic reduction of oxygen (Sui et al., 2017). Du et al. reported a
synergistic relationship between nitrifying bacteria and the cathodic
oxygen-reducing reaction (Du et al., 2014a). Nitrifiers could act as catalysts
for cathodic oxygen reduction and, in turn, use the extracellular electrons
derived from the cathode as an energy source, implying that biocathode
performance is highly dependent on the abundance of nitrifiers. Liang
et al. reported that biocathode acclimation at low temperature (10 °C)
with continuous electrical stimulation could improve the functioning stabil-
ity of cathodic microbial communities for chloramphenicol degradation
(Liang et al., 2016). Cold-adaptive biocathodes are of particular interest ei-
ther for accelerated pollutant removal in cold environments, or for improved
stability of the cathodic microbial populations towards environmental
changes.
Rozendal et al. applied a three-phase biocathode startup to naturally
select EAB mixed cultures (Rozendal et al., 2008). The current density ob-
tained by the biocathode was 4 times higher than the abiotic cathode
(−1.2 and −0.3 A·m−2 respectively). H2 production at the biocathode
was 0.63 m3 H2·m−3, significantly higher than the control cathode
(0.08 m3 H2·m−3), indicating the role of enriched microbial species on en-
hanced cathodic performance. Croese et al. studied the effect of substrate
and setup design (large or small) on microbial communities of MESs
biocathodes (Croese et al., 2014). Their study revealed that microbial diver-
sity, community composition, and biocathode activity were significantly in-
fluenced either by setup, substrate, or both. Interestingly, large and small
7
Science of the Total Environment 824 (2022) 153923
MES setups showed different microbial community composition, even with
the same substrate. The microbial community in acetate-fed small MES
setup (i.e., projected electrode area of 22 cm2) was dominated by Firmicutes
while in the large setup (i.e., projected electrode area of 100 cm2) fed with
the same substrate, Proteobacteria were the dominant phyla. They also com-
pared the microbial communities of large setups fed with different substrates.
In the large setup fed with acetate, the highest relative abundance within the
Proteobacteria (23% of the total clones) belonged to Kaistella koreensis. In the
large setup with bicarbonate as substrate, the dominant genera were affiliated
to Hydrogenophaga (13%), Desulfovibrio (13%), and Azonexus (13%). SEM im-
ages showed that microbial colonization happened on the whole surface of
the small electrode, while colonization was only partially observed on the
large setup electrode. The main reasons for the difference in microbial popu-
lations in large and small setup would be the different nutrient availability
due to mixing, and the shear forces on the electrode that may remove the sur-
face microorganisms (Croese et al., 2014).
Chen et al. studied the microbial communities and the pollutant re-
moval capacity of a biocathode fed by either acetate or NaHCO3 (Chen
et al., 2016). The predominant species in the biocathode with acetate
belonged to Proteobacteria (62.1%), Bacteroidetes (12.2%), Actinobacteria
(10.4%), and Firmicutes (14.2%). The abundant phyla using NaHCO3 as
catholyte were similar to the acetate-fed system, however, but at different
proportions: Proteobacteria (73.6%), Bacteroidetes (10.0%), Actinobacteria
(7.6%), and Firmicutes (7.7%).
In addition to the capability of microbial species at the biocathode, it
has been reported that anode robustness is an important factor affecting
the performance of biocathode. An optimum current output at the anode
supports the electron supply required for microbial metabolism at the
biocathode while lowers the demand for an external energy supply (Lim
et al., 2017).
Although coupling photocatalysis and MESs has been reported as a
promising strategy for enhanced removal of recalcitrant pollutants, the
number of studies that performed microbial community analysis either
for bioanodes or biocathodes of photo-assisted MESs are few. It is critical
to detect microbial species enriched in biofilms subjected to light illumina-
tion, to understand the mechanisms behind synergistic degradation of pol-
lutants, and improve the performance of MESs. The synergistic effect of
photocatalysis and biodegradation changes microbial community structure
and abundances of biofilm microorganisms, specially EAB. Relative abun-
dances of EAB as well as pollutants-degrading microbes in biofilms are crit-
ical for synergistic degradation of refractory compounds. Photocatalysis
can change the relative abundances of dominant microbial populations or
even result in the emergence of different microorganisms. The enrichment
of microbial communities to degrade 2,4,6-trichlorophenol (TCP) in a sin-
gle chamber MFC with a photobiocathode, indicated that relative abun-
dance of Thauera, a TCP-degrading microorganism increased by 7.1% in
biofilms compared to the non-photocathode (Zhu et al., 2021). A clear dif-
ference was observed in cathodic biofilms of photocathode-MFCs and non-
photocathode-MFCs treating 2,4,6-trichlorophenol. Photo-MFCs biofilms
were dominated by Geobacter (55.2%) (an exoelectrogenic microbe)
while in non-photo-MFCs, three genera (Dechlorobacter (8.6%), Thauera
(9.2%) and Arenimonas (4.9%)) had the highest relative abundances, and
the latter two are known to degrade phenol-containing pollutants (Zhu
et al., 2021). Enrichment of Geobacter could facilitate the extracellular elec-
tron transfer on electrodes (as it possesses and outer-membrane cyto-
chromes to transfer electrons), and substantially improve the MESs
performance (Long et al., 2019). A significant increase in the relative abun-
dances of Geobacter after the introduction of photocatalysis was reported by
several studies (Hou et al., 2020; Long et al., 2020; Zhang et al., 2021b).
The relative abundance of Geobacter increased from 6.5% to 12.8%, from
31.64% to 67.73%, and from 7.85% to 27.63% for dark and illuminated
conditions, respectively. MES configuration, inoculum type, and the nature
of recalcitrant pollutants affect the microbial community composition sub-
jected to photocatalysis. In a MES treating TCP, the relative abundance of
Geobacter decreased from 49.7% to 33.3% after illumination. However,
photocatalysis resulted in emergence of Pseudomonas with a relative
R. Rafieenia et al.
abundance of 8.4% (Zhu et al., 2021). Pseudomonas has a critical role in
biofilms as it is associated with the degradation of refractory pollutants
(Wang et al., 2019d). Another recent study showed that light illumination
increased the relative abundance of Pseudomonas from 21.9% to 54.3% in
MFCs with ICPB anode for the treatment of 2,4,6-trichlorophenol (Wang
et al., 2019d). A summary of the most abundant microorganisms detected
in photo-assisted MESs treating recalcitrant wastewaters is shown in
Table 2.
3.2. Photoelectrode-microbe interactions
The type of electrode and its physical and chemical characteristics have
a pivotal role on the adhesion of EAB, microbial growth, and electron trans-
fer to the electrode. Carbon is the most studied electrode material in MESs
as it supports microbial adhesion and biofilm formation (Fischer, 2018).
The electrode interface with EAB plays a key role on EET and subsequently
on MES performance. Some studies reported that the structure of the micro-
bial community of the biofilms and the current output of the MESs are di-
rectly related to the hydrophilicity/hydrophobicity of the electrode (Guo
et al., 2013; Santoro et al., 2014, 2015). These studies suggested that the
relative abundance of EAB on hydrophilic electrode surfaces was higher
than on hydrophobic electrodes, resulting from preferential bacterial adhe-
sion to hydrophilic surfaces during biofilm formation. In addition to the hy-
drophilicity/hydrophobicity of electrode surfaces, the surface charge
affects bacterial attachment and anodic biofilm formation (Santoro et al.,
2015). Positively charged electrode surfaces facilitate the adhesion of
EAB (which are negatively charged) and increase their abundance in the
anodic biofilm (Ishii et al., 2012). Artyushkova et al. investigated how func-
tional properties of S. oneidensis MR-1 biofilms and EET were influenced by
the electrode surface chemistry (Artyushkova et al., 2015). In accordance
with previous studies, they reported that EET to the anode was optimized
using positively charged hydrophilic electrodes. Song et al. fabricated 3D
macroporous graphene/ multiwalled carbon nanotubes (MWCNTs)/Fe3O4
foams to improve the microbial affinity towards S. oneidensis MR-1 (Song
et al., 2016). You et al. constructed a 3D microporous nitrogen-enriched
graphitic carbon scaffold with an open-cell structure (You et al., 2016).
The 3D open-cell structure, highly desirable for biofilm formation, pro-
moted EET and electricity generation by S. oneidensis MR-1. In addition,
the involvement of nitrogen into the graphitic scaffold played a dominant
role in the enhanced EET as it increased the interaction between the
anode and the active center of outer-membrane c-type cytochromes of
S. oneidensis MR-1. The feasibility of EET from electrogenic microorganisms
to photo-excited electrodes has been investigated by several researchers (Li
et al., 2014; Qian et al., 2014; Xiao et al., 2019; Zhou et al., 2018). Gene-
knock out experiments performed on Geobacter sulfurreducens revealed
that OmcB, an outer-membrane Cytochrome c, was the most important
electron carrier involved in EET from the organism to a CdS photocatalyst
(Huang et al., 2019). Another study indicated that in the presence of a
TiO2 photocatalyst, the expression levels of extracellular pilA protein in-
creased, resulting in the formation of conductive nanowires and the conse-
quent improvement of EET (Do et al., 2019). Some examples of electrode
materials used as a carrier in biophotoanodes include carbon foam (Zhou
Table 2
Abundant microorganisms enriched in photoassisted-MESs treating various recalcitrant compounds.
Source of inoculum Recalcitrant pollutant Source of biofilm Abundant microbial species without Abundant microbial species with illumination
illumination
Domestic wastewater Rhodamine B Biocathode – Acinetobacter (41.5%) and Shewanella (4.51%)
Domestic wastewater Nitrofurazone Bioanode Geobacter (31.64%)
Wetland MFC Aniline Biophotoanode Geobacter (6.5%)
Municipal wastewater 2,4,6-Trichlorophenol ICPB anode Pseudomonas (21.9%), Rhodococcus
(11.5%)
Anaerobic sludge Oxytetracycline Bioanode Geobacter (7.85%)
Municipal wastewater 2,4,6-trichlorophenol Bioanode Geobacter (49.7%) and Azospirillum
(8.5%)
Municipal wastewater 2,4,6-trichlorophenol Biophoto-cathode Geobacter (55.2%) and Thauera
(7.1%)
8
Science of the Total Environment 824 (2022) 153923
Fig. 3. Synergistic effect of photocatalysis and biofilms to degrade recalcitrant
pollutants in photo-assisted MESs.
et al., 2017), polyurethane sponge (Cai et al., 2019; Ding et al., 2018), car-
bon fiber (Zou et al., 2020), and carbon brush (Zou et al., 2021). These stud-
ies indicated that extracellular electrons released by EAB were attracted by
photocatalysts and acted as hole scavengers. Thus, the photo-excited elec-
trodes generate electrons for the photocatalytic degradation of pollutants
(Fig. 3). On the other hand, EAB can use photo-generated electrons for
cell maintenance and stimulated growth (Deng et al., 2020).
The interaction between biofilms and photocatalysts may not always re-
sult in better performances.
Intermediates produced during photocatalysis, including free radicals,
could attack biofilm microorganisms, damaging their cell wall and
inhibiting cellular growth, and eventually causing cell death (Deng et al.,
2020). To avoid any unnecessary damage to biofilm, the rate of photocata-
lytic processes need to be controlled to inhibit the accumulation of harmful
substances, resulting in the fast biodegradation of photocatalytic byproducts
(Yu et al., 2020a). It is critical to explore the photocatalysis byproducts and
their formation rates by analytical methods such as spectroscopy and chro-
matography to control the photocatalytic process and eventually optimize
the synergistic degradation of pollutants (Zhang et al., 2022).
In a recent study, the anodic microbial community structure was stud-
ied for MFCs consisting of a bioanode and a BiOCl/reduced graphene
oxide aerogel (BGA) photocathode. Photocathode irradiation increased
the cathodic reaction rate compared to dark conditions, improved electron
transfer, and subsequently resulted in the enrichment of EAB on anodic
biofilms. Applying a photocathode was correlated with higher abundances
of Geobacter, the most typical EAB. Geobacter could use nanowires and
outer-membrane cytochromes which facilitates the extracellular electron
transfer, resulting in higher performance of MFCs (Zhang et al., 2021b).
Degradation of pollutants by photo-assisted MESs could be significantly
affected by microbial diversity and the choice of photocatalysts. It has been
reported that the microbial community structure of biofilms was different
with varying loading amounts of the photocatalyst. Also, photocatalyst
load was reported to have a significant impact on mass transfer, oxygen dif-
fusion, nutrient supply, biofilm resistance, and microbial diversity (Zhang
et al., 2022; Zhu et al., 2021). Therefore, an optimized amount of
Reference
(Sui et al., 2017)
Geobacter (67.73%) (Hou et al., 2020)
Geobacter (12.8%) (Long et al., 2020)
Pseudomonas (54.3%), Rhodococcus (6.8%) (Wang et al., 2019d)
Geobacter (27.63%) (Zhang et al., 2021b)
Geobacter (33.3%), Pseudomonas (8.4%) and (Zhu et al., 2021)
Azospirillum (8.1%)
Dechlorobacter (8.6%), Thauera (9.2%) and (Zhu et al., 2021)
Arenimonas (4.9%)
R. Rafieenia et al.
photocatalyst could improve the activity of the anodic biofilm, resulting in
enhanced electrochemical performance and pollutant degradation.
Photo-enhanced EET could open new possibilities to improve pollutant
degradation and productivity of MESs. There is a lack of detailed information
on mechanisms of synergistic effects between biofilms and photocatalysts.
Understanding of the mechanisms of interaction between EAB and
photoelectrodes is essential to promote its widespread application. In addi-
tion, the design and fabrication of low-cost, efficient, and biocompatible
photocatalysts are necessary to enhance the synergistic effect between EAB
and photocatalysts.
4. Relieving toxicity of recalcitrant compounds on microorganisms
4.1. Substrate and by-product inhibition
In the bioelectrochemical degradation of recalcitrant compounds,
mixed microbial communities are often preferred as the contaminant-
degrading species, although they are not entirely electroactive. The recalci-
trant compounds can be degraded by planktonic microorganisms and/or
microorganisms in the electroactive biofilm, while the electroactive micro-
organisms grow by oxidizing the metabolites in the biofilm (Xu et al.,
2019). However, the contaminants can limit the growth of the electroactive
microorganisms if they exceed a threshold inhibitory limit. For example, Li
et al. studied the effect of formaldehyde on the electroactive microorgan-
isms and observed a 27% decrease in current with formaldehyde concentra-
tions as low as 1 ppm, while at 10 ppm the decrease was as high as 98% (Li
et al., 2020). Khan et al. observed that azo-dyes started to inhibit the
electroactive microorganisms when their concentration increased above
200 ppm (Danish Khan et al., 2015). While the toxicity of the recalcitrant
compounds could be reduced, for example, via chemical pre-treatment,
this would increase the cost of the process significantly. As the electroactive
microorganisms often form a biofilm, the outer layer of the biofilm can pro-
tect the inner electroactive microorganisms from any toxic substrates.
Bioelectrochemical systems have been used to treat waste streams contain-
ing phenolic compounds at concentrations higher than the minimal inhibi-
tory concentration (Marone et al., 2016).
The simple organic metabolites formed in the degradation of the con-
taminants are often good electron donors for the electroactive microorgan-
isms, but the formed metabolites can also be toxic to the microbial
communities. The bioelectrochemical degradation of halogenated com-
pounds can lead to the release of lower-grade chlorinated compounds
such as cis-1,2-dichloroethene (Chen et al., 2018), or even more toxic
vinyl chloride (Lai et al., 2015). The decolorization of azo dyes often
leads to the release of toxic metabolites (such as phenylenediamine and
5-aminosalicylic acid) which cannot be bioelectrochemically degraded
(Cui et al., 2020). To prevent the release of the toxic compounds to the en-
vironment, the effluent from the bioelectrochemical systems might require
post-treatment. Pan et al. integrated a membrane-less bioelectrochemical
system with a bio-contact oxidation reactor to degrade the toxic decolor-
ized byproducts of azo dye (Pan et al., 2017).
In the bioelectrochemical treatment of antibiotic-containing wastewa-
ters, the tolerance of the electroactive microorganisms to the antibiotics
can increase, resulting from the horizontal transfer of antibiotic resistance
genes from the antibiotic-degrading microorganisms to the electroactive mi-
croorganisms. The spreading of antibiotic resistance among microorganisms
constitutes, however, a significant health risk, and the release of antibiotic-
resistant microorganisms to the environment should be prevented. The
bioelectrochemical degradation of antibiotics and the transfer of antibiotic
resistance genes have been extensively reviewed elsewhere (Yan et al.,
2019). Integration of MESs and photocatalysis has the advantage of reducing
the spread of antibiotic-resistance genes. Due to the fast breakdown of anti-
biotics by photocatalysis, the chance of transfer of antibiotic-resistance
genes for microorganisms is reduced. A recent study indicated that the
biotoxicity of oxytetracycline was largely eliminated in MESs combined
with photocatalysis (Zhang et al., 2021b). Besides antibiotics, toxicity of
other recalcitrant pollutants on microorganisms might be alleviated when
9
Science of the Total Environment 824 (2022) 153923
MESs coupled with photocatalysis. As mentioned in section 2, photocatalysts
transforms recalcitrant substrates into less toxic compounds, and subse-
quently reduce their toxic effects on biofilm microorganisms. Liu et al. re-
ported that biotoxicity and mutagenicity of diclofenac was reduced during
photocatalysis (Liu et al., 2019). It should be noted that many photocatalysts
include toxic metals that might be deleterious to biofilm bacteria. Therefore,
the choice of efficient photocatalysts with negligible biotoxicity is critical
when designing the combined systems. Some studies used single species
such as E. coli to analyse the biotoxicity of pollutants and/or photocatalysts
during photocatalysis (2021). Although single species could be useful in
biotoxicity experiments, their responses towards toxics exposure might be
different from mixed microbial communities. Moreover, the microbial resis-
tance towards toxic compounds varies between different species. Hence, the
composition of microbial community has a significant effect on the tolerance
to toxicity.
4.2. Alternative electron acceptors
MESs are usually operated in anaerobic conditions since the intrusion of
oxygen decreases the Coulombic efficiency by acting as an alternative
electron acceptor; however, the presence of low oxygen concentrations
(microaerophilic conditions) can be beneficial, as it can accelerate the biodeg-
radation of recalcitrant compounds. The biodegradation of aromatic amines
among other recalcitrant compounds proceeds naturally via aerobic oxida-
tion and, unlike oxygen, the anode electrode cannot activate oxygenases
and thus cannot completely replace oxygen as the electron acceptor (Cheng
et al., 2015). Faster and more complete degradation of phenolic compounds
has been observed in microaerophilic conditions than in completely anaero-
bic conditions. Cheng et al. studied the bioelectrochemical degradation of an-
iline on the anode of a two-chamber microbial fuel cell and obtained a
removal efficiency of 91.2 ± 2.2% in micro-aerophilic conditions, while in
anaerobic conditions the removal efficiency did not exceed 15.8 ± 1.1%
(Cheng et al., 2015). However, the Coulombic efficiency for anaerobic MFC
was much higher than in microaerophilic conditions (11.9 ± 0.5% versus
5.1 ± 0.5%), implying that the current generation was mainly due to the ox-
idation of the formed metabolites rather than directly from the degradation of
aniline (Cheng et al., 2015). Similarly, Khan et al. observed that aeration in-
creased the removal of p-nitrophenol from 4% to 99.89% as compared to an-
aerobic bioelectrochemical degradation, which is consistent with other
research studies (Khan et al., 2019; Yang et al., 2018; Zhou et al., 2020).
Even though the anode chamber would not be intentionally aerated, ox-
ygen can leak through the membrane separating the anodic and cathodic
chambers. As high oxygen concentrations could also inhibit the growth of
EAB, aerobic microorganisms can thus assist in maintaining the oxygen con-
centrations at a level tolerated by electroactive microorganisms. Several
oxygen-respiring species have been detected from the anodic microbial
communities even when oxygen has not been intentionally provided to
the anode. Wang et al. studied the bioelectrochemical degradation of petro-
leum hydrocarbons and detected a high abundance of aerobic hydrocarbon-
degrading bacteria (Wang et al., 2019a). Oxygen is the main stimulant for
the oxidation of toxic recalcitrant compounds, but also other electron accep-
tors, such as sulfate, can assist in the degradation of contaminants by provid-
ing more reductive stress. Miran et al. provided sulfate as an alternative
electron acceptor for sulfate-reducing bacteria degrading chlorinated phe-
nol in the anode of a microbial fuel cell, but the chlorophenol removal
rate remained at 18.9% (Miran et al., 2017).
4.3. Co-metabolism strategy
The presence of additional more easily degradable electron donors can
enhance the degradation of certain recalcitrant compounds due to the in-
duction of oxidizing enzymes and the proliferation of microorganisms
(Friman et al., 2013). Shen et al. studied the co-metabolism of phenols
and several organic compounds and observed that higher phenol removal
rates were obtained in the presence of acetate (78.8%) than in the presence
of glucose (74.1%), sucrose (72.0%), or ethanol (63.9%) (Shen et al.,
R. Rafieenia et al.
2020). Yu et al. studied the degradation of chlorophenol in the presence of
acetate and the chlorophenol removal rate increased up to 93.7% (Yu et al.,
2019). Co-metabolism has also been observed to enhance the degradation
of 2,4,6-trichlorophenol (H. Xu et al., 2018b), and p-nitrophenol (Zhao
and Kong, 2018). The presence of an alternative electron donor not only as-
sists in reducing the toxicity of recalcitrant compounds, but also enhances
the electricity output, although the external addition of such organic com-
pounds can decrease the cost-effectiveness of the system. However, easily
degradable electron donors can significantly improve the stability and en-
ergy output of the bioelectrochemical treatment, especially for long-term
operation (Zhao and Kong, 2018).
5. Summary, challenges, and future perspective
Recalcitrant pollutant removal by MESs suffers from poor efficiencies
due to their inhibitory effect on electrogenic microorganisms and low bio-
degradability. Integrated MESs combining photocatalysis and biodegrada-
tion is an emerging technology and is expected to be a hot topic in the
field of wastewater treatment. Considering the number of publications,
the use of photo-assisted MESs is still negligible in comparison with stan-
dard MESs.
Nevertheless, the scarce data available strongly suggests that MESs com-
bining photocatalysis and microbial degradation show considerably high
removal efficiencies for recalcitrant pollutants. However, there is still a
lack of knowledge on synergistic mechanisms affecting pollutant degrada-
tion. In addition, this technology is still nascent and its application has
not been reported yet for other applications such as chemicals and fuels pro-
duction, soil remediation, and fabrication of biosensors. This opens up op-
portunities to new research fields for sustainable applications of coupled
systems.
To optimize the integrated configuration, various operational and de-
sign parameters (e.g. coating ratio of photocatalysts, carriers, light source
and intensity, reactor structure, and cost-effectiveness) need to be consid-
ered. Choice of economic photocatalysts which are yet stable towards
photocorrosion is crucial to enhance the degradation efficiency of refractory
pollutants at minimum operational cost. Loading amount of photocatalyst is
another critical factor to be considered, as it has a significant impact on ox-
ygen diffusion, mass transfer, and bioactivity of electrode biofilms (Zhu
et al., 2021). Monitoring microbial community dynamics in photo-assisted
MESs is critical for exploring synergistic effects on emerging pollutants re-
moval and degradation metabolic pathways. There are only a few studies
reporting the abundance of microbial species in composite electrode
biofilms subjected to light illumination.
The current photo-assisted MESs are confronted with certain limitations.
There is a lack of understanding of the degradation mechanisms in realistic
environments due to the complicated interactions among photocatalysts,
contaminants, and biofilms. Also, the attack of free radicals to complex pol-
lutants present in actual wastewaters can result in the production of harmful
substances (Zhang et al., 2022). Thus, efficient analytical techniques are re-
quired to detect low-concentrations of hazardous compounds during the
MESs operation. In the case of composite biophotoelectrodes, ICPB seems
to be a promising configuration as it protects microorganisms from UV
light and free radicals attack. However, the synergistic degradation of re-
fractory pollutants, especially in complex matrices, has not been elucidated
yet. There is a lack of detailed information on interactions between micro-
bial species in MESs biofilms treating multiple pollutants or actual recalci-
trant wastewaters and the corresponding mechanisms of photoenhanced
degradation.
As a newly developed technology, photo-assisted MESs has not been
studied at pilot scale yet. A major difficulty for scaling up is to maintain
the system efficiency, a challenging task due to the reduced EET efficiencies
as well as the increased energy loss (Kadier et al., 2020; Li et al., 2018).
Moreover, adequate light distribution inside the reactors, high surface
areas for the photocatalysts, and the cost of production for photobioreactors,
are the most important issues to be considered for scale-up (Vinayak et al.,
2021; Zuo et al., 2021). Another issue towards the industrial application
10
Science of the Total Environment 824 (2022) 153923
of photo-assisted MESs is the lack of studies performed using real wastewa-
ters. Currently, all the published studies on integrated MESs have used syn-
thetic wastewater with one single pollutant. To promote the scale-up of
photo-assisted MESs, synthetic wastewaters containing multiple recalcitrant
pollutants in the first stage and real recalcitrant wastewaters in the second
stage need to be studied in photo-assisted MESs. This is an exciting area
for research, and the need for environmentally friendly, sustainable ap-
proaches for wastewater treatment ensure impressive technological ad-
vances in the next few years.
CRediT authorship contribution statement
Razieh Rafieenia: Conceptualization, Investigation, Writing most of the
original draft, Reviewing, and Editing, Mira Sulonen: Investigation, Writing
original draft, Mohamed Mahmoud: Conceptualization, Reviewing, and
Editing, Fatma-El-Gohary: Reviewing, and Editing, Funding acquisition,
Claudio Avignone Rossa: Conceptualization, Supervision, Reviewing, and
Editing, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgments
RR, MM, FE-G and CAR are supported by an Institutional Link Grant from
the British Council (Newton-Mosharafa Fund) (Grant no. 352368074) and the
Science, Technology, and Innovation Funding Authority (STIFA), Egypt
(Grant no. 30901). MS and CAR would like to acknowledge support by the
EU Horizon 2020 Research project GREENER (Grant Agreement No. 826312).
References
Al Qarni, H., Collier, P., O’Keeffe, J., Akunna, J., 2016. Investigating the removal of some
pharmaceutical compounds in hospital wastewater treatment plants operating in Saudi
Arabia. Environ. Sci. Pollut. Res. 23, 13003–13014. https://doi.org/10.1007/s11356-
016-6389-7.
Anh Pham, C., Je Jung, S., Thu Phung, N., Lee, J., Seop Chang, I., Hong Kim, B., Yi, H., Chun,
J., 2003. A Novel Electrochemically Active and Fe(III)-reducing Bacterium Phylogeneti-
cally Related to Aeromonas Hydrophila, Isolated From a Microbial Fuel Cell. https://
doi.org/10.1016/S0378-1097(03)00354-9.
Anju Chanu, L., Joychandra Singh, W., Jugeshwar Singh, K., Nomita Devi, K., 2019. Effect of
operational parameters on the photocatalytic degradation of methylene blue dye solution
using manganese doped ZnO nanoparticles. Res. Phys. 12, 1230–1237. https://doi.org/
10.1016/J.RINP.2018.12.089.
Ansari, S.A., Khan, M.M., Ansari, M.O., Cho, M.H., 2016. Nitrogen-doped titanium dioxide (N-
doped TiO2) for visible light photocatalysis. New J. Chem. 40, 3000–3009. https://doi.
org/10.1039/c5nj03478g.
Antolini, E., 2019. Photoelectrocatalytic fuel cells and photoelectrode microbial fuel cells for
wastewater treatment and power generation. J. Environ. Chem. Eng. 7, 103241. https://
doi.org/10.1016/J.JECE.2019.103241.
Artyushkova, K., Cornejo, J.A., Ista, L.K., Babanova, S., Santoro, C., Atanassov, P., Schuler,
A.J., 2015. Relationship between surface chemistry, biofilm structure, and electron trans-
fer in shewanella anodes. Biointerphases 10, 019013. https://doi.org/10.1116/1.
4913783.
Banerjee, S., Pillai, S.C., Falaras, P., O’Shea, K.E., Byrne, J.A., Dionysiou, D.D., 2014. New in-
sights into the mechanism of visible light photocatalysis. J. Phys. Chem. Lett. 5,
2543–2554. https://doi.org/10.1021/jz501030x.
Boningari, T., Inturi, S.N.R., Suidan, M., Smirniotis, P.G., 2018. Novel one-step synthesis of
sulfur doped-TiO2 by flame spray pyrolysis for visible light photocatalytic degradation
of acetaldehyde. Chem. Eng. J. 339, 249–258. https://doi.org/10.1016/J.CEJ.2018.01.
063.
Cai, H., Sun, L., Wang, Y., Song, T., Bao, M., Yang, X., 2019. Unprecedented efficient degrada-
tion of phenanthrene in water by intimately coupling novel ternary composite Mn3O4/
MnO2-Ag3PO4 and functional bacteria under visible light irradiation. Chem. Eng. J.
369, 1078–1092. https://doi.org/10.1016/J.CEJ.2019.03.143.
Chang, C.J., Yang, T.L., Weng, Y.C., 2014. Synthesis and characterization of cr-doped ZnO
nanorod-array photocatalysts with improved activity. J. Solid State Chem. 214,
101–107. https://doi.org/10.1016/J.JSSC.2013.09.039.
Chen, F., Li, Z., Yang, J., Liang, B., Huang, C., Cai, W., Nan, J., Wang, A., 2018. Citation: elec-
tron fluxes in biocathode bioelectrochemical systems performing dechlorination of chlo-
rinated aliphatic hydrocarbons. Front. Microbiol. 9, 2306. https://doi.org/10.3389/
fmicb.2018.02306.
R. Rafieenia et al.
Chen, Xi, Katahira, R., Ge, Z., Lu, L., Hou, D., Peterson, D.J., Tucker, M.P., Chen, Xiaowen,
Jason Ren, Z., 2019. Microbial electrochemical treatment of biorefinery black liquor
and resource recovery. Green Chem. 21. https://doi.org/10.1039/c8gc02909a.
Chen, Y., Shen, J., Huang, L., Pan, Y., Quan, X., 2016. Enhanced Cd(II) removal with simulta-
neous hydrogen production in biocathode microbial electrolysis cells in the presence of
acetate or NaHCO3. Int. J. Hydrog. Energy 41, 13368–13379. https://doi.org/10.1016/
J.IJHYDENE.2016.06.200.
Cheng, H.Y., Liang, B., Mu, Y., Cui, M.H., Li, K., Wu, W.M., Wang, A.J., 2015. Stimulation of
oxygen to bioanode for energy recovery from recalcitrant organic matter aniline in micro-
bial fuel cells (MFCs). Water Res. 81, 72–83. https://doi.org/10.1016/J.WATRES.2015.
05.012.
Croese, E., Pereira, M.A., Euverink, G.-J.W., Stams, A.J.M., Geelhoed, J.S., 2011. Analysis of
the microbial community of the biocathode of a hydrogen-producing microbial electrol-
ysis cell. Appl. Microbiol. Biotechnol. 92, 1083–1093. https://doi.org/10.1007/s00253-
011-3583-x.
Croese, E., Jeremiasse, A.W., Marshall, I.P.G., Spormann, A.M., Euverink, G.J.W., Geelhoed,
J.S., Stams, A.J.M., Plugge, C.M., 2014. Influence of setup and carbon source on the bac-
terial community of biocathodes in microbial electrolysis cells. Enzym. Microb. Technol.
61–62, 67–75. https://doi.org/10.1016/J.ENZMICTEC.2014.04.019.
Cui, D., Cui, M.H., Liang, B., Liu, W.Z., Tang, Z.E., Wang, A.J., 2020. Mutual effect between
electrochemically active bacteria (EAB) and azo dye in bio-electrochemical system
(BES). Chemosphere 239, 124787. https://doi.org/10.1016/J.CHEMOSPHERE.2019.
124787.
Danish Khan, M., Abdulateif, H., Ismail, I.M., Sabir, S., Zain Khan, M., 2015. Bioelectricity
Generation and Bioremediation of an Azo-Dye in a Microbial Fuel Cell Coupled Activated
Sludge Process. https://doi.org/10.1371/journal.pone.0138448.
Deng, Y., Zhao, R., 2015. Advanced Oxidation Processes (AOPs) in Wastewater Treatment.
https://doi.org/10.1007/s40726-015-0015-z.
Deng, Y., Li, Z., Tang, R., Ouyang, K., Liao, C., Fang, Y., Ding, C., Yang, L., Ab, L.S., Gong, D.,
2020. Environmental science nano critical review what will happen when microorgan-
isms “meet” photocatalysts and photocatalysis? Cite this. Environ. Sci.: Nano 7, 702.
https://doi.org/10.1039/c9en01318k.
Dewan, A., Beyenal, H., Lewandowski, Z., 2008. Scaling up microbial fuel cells. Environ. Sci.
Technol. 42, 7643–7648. https://doi.org/10.1021/es800775d.
Ding, H., Li, Y., Lu, A., Jin, S., Quan, C., Wang, C., Wang, X., Zeng, C., Yan, Y., 2010.
Photocatalytically improved azo dye reduction in a microbial fuel cell with rutile-
cathode. Bioresour. Technol. 101, 3500–3505. https://doi.org/10.1016/J.BIORTECH.
2009.11.107.
Ding, R., Yan, W., Wu, Y., Xiao, Y., Gang, H., Wang, S., Chen, L., Zhao, F., 2018. Light-excited
photoelectrons coupled with bio-photocatalysis enhanced the degradation efficiency of
oxytetracycline. Water Res. 143, 589–598. https://doi.org/10.1016/J.WATRES.2018.
06.068.
Divya Priya, A., Deva, S., Shalini, P., Pydi Setty, Y., 2020. Antimony-tin based intermetallics
supported on reduced graphene oxide as anode and MnO2@rGO as cathode electrode
for the study of microbial fuel cell performance. Renew. Energy 150, 156–166. https://
doi.org/10.1016/J.RENENE.2019.12.109.
Do, T.C.M.V., Nguyen, D.Q., Nguyen, K.T., Le, P.H., 2019. TiO2 and au-TiO2 nanomaterials
for rapid photocatalytic degradation of antibiotic residues in aquaculture wastewater.
Materials 12. https://doi.org/10.3390/ma12152434.
Dong, H., Zeng, G., Tang, L., Fan, C., Zhang, C., He, X., He, Y., 2015. An overview on limita-
tions of TiO2-based particles for photocatalytic degradation of organic pollutants and the
corresponding countermeasures. Water Res. 79, 128–146. https://doi.org/10.1016/J.
WATRES.2015.04.038.
Du, Y., Feng, Y., Dong, Y., Qu, Y., Liu, J., Zhou, X., Ren, N., 2014a. Coupling Interaction of Ca-
thodic Reduction and Microbial Metabolism in Aerobic Biocathode of Microbial Fuel Cell
†. https://doi.org/10.1039/c4ra03441d.
Du, Y., Feng, Y., Qu, Y., Liu, J., Ren, N., Liu, H., 2014b. Electricity Generation and Pollutant
Degradation Using a Novel Biocathode Coupled Photoelectrochemical Cell. https://doi.
org/10.1021/es5011994.
Du, Y., Zhou, X., Qu, Y., Liu, J., Feng, Y., Ren, N., 2017. Enhanced electricity generation and
pollutant degradation by hybrid photoelectrochemical and microbial fuel cells. Energy
Technol. 5, 402–405. https://doi.org/10.1002/ente.201600339.
Escapa, A., Mateos, R., Martínez, E.J., Blanes, J., 2016. Microbial electrolysis cells: an emerg-
ing technology for wastewater treatment and energy recovery. From laboratory to pilot
plant and beyond. Renew. Sust. Energ. Rev. 55, 942–956. https://doi.org/10.1016/J.
RSER.2015.11.029.
Fedorovich, V., Knighton, M.C., Pagaling, E., Ward, F.B., Free, A., Goryanin, I., 2009. Novel
electrochemically active bacterium phylogenetically related to arcobacter butzleri, iso-
lated from a microbial fuel cell. Appl. Environ. Microbiol. 75, 7326–7334. https://doi.
org/10.1128/AEM.01345-09.
Feng, H., Liang, Y., Guo, K., Li, N., Shen, D., Cong, Y., Zhou, Y., Wang, Y., Wang, M., Long, Y.,
2016. Hybridization of photoanode and bioanode to enhance the current production of
bioelectrochemical systems. Water Res. 102, 428–435. https://doi.org/10.1016/J.
WATRES.2016.06.061.
Fernando, E.Y., Keshavarz, T., Kyazze, G., 2018. The Use of Bioelectrochemical Systems in En-
vironmental Remediation of Xenobiotics: A Review. https://doi.org/10.1002/jctb.5848.
Fischer, F., 2018. Photoelectrode, photovoltaic and photosynthetic microbial fuel cells.
Renew. Sust. Energ. Rev. 90, 16–27. https://doi.org/10.1016/J.RSER.2018.03.053.
Friman, H., Schechter, A., Nitzan, Y., Cahan, R., 2013. Phenol degradation in bio-
electrochemical cells. Int. Biodeterior. Biodegradation 84, 155–160. https://doi.org/10.
1016/J.IBIOD.2012.04.019.
Gadkari, S., Fontmorin, J.M., Yu, E., Sadhukhan, J., 2020. Influence of temperature and other
system parameters on microbial fuel cell performance: numerical and experimental inves-
tigation. Chem. Eng. J. 388, 124176. https://doi.org/10.1016/J.CEJ.2020.124176.
Gomes, J., Domingues, E., Gmurek, M., Quinta-Ferreira, R.M., Martins, R.C., 2020. Advanced
oxidation processes for recalcitrant compounds removal comparison with biofiltration by
11
Science of the Total Environment 824 (2022) 153923
Corbicula fluminea. Energy Rep. 6, 666–671. https://doi.org/10.1016/J.EGYR.2019.09.
047.
Goswami, R., Mishra, V.K., 2017. A Review of Design, Operational Conditions and Applica-
tions of Microbial Fuel Cells. https://doi.org/10.1080/17597269.2017.1302682.
Guayaquil-Sosa, J.F., Calzada, A., Serrano, B., Escobedo, S., De Lasa, H., 2017. Hydrogen Pro-
duction via Water Dissociation Using Pt-TiO 2 Photocatalysts: An Oxidation-Reduction
Network. https://doi.org/10.3390/catal7110324.
Gude, V.G., 2016. Wastewater treatment in microbial fuel cells – an overview. J. Clean. Prod.
122, 287–307. https://doi.org/10.1016/J.JCLEPRO.2016.02.022.
Guo, K., Freguia, S., Dennis, P.G., Chen, X., Donose, B.C., Keller, J., Gooding, J.J., Rabaey, K.,
2013. Effects of Surface Charge and Hydrophobicity on Anodic Biofilm Formation, Com-
munity Composition, and Current Generation in Bioelectrochemical Systems. https://
doi.org/10.1021/es400901u.
Guo, K., Prévoteau, A., Patil, S.A., Rabaey, K., 2015. Engineering electrodes for microbial
electrocatalysis. Curr. Opin. Biotechnol. 33, 149–156. https://doi.org/10.1016/J.
COPBIO.2015.02.014.
Gupta, A., Thakur, I.S., 2017. Treatment of organic recalcitrant contaminants in wastewater.
Biol. Wastewater Treat. Resour. Recover. https://doi.org/10.5772/66346.
Han, H.X., Shi, C., Yuan, L., Sheng, G.P., 2017. Enhancement of methyl orange degradation
and power generation in a photoelectrocatalytic microbial fuel cell. Appl. Energy 204,
382–389. https://doi.org/10.1016/J.APENERGY.2017.07.032.
He, D., Li, Y., Wang, I., Wu, J., Yang, Y., An, Q., 2017. Carbon wrapped and doped TiO2 meso-
porous nanostructure with efficient visible-light photocatalysis for NO removal. Appl.
Surf. Sci. 391, 318–325. https://doi.org/10.1016/J.APSUSC.2016.06.186.
Hodgson, D.M., Smith, A., Dahale, S., Stratford, J.P., Li, J.V., Grüning, A., Bushell, M.E.,
Marchesi, J.R., Rossa, C.A., 2016. Segregation of the anodic microbial communities in a
microbial fuel cell cascade. Front. Microbiol. 7. https://doi.org/10.3389/fmicb.2016.
00699.
Hou, Y., Gan, Y., Yu, Z., Chen, X., Qian, L., Zhang, B., Huang, L., Huang, J., 2017a. Solar pro-
moted azo dye degradation and energy production in the bio-photoelectrochemical sys-
tem with a g-C3N4/BiOBr heterojunction photocathode. J. Power Sources 371, 26–34.
https://doi.org/10.1016/J.JPOWSOUR.2017.10.033.
Hou, Y., Zhang, R., Yu, Z., Huang, L., Liu, Y., Zhou, Z., 2017b. Accelerated azo dye degrada-
tion and concurrent hydrogen production in the single-chamber photocatalytic microbial
electrolysis cell. Bioresour. Technol. 224, 63–68. https://doi.org/10.1016/J.BIORTECH.
2016.10.069.
Hou, Y., Yuan, G., Qin, S., Tu, L., Yan, Y., Yu, Z., Lin, H., Chen, Y., Zhu, H., Song, H., Wang, S.,
2020. Photocathode optimization and microbial community in the solar-illuminated bio-
photoelectrochemical system for nitrofurazone degradation. Bioresour. Technol. 302,
122761. https://doi.org/10.1016/J.BIORTECH.2020.122761.
Hua, T., Li, S., Li, F., Ondon, B.S., Liu, Y., Wang, H., 2019. Degradation performance and mi-
crobial community analysis of microbial electrolysis cells for erythromycin wastewater
treatment. Biochem. Eng. J. 146, 1–9. https://doi.org/10.1016/J.BEJ.2019.02.008.
Huang, L., Cheng, S., Chen, G., 2011. Bioelectrochemical Systems for Efficient Recalcitrant
Wastes Treatment. https://doi.org/10.1002/jctb.2551.
Huang, S., Tang, J., Liu, X., Dong, G., Zhou, S., 2019. Fast light-driven biodecolorization by a
geobacter sulfurreducens –CdS biohybrid. ACS Sustain. Chem. Eng. 7, 15427–15433.
https://doi.org/10.1021/acssuschemeng.9b02870.
Huang, W., Chen, J., Hu, Y., Zhang, L., 2018. Enhancement of Congo red decolorization by
membrane-free structure and bio-cathode in a microbial electrolysis cell. Electrochim.
Acta 260, 196–203. https://doi.org/10.1016/J.ELECTACTA.2017.12.055.
Ishii, S., Watanabe, K., Yabuki, S., Logan, B.E., Sekiguchi, Y., 2008. Comparison of electrode
reduction activities of geobacter sulfurreducens and an enriched consortium in an air-
cathode microbial fuel cell. Appl. Environ. Microbiol. 74, 7348–7355. https://doi.org/
10.1128/AEM.01639-08.
Ishii, S., Suzuki, S., Norden-Krichmar, T.M., Nealson, K.H., Sekiguchi, Y., 2012. Functionally
stable and phylogenetically diverse microbial enrichments from microbial fuel cells dur-
ing wastewater treatment. PLoS ONE 7, 30495. https://doi.org/10.1371/journal.pone.
0030495.
Jayashree, C., Sweta, S., Arulazhagan, P., Yeom, I.T., Iqbal, M.I.I., Rajesh Banu, J., 2015. Elec-
tricity generation from retting wastewater consisting of recalcitrant compounds using
continuous upflow microbial fuel cell. Biotechnol. Bioprocess Eng. 20, 753–759.
https://doi.org/10.1007/s12257-015-0017-0.
Kadier, A., Kalil, M.S., Abdeshahian, P., Chandrasekhar, K., Mohamed, A., Azman, N.F.,
Logroño, W., Simayi, Y., Hamid, A.A., 2016. Recent advances and emerging challenges
in microbial electrolysis cells (MECs) for microbial production of hydrogen and value-
added chemicals. Renew. Sust. Energ. Rev. 61, 501–525. https://doi.org/10.1016/J.
RSER.2016.04.017.
Kadier, A., Jain, P., Lai, B., Kalil, M.S., Kondaveeti, S., Alabbosh, K.F.S., Abu-Reesh, I.M.,
Mohanakrishna, G., 2020. Biorefinery perspectives of microbial electrolysis cells
(MECs) for hydrogen and valuable chemicals production through wastewater treatment.
Biofuel Res. J. 7, 1128–1142. https://doi.org/10.18331/BRJ2020.7.1.5.
Keong Ngaw, C., Wang, V.B., Liu, Z., Zhou, Y., Kjelleberg, S., Zhang, Q., Thatt, T., Tan, Y.,
Chye, S., Loo, J., 2015. ARTICLE OPEN Enhancement in Hydrogen Evolution Using Au-
TiO 2 Hollow Spheres With Microbial Devices Modified With Conjugated
Oligoelectrolytes 1. https://doi.org/10.1038/npjbiofilms.2015.20.
Khan, A., Chen, Z., Zhao, S., Ni, H., Pei, Y., Xu, R., Ling, Z., Salama, E.S., Liu, P., Li, X., 2019.
Micro-aeration in anode chamber promotes p-nitrophenol degradation and electricity
generation in microbial fuel cell. Bioresour. Technol. 285, 121291. https://doi.org/10.
1016/J.BIORTECH.2019.03.130.
Kim, B.H., Seop Chang, I., Gadd, G.M., 2007. Challenges in microbial fuel cell development
and operation. Appl. Microbiol. Biotechnol. 76, 485–494. https://doi.org/10.1007/
s00253-007-1027-4.
Kim, B.H., Lim, S.S., Daud, W.R.W., Gadd, G.M., Chang, I.S., 2015. The biocathode of micro-
bial electrochemical systems and microbially-influenced corrosion. Bioresour. Technol.
190, 395–401. https://doi.org/10.1016/J.BIORTECH.2015.04.084.
R. Rafieenia et al.
Kim, M.Y., Kim, C., Ainala, S.K., Bae, H., Jeon, B.H., Park, S., Kim, J.R., 2019. Metabolic shift
of Klebsiella pneumoniae L17 by electrode-based electron transfer using glycerol in a mi-
crobial fuel cell. Bioelectrochemistry 125, 1–7. https://doi.org/10.1016/J.BIOELECHEM.
2018.08.002.
Kundu, A., Sahu, J.N., Redzwan, G., Hashim, M.A., 2013. An overview of cathode material
and catalysts suitable for generating hydrogen in microbial electrolysis cell. Int.
J. Hydrog. Energy 38, 1745–1757. https://doi.org/10.1016/J.IJHYDENE.2012.11.031.
Kurt, A., Mert, B.K., Özengin, N., Sivrioğlu, Ö., Yonar, T., 2017. Treatment of antibiotics in
wastewater using advanced oxidation processes (AOPs). Physico-Chemical Wastewater
Treatment and Resource Recovery https://doi.org/10.5772/67538.
Lai, A., Verdini, R., Aulenta, F., Majone, M., 2015. Influence of nitrate and sulfate reduction in
the bioelectrochemically assisted dechlorination of cis-DCE. Chemosphere 125, 147–154.
https://doi.org/10.1016/J.CHEMOSPHERE.2014.12.023.
Li, D.-B., Cheng, Y.-Y., Li, L.-L., Li, W.-W., Huang, Y.-X., Pei, D.-N., Tong, Z.-H., Mu, Y., Yu, H.-
Q., 2014. Light-driven microbial dissimilatory electron transfer to hematite †. Phys.
Chem. Chem. Phys. 16, 23003. https://doi.org/10.1039/c4cp04065a.
Li, G., Park, S., Rittmann, B.E., 2012. Developing an efficient TiO2-coated biofilm carrier for
intimate coupling of photocatalysis and biodegradation. Water Res. 46, 6489–6496.
https://doi.org/10.1016/J.WATRES.2012.09.029.
Li, S., Chen, G., Anandhi, A., 2018. Applications of Emerging Bioelectrochemical Technologies
in Agricultural Systems: A Current Review. https://doi.org/10.3390/en11112951.
Li, Shuang, Cheng, Chong, Thomas, A., Li, S., Thomas Functional Materials, A., Cheng, C.,
2016. Carbon-Based Microbial-Fuel-Cell Electrodes: From Conductive Supports to Active
Catalysts. https://doi.org/10.1002/adma.201602547.
Li, T., Chen, F., Zhou, Q., Wang, X., Liao, C., Zhou, L., Wan, L., An, J., Wan, Y., Li, N., 2020.
Unignorable toxicity of formaldehyde on electroactive bacteria in bioelectrochemical sys-
tems. Environ. Res. 183, 109143. https://doi.org/10.1016/J.ENVRES.2020.109143.
Liang, B., Kong, D., Ma, J., Wen, C., Yuan, T., Lee, D.J., Zhou, J., Wang, A., 2016. Low temper-
ature acclimation with electrical stimulation enhance the biocathode functioning stability
for antibiotics detoxification. Water Res. 100, 157–168. https://doi.org/10.1016/J.
WATRES.2016.05.028.
Lianos, P., 2017. Review of recent trends in photoelectrocatalytic conversion of solar energy
to electricity and hydrogen. Appl. Catal. B Environ. 210, 235–254. https://doi.org/10.
1016/J.APCATB.2017.03.067.
Lim, S.S., Yu, E.H., Daud, W.R.W., Kim, B.H., Scott, K., 2017. Bioanode as a limiting factor to
biocathode performance in microbial electrolysis cells. Bioresour. Technol. 238,
313–324. https://doi.org/10.1016/J.BIORTECH.2017.03.127.
Lin, L., Lin, W., Zhu, Y., Zhao, B., Xie, Y., 2005. Phosphor-doped titania —a novel
photocatalyst active in visible light. Chem. Lett. 34, 284–285. https://doi.org/10.1246/
cl.2005.284.
Litter, M.I., 1999. Heterogeneous photocatalysis: transition metal ions in photocatalytic sys-
tems. Appl. Catal. B Environ. 23, 89–114. https://doi.org/10.1016/S0926-3373(99)
00069-7.
Liu, G., Zhao, Y., Sun, C., Li, F., Lu, G.Q., Cheng, H.-M., 2008. Synergistic effects of B/N doping
on the visible-light photocatalytic activity of mesoporous TiO2. Angew. Chem. Int. Ed.
47, 4516–4520. https://doi.org/10.1002/anie.200705633.
Liu, P.C., Ma, X.L., Li, T.T., Yan, F., Wu, L.J., Xiao, X., 2020. Elucidation of photodegradation
of p-chlorophenol in a biophotoelectric reductive degradation system by density func-
tional theory calculations. Int. Biodeterior. Biodegradation 151, 104969. https://doi.
org/10.1016/J.IBIOD.2020.104969.
Liu, W., Li, Y., Liu, F., Jiang, W., Zhang, D., Liang, J., 2019. Visible-light-driven photocatalytic
degradation of diclofenac by carbon quantum dots modified porous g-C3N4: mecha-
nisms, degradation pathway and DFT calculation. Water Res. 151, 8–19. https://doi.
org/10.1016/j.watres.2018.11.084.
Liu, W., Zhou, Z., Li, Z., Yang, Y., Zhao, J., Zhu, Y., Miao, W., 2021. Cobalt phosphide embed-
ded N-doped carbon nanopolyhedral as an efficient cathode electrocatalyst in microbial
fuel cells. J. Environ. Chem. Eng. 9, 104582. https://doi.org/10.1016/J.JECE.2020.
104582.
Liu, X., Liu, Y., Guo, X., Lu, S., Wang, Y., Zhang, J., Guo, W., Xi, B., 2020. High degree of con-
taminant removal and evolution of microbial community in different electrolysis-
integrated constructed wetland systems. Chem. Eng. J. 388, 124391. https://doi.org/
10.1016/J.CEJ.2020.124391.
Logan, B.E., Regan, J.M., 2006. Electricity-producing bacterial communities in microbial fuel
cells. Trends Microbiol. 14, 512–518. https://doi.org/10.1016/J.TIM.2006.10.003.
Long, X., Wang, H., Wang, C., Cao, X., Li, X., 2019. Enhancement of azo dye degradation and
power generation in a photoelectrocatalytic microbial fuel cell by simple cathodic reduc-
tion on titania nanotube arrays electrode. J. Power Sources 415, 145–153. https://doi.
org/10.1016/J.JPOWSOUR.2019.01.069.
Long, X., Wang, H., Wang, C., Li, X., 2020. The synergistic effect of biophoto anode for the en-
hancement of current generation and degradation. Environ. Technol. 41, 3420–3430.
https://doi.org/10.1080/09593330.2019.1611936.
Mahmoud, M., Parameswaran, P., Torres, C.I., Rittmann, B.E., 2014. Fermentation pre-treatment
of landfill leachate for enhanced electron recovery in a microbial electrolysis cell. Bioresour.
Technol. 151, 151–158. https://doi.org/10.1016/J.BIORTECH.2013.10.053.
Man, H.W., Tsang, C.S., Li, M.M.J., Mo, J., Huang, B., Lee, L.Y.S., Leung, Y.Chung, Wong, K.Y.,
Tsang, S.C.E., 2019. Transition metal-doped nickel phosphide nanoparticles as electro-
and photocatalysts for hydrogen generation reactions. Appl. Catal. B Environ. 242,
186–193. https://doi.org/10.1016/J.APCATB.2018.09.103.
Marone, A., Carmona-Martínez, A.A., Sire, Y., Meudec, E., Steyer, J.P., Bernet, N., Trably, E.,
2016. Bioelectrochemical treatment of table olive brine processing wastewater for biogas
production and phenolic compounds removal. Water Res. 100, 316–325. https://doi.org/
10.1016/J.WATRES.2016.05.008.
Marsolek, M.D., Torres, C.I., Hausner, M., Rittmann, B.E., 2008. ARTICLE intimate coupling of
photocatalysis and biodegradation in a photocatalytic circulating-bed biofilm reactor.
Wiley InterScience (www.Interscience.Wiley.com). Biotechnol. Bioeng. 101, 83–92.
https://doi.org/10.1002/bit.21889.
12
Science of the Total Environment 824 (2022) 153923
Marsolek, M.D., Kirisits, M.J., Gray, K.A., Rittmann, B.E., 2014. Coupled photocatalytic-
biodegradation of 2,4,5-trichlorophenol: effects of photolytic and photocatalytic effluent
composition on bioreactor process performance, community diversity, and resistance and
resilience to perturbation. Water Res. 50, 59–69. https://doi.org/10.1016/J.WATRES.
2013.11.043.
Martin, E., Savadogo, O., Guiot, S.R., Tartakovsky, B., 2010. The influence of operational con-
ditions on the performance of a microbial fuel cell seeded with mesophilic anaerobic
sludge. Biochem. Eng. J. 51, 132–139. https://doi.org/10.1016/J.BEJ.2010.06.006.
Miran, W., Nawaz, M., Jang, J., Lee, D.S., 2017. Chlorinated phenol treatment and in situ hy-
drogen peroxide production in a sulfate-reducing bacteria enriched bioelectrochemical
system. Water Res. 117, 198–206. https://doi.org/10.1016/J.WATRES.2017.04.008.
Munoz-Cupa, C., Hu, Y., Xu, C., Bassi, A., 2021. An overview of microbial fuel cell usage in
wastewater treatment, resource recovery and energy production. Sci. Total Environ.
754, 142429. https://doi.org/10.1016/J.SCITOTENV.2020.142429.
Nakata, K., Fujishima, A., 2012. TiO2 photocatalysis: design and applications. J Photochem
Photobiol C: Photochem Rev 13, 169–189. https://doi.org/10.1016/J.JPHOTOCHEMREV.
2012.06.001.
Ni, M., Leung, M.K.H., Leung, D.Y.C., Sumathy, K., 2007. A review and recent developments
in photocatalytic water-splitting using TiO2 for hydrogen production. Renew. Sust.
Energ. Rev. 11, 401–425. https://doi.org/10.1016/J.RSER.2005.01.009.
Nimje, V.R., Chen, C.Y., Chen, H.R., Chen, C.C., Huang, Y.M., Tseng, M.J., Cheng, K.C., Chang,
Y.F., 2012. Comparative bioelectricity production from various wastewaters in microbial
fuel cells using mixed cultures and a pure strain of shewanella oneidensis. Bioresour.
Technol. 104, 315–323. https://doi.org/10.1016/J.BIORTECH.2011.09.129.
Oros-Ruiz, S., Zanella, R., López, R., Hernández-Gordillo, A., Gómez, R., 2013. Photocatalytic
hydrogen production by water/methanol decomposition using Au/TiO2 prepared by
deposition–precipitation with urea. J. Hazard. Mater. 263, 2–10. https://doi.org/10.
1016/J.JHAZMAT.2013.03.057.
Paitier, A., Godain, A., Lyon, D., Haddour, N., Vogel, T.M., Monier, J.M., 2017. Microbial fuel
cell anodic microbial population dynamics during MFC start-up. Biosens. Bioelectron. 92,
357–363. https://doi.org/10.1016/J.BIOS.2016.10.096.
Palanisamy, G., Jung, H.Y., Sadhasivam, T., Kurkuri, M.D., Kim, S.C., Roh, S.H., 2019. A com-
prehensive review on microbial fuel cell technologies: processes, utilization, and ad-
vanced developments in electrodes and membranes. J. Clean. Prod. 221, 598–621.
https://doi.org/10.1016/J.JCLEPRO.2019.02.172.
Pan, Y., Wang, Y., Zhou, A., Wang, A., Wu, Z., Lv, L., Li, X., Zhang, K., Zhu, T., 2017. Removal of
azo dye in an up-flow membrane-less bioelectrochemical system integrated with bio-contact
oxidation reactor. Chem. Eng. J. 326, 454–461. https://doi.org/10.1016/J.CEJ.2017.05.146.
Pandey, P., Shinde, V.N., Deopurkar, R.L., Kale, S.P., Patil, S.A., Pant, D., 2016. Recent ad-
vances in the use of different substrates in microbial fuel cells toward wastewater treat-
ment and simultaneous energy recovery. Appl. Energy 168, 706–723. https://doi.org/
10.1016/J.APENERGY.2016.01.056.
Pant, D., Arslan, D., Van Bogaert, G., Gallego, Y.A., De Wever, H., Diels, L., Vanbroekhoven,
K., 2013. Integrated conversion of food waste diluted with sewage into volatile fatty
acids through fermentation and electricity through a fuel cell. Environ. Technol. 34,
1935–1945. https://doi.org/10.1080/09593330.2013.828763.
Patil, S.A., Harnisch, F., Kapadnis, B., Schröder, U., 2010. Electroactive mixed culture biofilms
in microbial bioelectrochemical systems: the role of temperature for biofilm formation
and performance. Biosens. Bioelectron. 26, 803–808. https://doi.org/10.1016/J.BIOS.
2010.06.019.
Peiris, S., Silva, H.B., Ranasinghe, K.N., Bandara, S.V., Perera, I.R., 2021. Recent development
and future prospects of <scp> TiO 2 </scp> photocatalysis. J. Chin. Chem. Soc. 68,
738–769. https://doi.org/10.1002/jccs.202000465.
Qian, F., Wang, H., Ling, Y., Wang, G., Thelen, M.P., Li, Y., 2014. Photoenhanced electrochem-
ical interaction between shewanella and a hematite nanowire photoanode. Nano Lett. 14,
24. https://doi.org/10.1021/nl501664n.
Rajasulochana, P., Preethy, V., 2016. Comparison on efficiency of various techniques in treat-
ment of waste and sewage water – a comprehensive review. Resour. Efficient Technol. 2,
175–184. https://doi.org/10.1016/J.REFFIT.2016.09.004.
Reginato, G., Zani, L., Calamante, M., Mordini, A., Dessì, A., 2020. Dye-sensitized heteroge-
neous photocatalysts for green redox reactions. Eur. J. Inorg. Chem. 2020, 899–917.
https://doi.org/10.1002/ejic.201901174.
Ren, X., Philo, D., Li, Y., Shi, L., Chang, K., Ye, J., 2020. Recent advances of low-dimensional
phosphorus-based nanomaterials for solar-driven photocatalytic reactions. Coord. Chem.
Rev. 424, 213516. https://doi.org/10.1016/J.CCR.2020.213516.
Rittmann, B.E., 2018. Biofilms, active substrata, and me. Water Res. 132, 135–145. https://
doi.org/10.1016/J.WATRES.2017.12.043.
Roccuzzo, S., Beckerman, A.P., Trögl, J., 2021. New perspectives on the bioremediation of en-
docrine disrupting compounds from wastewater using algae-, bacteria- and fungi-based
technologies. Int. J. Environ. Sci. Technol. 18, 89–106. https://doi.org/10.1007/
s13762-020-02691-3.
Rozendal, R.A., Jeremiasse, A.W., Hamelers, H.V.M., Buisman, C.J.N., 2008. Hydrogen pro-
duction with a microbial biocathode. Environ. Sci. Technol. 42, 629–634. https://doi.
org/10.1021/es071720+.
San-Martín, M.I., Escapa, A., Alonso, R.M., Canle, M., Morán, A., 2020. Degradation of 2-
mercaptobenzothizaole in microbial electrolysis cells: intermediates, toxicity, and micro-
bial communities. Sci. Total Environ. 733, 139155. https://doi.org/10.1016/J.
SCITOTENV.2020.139155.
Santoro, C., Guilizzoni, M., Correa Baena, J.P., Pasaogullari, U., Casalegno, A., Li, B.,
Babanova, S., Artyushkova, K., Atanassov, P., 2014. The effects of carbon electrode sur-
face properties on bacteria attachment and start up time of microbial fuel cells. Carbon
67, 128–139. https://doi.org/10.1016/J.CARBON.2013.09.071.
Santoro, C., Babanova, S., Artyushkova, K., Cornejo, J.A., Ista, L., Bretschger, O., Marsili, E.,
Atanassov, P., Schuler, A.J., 2015. Influence of anode surface chemistry on microbial
fuel cell operation. Bioelectrochemistry 106, 141–149. https://doi.org/10.1016/J.
BIOELECHEM.2015.05.002.
R. Rafieenia et al.
Shen, J., Du, Z., Li, J., Cheng, F., 2020. Co-metabolism for enhanced phenol degradation and
bioelectricity generation in microbial fuel cell. Bioelectrochemistry 134, 107527. https://
doi.org/10.1016/J.BIOELECHEM.2020.107527.
Shen, R., Xie, J., Xiang, Q., Chen, X., Jiang, J., Li, X., 2019. Ni-based photocatalytic H2-
production cocatalysts2. Chin. J. Catal. 40, 240–288. https://doi.org/10.1016/S1872-
2067(19)63294-8.
Slate, A.J., Whitehead, K.A., Brownson, D.A.C., Banks, C.E., 2019. Microbial fuel cells: an
overview of current technology. Renew. Sust. Energ. Rev. 101, 60–81. https://doi.org/
10.1016/J.RSER.2018.09.044.
Sobczyński, A., Duczmal, L., Zmudziński, W., 2004. Phenol destruction by photocatalysis on
TiO2: an attempt to solve the reaction mechanism. J. Mol. Catal. A Chem. 213,
225–230. https://doi.org/10.1016/J.MOLCATA.2003.12.006.
Song, R.-B., Zhao, C.-E., Jiang, L.-P., Sayed Abdel-Halim, E., Zhang, J.-R., Zhu, J.-J., 2016.
Bacteria-affinity 3D macroporous graphene/MWCNTs/Fe 3 O 4 foams for high-
performance microbial fuel cells. ACS Appl. Mater. Interfaces 8, 16170–16177. https://
doi.org/10.1021/acsami.6b03425.
Su, S., Zhang, Y., Hu, W., Zhang, X., Ju, D., Jia, C., Liu, J., 2020. Efficient and synergistic
decolourization and nitrate removal using a single-chamber with a coupled biocathode-
photoanode system. Bioelectrochemistry 132, 107439. https://doi.org/10.1016/J.
BIOELECHEM.2019.107439.
Sui, M., Dong, Y., Wang, Z., Wang, F., You, H., 2017. A biocathode-driven photocatalytic fuel
cell using an ag-doped TiO2/Ti mesh photoanode for electricity generation and pollutant
degradation. J. Photochem. Photobiol. A Chem. 348, 238–245. https://doi.org/10.1016/
J.JPHOTOCHEM.2017.08.047.
Tahir, K., Miran, W., Nawaz, M., Jang, J., Shahzad, A., Moztahida, M., Kim, B., Azam, M.,
Jeong, S.E., Jeon, C.O., Lim, S.R., Lee, D.S., 2019. Investigating the role of anodic poten-
tial in the biodegradation of carbamazepine in bioelectrochemical systems. Sci. Total En-
viron. 688, 56–64. https://doi.org/10.1016/J.SCITOTENV.2019.06.219.
Tojo, S., Tachikawa, T., Fujitsuka, M., Majima, T., 2008. Iodine-doped TiO 2 photocatalysts:
correlation between band structure and mechanism. J. Phys. Chem. C 112,
14948–14954. https://doi.org/10.1021/jp804985f.
Trapero, J.R., Horcajada, L., Linares, J.J., Lobato, J., 2017. Is microbial fuel cell technology
ready? An economic answer towards industrial commercialization. Appl. Energy 185,
698–707. https://doi.org/10.1016/J.APENERGY.2016.10.109.
Tremouli, A., Martinos, M., Lyberatos, Gerasimos, 2017. The effects of salinity, pH and tem-
perature on the performance of a microbial fuel cell. Waste Biomass Valoriz. 8,
2037–2043. https://doi.org/10.1007/s12649-016-9712-0.
Tu, L., Hou, Y., Yuan, G., Yu, Z., Qin, S., Yan, Y., Zhu, H., Lin, H., Chen, Y., Wang, S., 2020.
Bio-photoelectrochemcial system constructed with BiVO4/RGO photocathode for 2,4-di-
chlorophenol degradation: BiVO4/RGO optimization, degradation performance and
mechanism. J. Hazard. Mater. 389, 121917. https://doi.org/10.1016/J.JHAZMAT.
2019.121917.
Verlicchi, P., Al Aukidy, M., Zambello, E., 2012. Occurrence of pharmaceutical compounds in
urban wastewater: removal, mass load and environmental risk after a secondary treat-
ment—a review. Sci. Total Environ. 429, 123–155. https://doi.org/10.1016/J.
SCITOTENV.2012.04.028.
Vinayak, V., Khan, M.J., Varjani, S., Saratale, G.D., Saratale, R.G., Bhatia, S.K., 2021. Micro-
bial fuel cells for remediation of environmental pollutants and value addition: special
focus on coupling diatom microbial fuel cells with photocatalytic and photoelectric fuel
cells. J. Biotechnol. 338, 5–19. https://doi.org/10.1016/J.JBIOTEC.2021.07.003.
Wang, A.J., Cui, D., Cheng, H.Y., Guo, Y.Q., Kong, F.Y., Ren, N.Q., Wu, W.M., 2012. A
membrane-free, continuously feeding, single chamber up-flow biocatalyzed electrolysis
reactor for nitrobenzene reduction. J. Hazard. Mater. 199–200, 401–409. https://doi.
org/10.1016/J.JHAZMAT.2011.11.034.
Wang, H., Liu, J., He, W., Qu, Y., Li, D., Jiang, Q., Feng, Y., 2016. Enhanced power generation
of oxygen-reducing biocathode with an alternating hydrophobic and hydrophilic surface.
ACS Appl. Mater. Interfaces 8, 31995–32003. https://doi.org/10.1021/acsami.6b10876.
Wang, H., Lu, L., Mao, D., Huang, Z., Cui, Y., Jin, S., Zuo, Y., Ren, Z.J., 2019. Dominance of
electroactive microbiomes in bioelectrochemical remediation of hydrocarbon-
contaminated soils with different textures. Chemosphere 235, 776–784. https://doi.
org/10.1016/J.CHEMOSPHERE.2019.06.229.
Wang, Q., Cai, Z., Huang, L., Pan, Y., Quan, X., Li Puma, G., 2019. Intensified degradation and
mineralization of antibiotic metronidazole in photo-assisted microbial fuel cells with mo-
W catalytic cathodes under anaerobic or aerobic conditions in the presence of Fe(III).
Chem. Eng. J. 376, 119566. https://doi.org/10.1016/J.CEJ.2018.07.168.
Wang, S.-S., Sharif, H.M.A., Cheng, H.-Y., Wang, A.-J., B, L., ZL, L., HY, C., 2019.
Bioelectrochemical system integrated with photocatalysis: principle and prospect
in wastewater treatment. In: AJ, W. (Ed.), Bioelectrochemistry Stimulated Environ-
mental Remediation. Springer, Singapore https://doi.org/10.1007/978-981-10-
8542-0.
Wang, X., Hu, J., Chen, Q., Zhang, P., Wu, L., Li, J., Liu, B., Xiao, K., Liang, S., Huang, L., Hou,
H., Yang, J., 2019. Synergic degradation of 2,4,6-trichlorophenol in microbial fuel cells
with intimately coupled photocatalytic-electrogenic anode. Water Res. 156, 125–135.
https://doi.org/10.1016/J.WATRES.2019.03.001.
Wangab, Y., Ma, X., Li, Hao, Liu, B., Li, Huihui, Yin, S., Sato, T., 2016. Recent Advances in
Visible-Light Driven Photocatalysis. Intech, pp. 337–357 https://doi.org/10.5772/
61864.
Watson, V.J., Logan, B.E., 2010. ARTICLE power production in MFCs inoculated with
shewanella oneidensis MR-1 or mixed cultures. Biotechnol. Bioeng. 105, 489–498.
https://doi.org/10.1002/bit.22556.
Wei, J., Liang, P., Huang, X., 2011. Recent progress in electrodes for microbial fuel cells.
Bioresour. Technol. 102, 9335–9344. https://doi.org/10.1016/J.BIORTECH.2011.07.
019.
Wen, Q., Yang, T., Wang, S., Chen, Y., Cong, L., Qu, Y., 2013. Dechlorination of 4-
chlorophenol to phenol in bioelectrochemical systems. J. Hazard. Mater. 244–245,
743–749. https://doi.org/10.1016/J.JHAZMAT.2012.11.002.
13
Science of the Total Environment 824 (2022) 153923
Xiao, X., Ma, X.L., Liu, Z.Y., Li, W.W., Yuan, H., Ma, X.B., Li, L.X., Yu, H.Q., 2019. Degradation
of rhodamine B in a novel bio-photoelectric reductive system composed of shewanella
oneidensis MR-1 and Ag3PO4. Environ. Int. 126, 560–567. https://doi.org/10.1016/J.
ENVINT.2019.03.010.
Xing, F., Liu, Q., Huang, C., 2019. Mo-Doped ZnIn 2 S 4 Flower-Like Hollow Microspheres for
Improved Visible Light-Driven Hydrogen Evolution. https://doi.org/10.1002/solr.
201900483.
Xiong, H., Zou, D., Zhou, D., Dong, S., Wang, J., Rittmann, B.E., 2017. Enhancing degradation
and mineralization of tetracycline using intimately coupled photocatalysis and biodegra-
dation (ICPB). Chem. Eng. J. 316, 7–14. https://doi.org/10.1016/J.CEJ.2017.01.083.
Xu, F., Cao, F.Qian, Kong, Q., Zhou, L.Lu, Yuan, Q., Zhu, Y.Jie, Wang, Q., Du, Y.Da, Wang, Z.
De, 2018. Electricity production and evolution of microbial community in the con-
structed wetland-microbial fuel cell. Chem. Eng. J. 339, 479–486. https://doi.org/10.
1016/J.CEJ.2018.02.003.
Xu, H., Tong, N., Huang, S., Zhou, S., Li, S., Li, J., Zhang, Y., 2018. Degradation of 2,4,6-
trichlorophenol and determination of bacterial community structure by micro-electrical
stimulation with or without external organic carbon source. Bioresour. Technol. 263,
266–272. https://doi.org/10.1016/J.BIORTECH.2018.05.015.
Xu, P., Zheng, D., He, Q., Yu, J., 2020a. The feasibility of ofloxacin degradation and electricity
generation in photo-assisted microbial fuel cells with LiNbO3/CF photocatalytic cathode.
Sep. Purif. Technol. 250, 117106. https://doi.org/10.1016/J.SEPPUR.2020.117106.
Xu, P., Zheng, D., Xie, Z., He, Q., Yu, J., 2020b. The degradation of ibuprofen in a novel mi-
crobial fuel cell with PANi@CNTs/SS bio-anode and CuInS2 photocatalytic cathode:
property, efficiency and mechanism. J. Clean. Prod. 265, 121872. https://doi.org/10.
1016/J.JCLEPRO.2020.121872.
Xu, Y., Ge, Z., Zhang, X., Feng, H., Ying, X., Huang, B., Shen, D., Wang, M., Zhou, Y., Wang, Y.,
Yu, H., 2019. Validation of effective roles of non-electroactive microbes on recalcitrant
contaminant degradation in bioelectrochemical systems. Environ. Pollut. 249, 794–800.
https://doi.org/10.1016/J.ENVPOL.2019.03.036.
Yan, Weifu, Xiao, Y., Yan, Weida, Ding, R., Wang, S., Zhao, F., 2019. The effect of
bioelectrochemical systems on antibiotics removal and antibiotic resistance genes: a re-
view. Chem. Eng. J. 358, 1421–1437. https://doi.org/10.1016/J.CEJ.2018.10.128.
Yang, L., Zhang, Y., Bai, Q., Yan, N., Xu, H., Rittmann, B.E., 2015. Intimately coupling of pho-
tolysis accelerates nitrobenzene biodegradation, but sequential coupling slows biodegra-
dation. J. Hazard. Mater. 287, 252–258. https://doi.org/10.1016/J.JHAZMAT.2015.01.
055.
Yang, L.H., Zhu, T.T., Cai, W.W., Haider, M.R., Wang, H.C., Cheng, H.Y., Wang, A.J., 2018.
Micro-oxygen bioanode: an efficient strategy for enhancement of phenol degradation
and current generation in mix-cultured MFCs. Bioresour. Technol. 268, 176–182.
https://doi.org/10.1016/J.BIORTECH.2018.07.025.
You, S., Ma, Ming, Wang, Wei, Qi, Dianpeng, Chen, Xiaodong, Qu, Jiuhui, You, Ren, Ma, M.,
Wang, W., Ren, N., Qi, D., Chen, X., Qu, J., N.S, 2016. 3D Macroporous Nitrogen-
Enriched Graphitic Carbon Scaffold for Efficient Bioelectricity Generation in Microbial
Fuel Cells This Work Provides a Proof-of-concept Demonstration of a High-efficiency,
Cost-effective, Easily Scaling-up, and Environmentally Fri. https://doi.org/10.1002/
aenm.201601364.
Yu, C., Fan, Q., Xie, Y., Chen, J., Shu, Q., Yu, J.C., 2012. Sonochemical fabrication of novel
square-shaped F doped TiO2 nanocrystals with enhanced performance in photocatalytic
degradation of phenol. J. Hazard. Mater. 237–238, 38–45. https://doi.org/10.1016/J.
JHAZMAT.2012.07.072.
Yu, M., Wang, J., Tang, L., Feng, C., Liu, H., Zhang, H., Peng, B., Chen, Z., Xie, Q., 2020. Inti-
mate coupling of photocatalysis and biodegradation for wastewater treatment: mecha-
nisms, recent advances and environmental applications. Water Res. 175, 115673.
https://doi.org/10.1016/J.WATRES.2020.115673.
Yu, Q., Xiong, W., Huang, D., Luo, C., Yang, Q., Guo, T., Wei, Q., 2020. Cathodic reduction
characteristics of 2-chloro-4-nitrophenol in microbial electrolysis cell. Environ. Eng.
Res. 25, 854–861. https://doi.org/10.4491/eer.2019.387.
Yu, Y., Ndayisenga, F., Yu, Z., Zhao, M., Lay, C.H., Zhou, D., 2019. Co-substrate strategy for
improved power production and chlorophenol degradation in a microbial fuel cell. Int.
J. Hydrog. Energy 44, 20312–20322. https://doi.org/10.1016/J.IJHYDENE.2019.05.
221.
Yuan, S.-J., Sheng, G.-P., Li, W.-W., Lin, Z.-Q., Zeng, R.J., Tong, Z.-H., Yu, H.-Q., 2010. Degra-
dation of Organic Pollutants in a Photoelectrocatalytic System Enhanced by a Microbial
Fuel Cell. https://doi.org/10.1021/es101317z.
Zeng, L., Li, X., Zhao, Q., Fan, S., Zhang, M., Yin, Z., Chen, A., 2019. Boosting interfacial
charge transfer and electricity generation for levofloxacin elimination in a self-driven
bio-driven photoelectrocatalytic system †. Nanoscale 11. https://doi.org/10.1039/
c9nr05520g.
Zhang, B., Wang, Z., Zhou, X., Shi, C., Guo, H., Feng, C., 2015. Electrochemical decolorization
of methyl orange powered by bioelectricity from single-chamber microbial fuel cells.
Bioresour. Technol. 181, 360–362. https://doi.org/10.1016/J.BIORTECH.2015.01.076.
Zhang, C., Li, Y., Shen, H., Shuai, D., 2021. Simultaneous coupling of photocatalytic and bio-
logical processes: a promising synergistic alternative for enhancing decontamination of
recalcitrant compounds in water. Chem. Eng. J. 403, 126365. https://doi.org/10.1016/
J.CEJ.2020.126365.
Zhang, H., Lu, Y., Li, Y., Wang, C., Yu, Y., Zhang, W., Wang, L., Niu, L., Zhang, C., 2022. Pro-
pelling the practical application of the intimate coupling of photocatalysis and biodegra-
dation system: system amelioration, environmental influences and analytical strategies.
Chemosphere 287, 132196. https://doi.org/10.1016/J.CHEMOSPHERE.2021.132196.
Zhang, J., Wang, Z., Chu, L., Chen, R., Zhang, C., Toan, S., Bagley, D.M., Sun, J., Dong, S., Fan,
M., 2021. Unified photoelectrocatalytic microbial fuel cell harnessing 3D binder-free pho-
tocathode for simultaneous power generation and dual pollutant removal. J. Power
Sources 481, 229133. https://doi.org/10.1016/J.JPOWSOUR.2020.229133.
Zhang, L., Zhang, Y., Xiao, K., Shi, J., Du, X., Wang, L., Wu, X., 2021. An intimate coupling of
photocatalysis and biodegradation for the degradation and mineralization of atrazine in
water. New J. Chem. https://doi.org/10.1039/d1nj00134e.
R. Rafieenia et al.
Zhang, T., Nie, H., Bain, T.S., Lu, H., Cui, M., Snoeyenbos-West, O.L., Franks, A.E., Nevin, K.P.,
Russell, T.P., Lovley, D.R., 2013. Improved cathode materials for microbial electrosynthesis.
Energy Environ. Res. 6, 217–224. https://doi.org/10.1039/c2ee23350a.
Zhang, Y., Pu, X., Fang, M., Zhu, J., Chen, L., Rittmann, B.E., 2012. 2,4,6-trichlorophenol
(TCP) photobiodegradation and its effect on community structure. Biodegradation 23,
575–583. https://doi.org/10.1007/s10532-012-9534-0.
Zhang, Y., Liu, M., Zhou, M., Yang, H., Liang, L., Gu, T., 2019. Microbial fuel cell hybrid sys-
tems for wastewater treatment and bioenergy production: synergistic effects, mechanisms
and challenges. Renew. Sust. Energ. Rev. 103, 13–29. https://doi.org/10.1016/J.RSER.
2018.12.027.
Zhao, H., Kong, C.H., 2018. Enhanced removal of p-nitrophenol in a microbial fuel cell after
long-term operation and the catabolic versatility of its microbial community. Chem. Eng.
J. 339, 424–431. https://doi.org/10.1016/J.CEJ.2018.01.158.
Zhao, K., Zeng, Q., Bai, J., Li, J., Xia, L., Chen, S., Zhou, B., 2017. Enhanced organic pollutants
degradation and electricity production simultaneously via strengthening the radicals re-
action in a novel Fenton-photocatalytic fuel cell system. Water Res. 108, 293–300.
https://doi.org/10.1016/J.WATRES.2016.11.002.
Zheng, T., Li, J., Ji, Y., Zhang, W., Fang, Y., Xin, F., Dong, W., Wei, P., Jiang, M., 2020. Prog-
ress and prospects of bioelectrochemical systems: electron transfer and its applications in
the microbial metabolism. Front. Bioeng. Biotechnol. 8, 10. https://doi.org/10.3389/
fbioe.2020.00010.
Zhou, D., Dong, S., Shi, J., Cui, X., Ki, D., Torres, C.I., Rittmann, B.E., 2017. Intimate coupling
of an N-doped TiO2 photocatalyst and anode respiring bacteria for enhancing 4-
chlorophenol degradation and current generation. Chem. Eng. J. 317, 882–889.
https://doi.org/10.1016/J.CEJ.2017.02.128.
14
Science of the Total Environment 824 (2022) 153923
Zhou, D., Dong, S., Ki, D., Rittmann, B.E., 2018. Photocatalytic-induced electron transfer via
anode-respiring bacteria (ARB) at an anode that intimately couples ARB and a TiO2
photocatalyst. Chem. Eng. J. 338, 745–751. https://doi.org/10.1016/J.CEJ.2018.01.
094.
Zhou, L., Yan, X., Yan, Y., Li, T., An, J., Liao, C., Li, N., Wang, X., 2020. Electrode potential
regulates phenol degradation pathways in oxygen-diffused microbial electrochemical sys-
tem. Chem. Eng. J. 381, 122663. https://doi.org/10.1016/J.CEJ.2019.122663.
Zhu, D., Zhou, Q., 2019. Action and mechanism of semiconductor photocatalysis on degrada-
tion of organic pollutants in water treatment: a review. Environ. Nanotechnology Monit.
Manag. 12, 100255. https://doi.org/10.1016/J.ENMM.2019.100255.
Zhu, Q., Wang, X., Hu, J., Chen, S., Hu, S., Wu, Y., Liu, B., Xiao, K., Liang, S., Yang, J., Hou, H.,
2021. Efficient degradation of refractory pollutant in a microbial fuel cell with novel hy-
brid photocatalytic air-cathode: intimate coupling of microbial and photocatalytic pro-
cesses. Bioresour. Technol. 340, 125717. https://doi.org/10.1016/J.BIORTECH.2021.
125717.
Zou, R., Tang, K., Angelidaki, I., Andersen, H.R., Zhang, Y., 2020. An innovative microbial
electrochemical ultraviolet photolysis cell (MEUC) for efficient degradation of carbamaz-
epine. Water Res. 187, 116451. https://doi.org/10.1016/J.WATRES.2020.116451.
Zou, R., Tang, K., Hambly, A.C., Chhetri, R.K., Yang, X., Xu, M., Su, Y., Andersen, H.R.,
Angelidaki, I., Zhang, Y., 2021. A novel persulfate-photo-bioelectrochemical hybrid sys-
tem promoting the degradation of refractory micropollutants at neutral pH. J. Hazard.
Mater. 416, 125905. https://doi.org/10.1016/J.JHAZMAT.2021.125905.
Zuo, W., Zhang, L., Zhang, Z., Tang, S., Sun, Y., Huang, H., Yu, Y., 2021. Degradation of or-
ganic pollutants by intimately coupling photocatalytic materials with microbes: a review.
Crit. Rev. Biotechnol. 41, 273–299. https://doi.org/10.1080/07388551.2020.1869689.