Water Research 175 (2020) 115673

Contents lists available at ScienceDirect

Water Research
journal homepage: www.elsevier.com/locate/watres

Review

Intimate coupling of photocatalysis and biodegradation for

wastewater treatment: Mechanisms, recent advances and
environmental applications
Mingliang Yu a, b, 1, Jiajia Wang a, b, 1, Lin Tang a, b, *, Chengyang Feng a, b, Haoyu Liu a, b,
Hao Zhang a, b, Bo Peng a, b, Zhaoming Chen a, b, Qingqing Xie a, b
a
College of Environmental Science and Engineering, Hunan University, Changsha, 410082, China
b
Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha, 410082, China

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

Article history: Due to the increase of emerging contaminants in water, how to use new treatment technology to make
Received 26 August 2019 up for the defects of traditional wastewater treatment method has become one of the research hotspots
Received in revised form at present. Intimate coupling of photocatalysis and biodegradation (ICPB) as a novel wastewater treat-
24 February 2020
ment method, which combines the advantages of biological treatment and photocatalytic reactions, has
Accepted 27 February 2020
shown a great potential as a low-cost, environmental friendly and sustainable treatment technology. The
Available online 28 February 2020
system mainly consists of photocatalytic materials, porous carriers and biofilm. The key principle of ICPB
is to transform bio-recalcitrant pollutants into biodegradable products by photocatalysis on the surface of
Keywords:
Intimate coupling
porous carriers. The biodegradable products were mineralized simultaneously through the biofilm inside
Photocatalysis the carriers. Because of the protection of the carriers, the microorganism can remain active even under
Biodegradation the UV-light, the mechanical force of water flow or the attack of free radicals. ICPB breaks the traditional
Wastewater treatment concept that photocatalytic reaction and biodegradation must be separated in different reactors, im-
Mechanisms proves the purification capacity of sewage and saves the cost. This review summarizes the recent ad-
vances of ICPB photocatalysts, carriers and biofilm being applied, and focuses on the mechanisms and
reactor configurations which is particularly novel. Furthermore, the possible ongoing researches on ICPB
are also put forward. This review will provide a valuable insight into the design and application of ICPB in
environment and energy field.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Mechanisms of ICPB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. The synergistic effect of adsorption, photocatalysis and biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. Self-regulation mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Co-substrate and competition mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Advances in photocatalytic materials, carriers and biofilms for ICPB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Photocatalytic materials for ICPB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1.1. Ultraviolet-light photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1.2. Visible-light photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Carriers of ICPB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1. The cellulose carrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.2. The ceramic carrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

* Corresponding author. College of Environmental Science and Engineering,

Hunan University, Changsha, 410082, China.
E-mail address: tanglin@hnu.edu.cn (L. Tang).
1
These authors contribute equally to this work.

https://doi.org/10.1016/j.watres.2020.115673
0043-1354/© 2020 Elsevier Ltd. All rights reserved.
2 M. Yu et al. / Water Research 175 (2020) 115673

3.2.3. The polyurethane sponge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.2.4. The polyurethane foam . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3. Biofilms of ICPB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Configurations of PCBBR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1. PCBBR with suspended photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2. PCBBR with immobilized photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.1. Degradation of nitrogenous compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.2. Degradation of phenolic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5.3. Degradation of reactive dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.4. Degradation of antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.5. Current generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. Conclusions and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction et al. (2008) have successfully proved the idea of ICPB for the first
time in a photocatalytic circulating-bed biofilm reactor (PCBBR)
With the increasing of the varied emerging contaminants in that utilized macroporous cellulose carriers and TiO2 to remove 2,
water, the traditional sewage treatment technology, represented by 4, 5-trichlorophenol (TCP). Depending on the type of light source,
the activated sludge process, is difficult to degrade the emerging ICPB can be divided into two types: UV-light induced photo-
recalcitrant contaminants with high concentrations and complex catalysis and biodegradation (UPCB) and visible-light induced
structures (Deng et al. 2017b, 2018b; Tang et al., 2016b; van photocatalysis and biodegradation (VPCB) (Zhou et al., 2015). In
Loosdrecht and Brdjanovic, 2014). Even though some organic pol- ICPB, the photodegradation and biodegradation processes work
lutants are biodegradable, their biodegradation tends to be slow together in one reactor, so that the biodegradable intermediates
and happens only at low concentration due to inhibition (Marsolek produced by photodegradation can be biodegraded at once. ICPB
et al., 2007). Therefore, how to preserve the advantages of biolog- offered potential for the photodegradation and biodegradation of a
ical treatment technology and to integrate it with new sewage range of recalcitrant and toxic organic pollutants, including TCP
treatment technologies to realize win-win has become the current (Marsolek et al., 2014), dinitrotoluene (Wen et al., 2012), nitro-
research hotspot. benzene (Yang et al., 2015a), dyes (Li et al., 2012a) and tetracycline
Microbial treatment technology has been coupled with mem- hydrochloride (TCH) (Xiong et al., 2018). There are some works on
brane technology, advanced oxidation processes (AOPs), electro- ICPB, but the research on ICPB is still in its infancy. Their charac-
chemical techniques and other emerging treatment technologies teristics are still difficult to understand, and more potential are
(Wang et al. 2016b, 2016c; Yan et al., 2012; Yang et al., 2015a). For largely undiscovered. The importance of this emerging field re-
AOPs, most of the previous attempts to combine treatments have quires timely review of recent developments to promote progress
been done by carrying out AOPs and biological treatment sepa- in this area.
rately, or by sequential coupling method (Brosillon et al., 2008; The aim of this review is to summarize the state-of-the-art
Hong and Zeng, 2002; Sirtori et al., 2009). AOPs are fast-acting progresses of ICPB system, from the mechanisms possibly
but indiscriminate degradation relying on free radical reactions, involved in ICPB, to the development of photocatalysis materials,
which can produce a series of excessive oxidation (Li et al., 2011; carriers, biofilms and reactor configurations, and finally the varied
Marsolek et al., 2008). Photocatalytic oxidation technology began application in recent years. Conclusions and future prospects are
as early as 1972 (Zhang et al., 2012a). Some semiconductor pho- also proposed. This review will provide theoretical principles and
tocatalytic materials (e.g. TiO2, Bi2WO6) can produce
OH,
O 2 and novel insights for better future applications and innovative design
other reactive oxidative species (ROS) under light excitation, and of ICPB in wastewater treatment.
the generated ROS can attack the ring and chain, so that the re-
fractory organic matters can be transformed into the biodegradable
intermediates (Deng et al. 2016, 2018a; Feng et al., 2018; Tang et al., 2. Mechanisms of ICPB
2016a; Wang et al. 2016a, 2018). The traditional idea that photo-
catalytic reaction and biological treatment are difficult to be carried 2.1. The synergistic effect of adsorption, photocatalysis and
biodegradation
out in the same reactor is mainly due to the fact that the photo-
catalytic reaction is fast and indiscriminate, so it is hard to control
the products of photocatalytic reaction to the biodegradable cate- ICPB as a novel wastewater treatment technology has shown
gory (Yan et al., 2016). great potential for enhancing the removal and mineralization of
However, if photocatalysis and biodegradation occur at the same bio-refractory pollutants. The mechanisms possibly acting in ICPB
time, problems in sequential treatment can be optimized and are proposed in Fig. 1. The porous carrier can adsorb bio-refractory
reduced, which is named intimate coupling (Li et al., 2012b). Inti- pollutants from the solution and enhance its mass transfer to the
mate coupling of photocatalysis and biodegradation (ICPB) is one surface of the photocatalysts, where various ROS are generated,
way to overcome the uncertainties of sequential processing, such as thus promoting the photocatalytic degradation of the pollutants. In
the uncertainty of photocatalysis intermediates. ICPB not only the process of photocatalytic degradation, photocatalyst absorbs
removed the recalcitrant organic pollution, but also increased photon energy (photons energy (hv)  bandgap energy (Eg) of
mineralization efficiency and lowered operating costs. Marsolek photocatalyst) which causes electron (e) to transfer from the
valence band (VB) to the conduction band (CB) and generates
 M. Yu et al. / Water Research 175 (2020) 115673
Fig. 1. The proposed mechanisms possibly acting in the ICPB system: the synergistic effect of adsorption, photocatalysis and biodegradation.
electron-hole pairs. At the same time, organic contaminants are
attacked and destroyed by ROS, such as
OH,
O þ
2 and h (Deng
et al., 2017a; Lin et al., 2011; Tang et al., 2018; Wang et al., 2017).
The products produced by photocatalysis are transferred into the
carrier and biodegraded within the biofilms, which is further
completely mineralized into CO2 and water. The biodegradation
process also involves that photoelectrons generated by photo-
catalyst can be transferred to biofilms through c-type cytochromes.
The timely biodegradation of photocatalytic products avoids the
damage of microbial metabolism and unfavorable oxidation. Un-
doubtedly, adsorption, photocatalysis and biodegradation in the
ICPB system occur simultaneously rather than completely inde-
pendent. In ICPB, the shear forces and the generated free radicals
can cause the biofilm detaching from the carrier surface, particu-
larly the biofilm that are directly adhered to the photocatalyst
material. Thus, biodegradation gradually decreases with the
continuous enhancement of photocatalysis (Rittmann, 2018). When
the photocatalytic effect increases to a certain degree to produce
more biodegradable intermediates, the organics in the solution
could be conducive to the formation of biofilms. In return,
biodegradation increases, biofilms may begin to recover on the
photocatalyst. This process plays a balancing role in ICPB. This
balance adjustment is called synergistic effect (Dong et al., 2016).
2.2. Self-regulation mechanism
Self-regulation is of great significance for reaching a balance
between photocatalysis and biodegradation to achieve ICPB. In an
ideal ICPB, most microorganisms are located into the carriers, and
almost no biofilm attached to the outside of the carrier. Marsolek’s
work showed that biomass initially separated from the outer sur-
faces of carrier, possibly owing to physical loss and exposure to UV-
light, then the biomass regrew associated with acetate degradation,
which confirmed that bacteria were protected in the interior of the
macroporous carrier (Marsolek et al., 2008). Bacteria may produce
soluble microbial products (SMPs) and extracellular polymeric
substances (EPSs) to protect themselves probably by scavenging
free radicals. The enhanced consumption of acetate and production
of SMPs and EPSs supported that bacteria are active. Then, bacteria
close to where photocatalytic reactions occurred could remove
biodegradable products that were initially produced, leaving ROS
concentrated nearby the bio-recalcitrant compounds. Live cells
grow inside the carrier but most cells near the outer surface are
dead due to the attack by the radicals and light irradiation. Even
3
inside the carrier, the biofilm layer shows a gradient from live to
dead, suggesting the self-regulation mechanism of ICPB when the
photocatalytic reactants invaded the macropores (Dong et al.,
2016).
2.3. Co-substrate and competition mechanism
As reported by previous studies, non-chlorinated phenols can
improve the biodegradation efficiency of 4-chlorophenol (4-CP), by
promoting microbial growth through the use of less toxic sub-
strates (Zhang and Tay, 2015) and biological activity of the induced
non-specific enzymes (Monsalvo et al., 2009). They can also be
photodegraded, thus competing with 4-CP for photo-generated
ROS involved in the photodegradation. One method for enhancing
biodegradation is to offer an easily biodegradable substrate to
stimulate an active biofilm community (Marsolek and Rittmann,
2016). An organic small molecule as a co-substrate can supply
electron donor with more biomass synthesis and promote photo-
catalytic reactions (Bai et al., 2015; Kim et al., 2014). For example,
Xiong et al. used sodium acetate (NaAC) as the electron donor and
carbon source for microbial growth. The addition of acetate led to
more active biomass which promoted faster biodegradation of non-
recalcitrant organics, thus reducing competition for free radicals
among the recalcitrant fraction (Xiong et al., 2018).
3. Advances in photocatalytic materials, carriers and biofilms
for ICPB
3.1. Photocatalytic materials for ICPB
To date, many photocatalytic materials have been developed to
treat wastewater in ICPB. The most studied photocatalytic materials
are TiO2-based photocatalysts, such as SiO2eTiO2 (Zhang et al.,
2016a), AgeTiO2 (Xiong et al., 2017), NeTiO2 (Zhou et al., 2017)
and Er3þ: YAlO3/TiO2 (Zhou et al., 2015). Other photocatalysts have
also been developed to enhance the degradation efficiency of re-
fractory pollutants in these two years, such as Bi12O17Cl2 (Ding
et al., 2018) and Mn3O4/MnO2eAg3PO4 (Cai et al., 2019), more
detailed information in Table 1.
3.1.1. Ultraviolet-light photocatalysts
TiO2 has great photocatalytic activities due to its good chemical
stability, non-toxicity, cost effectiveness and high reactivity under
ultraviolet light irradiation. The easy separation of TiO2 catalyst
4 M. Yu et al. / Water Research 175 (2020) 115673

Table 1
The effects of different photocatalysts, carriers and coating methods on pollutants removal efficiency in ICPB.

Photocatalysts Carriers Coating methods Main results Ref.

P25 TiO2 The cellulose cubes Sol-gel method TCP removal: 23.6% Marsolek et al. (2008)
Acetate removal: 100%
TiO2 The sponge Modified low temperature sintering method RB5 removal: 97% Li et al., 2012a
COD removal: 65%
The ordered mesoporous TiO2 The ceramic Camphene-based freeze-casting method Octane removal: 99.9% Xing et al. (2014)
RhB removal:99.4%
SiO2eTiO2 PUF Ultrasonic vibration and deposition approach Phenol/2,4,5-TCP removal: 100% Zhang et al. (2016a)
TOC removal: 97.5%
Ag/TiO2 The polyurethane sponge Sol-gel and evaporation-induced self-assembly (EISA) TCH removal: 95% Xiong et al. (2018)
SCOD removal: 95%
NeTiO2 The carbon foam Ultrasonicated and dried 4-CP removal: 90.5% Zhou et al. (2017)
Current density:0.40A/m2
Er3þ:YAlO3/TiO2 The sponge Self-assembly Phenol removal: 99.8% Dong et al. (2016)
MO removal: 94.8%
COD removal: 65.2%
Bi12O17Cl2 The polyurethane sponge Ultrasonically dispersed and evaporation Oxytetracycline removal: 94% Ding et al. (2018)
TOC removal: 26.3%
Mn3O4/MnO2eAg3PO4 The polyurethane sponge Self-polymerization PHE removal: 96.2% Cai et al. (2019)
TOC removal: 31.93%

accommodated in PCBBR after wastewater treatment can help
apply this catalyst in industrial practice (Pelaez et al., 2012;
Schneider et al., 2014; Wu et al., 2014; Zhang et al., 2014a). Mar-
solek et al. directly coated TiO2 on the surface of the carrier, pro-
ducing a hybrid photocatalytic-biological carrier for the first time
by using a sol-gel technique (Marsolek et al., 2008). However, the
practical application of TiO2 is restricted by three major limitations:
(i) the low load ratio of TiO2 on the carrier (Sun et al., 2013; Xiong
and Zhao, 2013; Yoo et al., 2013); (ii) the low photon utilization rate
(Luo et al., 2013; Zhang et al., 2013; Zhou et al., 2013); (iii) the low
recovery of TiO2 (Chalasani and Vasudevan, 2013; Tang et al., 2013).
In order to increase the load ratio of TiO2 on the carrier in ICPB,
Li et al., 2012b increased the loading amount of TiO2 on the carrier
by a modified method. Firstly, titanium isopropanol, nitric acid,
trimesic acid were mixed with the blank carrier and then the liquid
was vaporized at 80  C. Then they changed the loading method by
reducing the content of titanium in the mixture from 134 g/L to
100 g/L. Finally, the carrier loaded with 0.40 g/L TiO2 was obtained
by removing the additive trimesic acid and the coating efficiency
reached 83%. The optimization of new carrier coating method ob-
tained a thinner and well-distributed TiO2 coating, greatly
enhancing the photocatalytic efficiency and adherence strength.
Xing et al. (2014) designed a novel porous crystalline anatase TiO2
by frozen-casting method based on camphene. The ordered mes-
oporous TiO2 with good thermal stability could enhance photon
utilization ratio and the photocatalytic efficiency (Li et al., 2013; Shi
et al., 2013). Besides, mesoporous nano-TiO2 has been proved to be
an excellent photocatalyst owing to its large surface area and or-
dered porous structure, thus improving the surface reactive sites
and contaminants adsorption (Jiang et al., 2013).
As is known to all, good crystallinity of anatase type TiO2 is one
of the key factors to improve its photocatalytic performance (Er
et al., 2014; Xing et al., 2014). The heat treatment method is used
to change mesoporous TiO2 from amorphous to crystalline, but it
leads to unnecessary growth and complete destruction of ordered
structure (Deng et al., 2013; Li et al., 2014; Wang et al., 2014). Zhang
et al. (2016a) induced the good thermal stability ordered meso-
porous SiO2eTiO2 compounds in order to improve the photo-
catalytic performance of TiO2. The introduction of SiO2 can restrain
the anatase-to-rutile phase transformation, and preserve the or-
dered mesoporous structure and high crystallinity of TiO2 even
after being calcined at 800  C. The prepared ordered mesoporous
mixed materials not only have good thermal stability, but also
improve the specific surface area and the recovery of
photocatalysts.
3.1.2. Visible-light photocatalysts
The range of the photocatalysts induction to light and the
penetration of light in water are two extremely important factors
for ICPB (Lim and Kim, 2004). The UV spectrum response for pho-
tocatalysts activation is often accompanied by high operating costs,
and can damage the biofilm outside the carrier. In order to expand
the range of photo-response of TiO2 for solar spectrum, different
methods have been designed, such as noble metals incorporation
(Ni et al., 2007), non-metals (Fujishima et al., 2008) and transition
metals doping (Litter, 1999).
Firstly, noble metals have a lower Fermi level than TiO2 photo-
catalyst is deposited on the surface of TiO2 to enhance charge
separation (Ni et al., 2007). Xiong et al. prepared visible light driven
Ag-doped TiO2 in ICPB (Xiong et al., 2017). The photocatalyst
coating process used a sol-gel and evaporation induced self-
assembly (EISA) method. Ag doped on the crystal lattice or sur-
face of TiO2 could trap photo-generated electrons or holes, thus
promoting electron-hole separation in photocatalysis process
(Xiong et al., 2018). This new ICPB method had a good ability to
mineralize pollutants and protect the biofilm under visible light
irradiation, which was called VPCB (Dong et al., 2016; Zhou et al.,
2015).
In addition to doping with noble metals, non-metal doping can
also enhance the photocatalytic performance and practicability of
TiO2 catalysts (Fujishima et al., 2008). Among the various dopants,
nitrogen (N) is the most widely investigated, and the most prom-
ising results have been obtained, extending the absorption edge of
TiO2 to the visible region (Fujishima et al., 2008; Qiu and Burda,
2007). By using N-doped TiO2 (NeTiO2), the ICPB photo-anode
could respond to visible light (Teng et al., 2013; Wen et al., 2012).
Zhou et al. (2017) successfully fabricated an electrochemical cell
with the carbon-foam based on NeTiO2 ICPB-anode. The unique
properties of NeTiO2 made it have high reactivity and suitability.
The enhanced visible light activity of NeTiO2 was attributed to the
bandgap reduction by N doping in TiO2 structure, or as an alter-
native to the oxygen lattice sites (Ananpattarachai et al., 2009).
It was found that self-assembly technique was useful for pre-
paring monodispersed TiO2 layers with high loading amount at low
temperatures. A visible light responsive photocatalyst Er3þ: YAlO3/
TiO2 hybrid composite was prepared by sol-gel technique and
 M. Yu et al. / Water Research 175 (2020) 115673
hydrothermal treatment in the range of 90e170  C (Dong et al.
2015, 2016; Zhang et al., 2017b; Zhou et al., 2015). Possible mech-
anism of the enhanced photocatalytic reactivity in Er3þ: YAlO3/TiO2
was proposed in Fig. 2 (Dong et al., 2015). Er3þ: YAlO3/TiO2 was an
effective up-conversion system that converted visible light into
ultraviolet light. Under the excitation light, the Er3þ: YAlO3/TiO2 as
an up-conversion agent firstly absorbed the visible light and then
emitted UV. Thus, the UV effectively excited the TiO2 to start the
photocatalytic process (as described in Fig. 1), leading to the
enhanced photocatalytic degradation of MO in the VPCB.
In a sum, the conventional photocatalytic materials in ICPB
system are mainly TiO2-based photocatalysts. The trend is to
develop more efficient and inexpensive visible light photocatalysts,
for which more researches need to be carried out. Ding et al. used
an inexpensive and highly efficient belt-shaped one-dimensional
oxygen-rich Bi12O17Cl2 as a visible light photocatalyst in ICPB sys-
tem (Ding et al., 2018). The result showed a removal rate of
oxytetracycline of 94%. Moreover, many potential efficient photo-
catalysts are proposed here as substitutes for classical TiO2-based
photocatalysts, including (i) geC3N4ebased photocatalysts, such as
P-doped g-C3N4 (Deng et al., 2017b) and W18O49/g-C3N4 (Deng
et al., 2018a); (ii) Bi-based photocatalysts, such as Bi2WO6 (Wang
et al., 2018) and BiVO4 (Chen et al., 2017); (iii) AgPO4-based pho-
tocatalysts, such as Mn3O4/MnO2eAg3PO4 (Cai et al., 2019) and
Ag3PO4@Fe3O4 (Wang et al., 2019). These photocatalytic materials
not only extend the range of photo-response to visible or even near-
infrared light, but also promote the separation of photoinduced
charges and holes, which has great application potential in ICPB
system.
3.2. Carriers of ICPB
As one of the important components of the ICPB system, the
carrier needs to have a wet density similar to that of water in order
to be adequately stirred during aeration. This can not only keep the
carrier in contact with pollutants, but also ensure the continuous
exchange of degradation products. Besides, large porosity and good
biocompatibility are also required. On the one hand, it provides the
loading matrix for the photocatalytic materials; on the other hand,
it provides the sites for the adhesion of the biofilm. At the same
time, the microbes growing in the pores can keep their own activity
because they can avoid the impact of UV light, free radicals and
abrasion, which can guarantee the ICPB system to work well
(Rittmann, 2018). The following sections outline a few represen-
tative carriers that are suitable to be used in ICPB system, such as
cellulose carrier (Marsolek et al., 2008), ceramic carrier (Xing et al.,
2014), polyurethane sponge (Li et al., 2011) and polyurethane foam
(PUF) (Zhang et al., 2016a).
Fig. 2. Schematic illustration for the enhanced photocatalytic reactivity degradation of
MO in Er3þ: YAlO3/TiO2 coated carrier under visible light irradiation. Adapted from
(Dong et al., 2015).
5
3.2.1. The cellulose carrier
When Marsolek et al. first put forward the concept of ICPB in
2008, the carrier was porous cellulose with side length of 4 mm
(Marsolek et al., 2008). The surface of the material was positively
charged, and it had certain adsorption ability for the pollutants in
water. The density of this cellulose dressing of 1.04 g cm 3 was
close to that of water, and the average porosity was 0.93. The
dressing had good biocompatibility, and the microorganism could
be loaded well on the whole carrier during the process of biofilm
hanging. In the cellulose carrier supported ICPB, the removal effi-
ciency of acetate was 100%. It also confirmed that the process of
photocatalytic reaction and biodegradation could exist in the same
reactor under reasonable experimental design. The porous cellu-
lose was also used in fluidized bed biodegradation of quinolone
(Machado et al., 2006).
3.2.2. The ceramic carrier
Although the cellulose carrier have an ideal pore structure and
can be used to accumulate and protect the bacteria, the carrier will
be oxidized and charred gradually under the attack of hydroxyl
radical (Marsolek et al., 2008). Besides, the low loading capacity of
cellulose dressing carrier for photocatalytic materials can not
maintain the photocatalytic property of ICPB for a long time.
Ceramic carrier with rough surface is resistant to radical attack and
helpful to increase the loaded amount of photocatalytic material. Its
wet density ranges from 1.03 to 1.05 g∕cm3, which can float on the
surface of liquid under aeration condition, so it is suitable for cir-
culation. In application, it could strongly adsorb pollutants in the
solution and protect microorganisms inside from UV irradiation
and free radicals (Wen et al., 2012; Zhang et al., 2012b). Xing et al.
(2014) reported that camphor, as a three-dimensional (3D) con-
nected network of frozen vehicles, could sublimate in the ceramic
body and leave macroporous channels. The obtained ceramic had a
layered mesoporous structure with average size of 8  8  2 mm3,
and the average mass of one piece was 20 mg. The prepared mes-
oporous TiO2 ceramic carrier exhibited both great mechanical sta-
bility and good recyclability. The obtained ceramics supported ICPB
had good adsorption and photocatalytic activity for the degradation
of octane and rhodamine B (RhB). The total organic carbon (TOC)
removal rate after degradation for 3 h reached 98.8% and 98.6%,
respectively.
3.2.3. The polyurethane sponge
Ideally, the carrier should have a proportion similar to that of
water in order to have a good circulation in PCBBR, a suitable size of
macroporous structure to accumulate biomass and protect them
from the influence of UV/free radical attack. Polyurethane sponge
as a commercial product has both large porosity and good
biocompatibility. It has been used in biological packing, air filter
and cosmetics industry (Li et al., 2012b). Li et al. (2011) used the
commercial polyurethane sponge (Fig. 3) as the carrier of photo-
catalytic materials and microbes. The size of this sponge-type cube
was 3.5 ± 0.3 mm, which was beneficial to shelter biofilm inside
while enhancing photocatalysis outside the surface. The carrier had
a specific surface area of 4.8 m2∕g, and high porosity (88%). The
internal pore size was 50e500 mm and its wet density
(1.01e1.02 g∕cm3) was close to the water. These properties not only
provided sufficient porosity to support the loading of photo-
catalytic materials and growth of microorganisms, but also ensured
the free flow of water in the polyurethane sponge. At the same
time, Wen et al. compared the porous ceramic materials with the
polyurethane sponge (Wen et al., 2012). They found that the time
for biofilm growth in polyurethane foam was about 10 d, while
porous ceramics needed about 30 d. Furthermore, it was also found
that smaller carriers may provide a larger surface-area-to-volume
6 M. Yu et al. / Water Research 175 (2020) 115673

activity of microbe is reduced after attack by UV irradiation. Zhou

et al. compared UPCB with VCPB for the degradation of phenol for
the first time (Zhou et al., 2015). It was found that the microbial
communities in the carrier were well protected under visible light
irradiation and the secretion of EPSs was also enhanced. As we
mentioned before, bacteria may produce EPSs to protect them-
selves by scavenging free radicals.
In the ICBP process, biofilm has considerable substrate removal
capability, which is a major factor in the removal of chemical ox-
ygen demand (COD) or dissolved organic carbon (DOC) (Li et al.,
2011; Marsolek et al., 2008; Zhang et al., 2010). Xiong et al.
(2017) cultured un-acclimated activated sludge to form biofilm in
the porous carriers. A rich biofilm adhered on the core and outer
surface of the carriers, and it was bridged with a large number of
Fig. 3. The picture of the sponge-type cube and SEM images of the interior and EPSs. The biofilm in VPCB was adapted to the utilization of photo-
exterior of the polyurethane sponge. Adapted from (Li et al., 2011). catalytic intermediates, which enhanced by 20% in COD removal.
Fig. 4 shows the changes to the genus-level microbial community
structure during VPCB. Before tetracycline hydrochloride was
ratio to enable more catalysts to be exposed on the surface of the degraded, the prevailing genus were Massilia, Acinetobacter, Jan-
carrier. Zhou et al. reported a polyurethane cube with a side length thinobacterium, and Pseudomonas, which were common genus in
of 2 mm as an ideal smaller porous sponge carrier for the ICPB the treatment of biological wastewater (Zhang et al., 2011a). After
reaction. Finally, removal efficiency of phenol by VPCB was pro- the degradation of TCH, Methylibium, Runella, Comamonas, and
moted to 99.8%. The wet density of the original and photocatalyst Pseudomonas were enriched in the biofilms in the VPCB carriers,
coated sponge was 0.89 and 1.04 g/mL, respectively, with which were known for their biodegradation of aromatics and TCH
100e300 mm in the pore size and 87% in porosity (Xiong et al., 2018; resistance. It indicated that VPCB worked well during the TCH
Zhou et al., 2015). degradation process. ICPB can overcome the bio-refractory nature
of organic contaminants by using active biofilms and
photocatalysis.
3.2.4. The polyurethane foam
In addition to the aforementioned carriers (Zhang et al., 2016a),
designed ordered mesoporous SiO2eTiO2 composite with high
4. Configurations of PCBBR
thermal stability, and firstly coated it on the macroporous PUF as a
layered mesoporous biofilm carrier. The PUF carrier had a 3D
According to the deployment of photocatalysts, PCBBR for
macroporous network structure with an average length of 1 cm and
wastewater treatment can usually be divided into two major con-
an average pore size of 2 mm. Its density was 0.8 g/cm3, and it was
figurations: (1) PCBBR with suspended photocatalysts and (2)
easy to fluidize PUF in water under the normal aeration intensity.
PCBBR with immobilized photocatalysts. The two major configu-
The total organic carbon (TOC) removal efficiency of 2, 4, 5-TCP was
rations differ in that the first needs further separation from water to
up to 97.5% in the macroporous PUF supported ICPB. In general, PUF
recover the photocatalysts, while the latter allows a continuous
has been commercialized for ICPB system with good economic
operation. For the latter one, there are two groups according to the
viability.
types of the light source: (1) UV-light responsive photocatalytic
Moreover, many potential alternatives to carriers in ICPB system
circulating-bed biofilm reactor (UPCBBR) and (2) visible-light
are proposed: (i) three-dimensional graphene gels such as hydro-
responsive photocatalytic circulating-bed biofilm reactor (VPCBBR).
gels and aerogels have been widely used in various fields due to
their high porosity, low density, and conductivity (He et al., 2018);
(ii) MOFs have attracted a lot of interests in adsorption, catalysis,
optoelectronic devices, gas storage and separation, and drug de-
livery, owing to the easy tunability of pore size and shape and large
specific surface areas (Wu et al., 2017); (iii) agar is widely used in
the preparation of medium and polymer hybrid hydrogels, and can
also be used in the field of catalysis (Zhang et al., 2016b); (iv)
melamine foam has been applied to the loading of photocatalysts
due to its porous structure and superhydrophilicity (Geng et al.,
2019). These potential carriers are promising materials used in
ICPB system for the treatment of water pollutants.

3.3. Biofilms of ICPB

Biofilms are the accumulation of microorganisms attached to a

solid surface and exist ubiquitous in natural environment
(Rittmann, 2018). In ICPB system, biofilms biodegrade photo-
catalytic intermediates to realize further mineralization. UPCB have
worse mineralization capability because of the release of SMPs
Fig. 4. Relative abundances of the biofilm genera from the initial inoculum to the end
caused by cell lysis. SMPs are likely to be released into the effluent of cycle 6. The abundance is presented in terms of the percentage of total effective
when radicals attacked the biofilm. The poor mineralization of microbial sequences in each sample. The gray bar represents the sum of all low-
UPCB is also due to the serious separation of the biofilms, and the abundance genera. Adapted from (Xiong et al., 2017).
 M. Yu et al. / Water Research 175 (2020) 115673
4.1. PCBBR with suspended photocatalysts
In PCBBR with suspended photocatalysts, the photocatalysts are
uniformly dispersed in the feed solution, and carriers are inde-
pendently applied to protect the biofilms. An obvious advantage of
this system is that the photocatalysts have sufficient contact with
pollutants due to the large specific surface area, while the PCBBR
with immobilized photocatalysts is often hindered by the mass
transfer limitation on the photocatalyst coated carriers. In addition,
a large amount of photocatalyst is feasible to be applied in the
suspension system, but in the immobilized PCBBR system, photo-
catalyst is much less due to the limited surface area of the carrier.
As shown in Fig. 5, a typical slurry-typed PCBBR system was
used for 2, 4, 5-TCP and acetate removal (Marsolek et al., 2008). The
biofilms in PCBBR accumulated in the macroporous carriers were
well protected from UV light, chemical toxicity, ROS, and physical
loss, while oxidation reaction occurred on the slurry-typed TiO2-
photocatalyst. The volume of the liquid in the laboratory-scale
PCBBR was 122 mL. Liquid circulation was realized by aeration,
which also supplied dissolved oxygen (DO) for photodegradation
and biodegradation. The influent entered the reactor by a micro-
pulse pump. UV-light illuminated at the lower half of a reactor,
increasing the reflection of high intensity light. The results showed
that the slurry-typed PCBBR system almost completely removed
TCP, in which photocatalysts were responsible for the rapid removal
of TCP and biofilms inside the carriers contributed to removing the
COD. Photocatalysts can be separated through adding a sedimen-
tation basin or a filtration system, so that the slurry reactor can be
continuously operated (Chong et al., 2010).
4.2. PCBBR with immobilized photocatalysts
In PCBBR with immobilized photocatalysts, the photocatalysts
are fixed on the surface of carriers, which are beneficial to the
separation of the photocatalysts from the wastewater, and avoids
secondary pollution and photocatalysts loss. The carriers can act as
not only the support for photocatalysts but also the ideal place for
biofilm accumulation. We have summarized the different methods
of coating carriers with a catalyst layer on the surface, including sol-
gel, low temperature sintering method, EISA, and ultrasonically
dispersed and evaporation (Table 1). The following part describes
typical configurations of different light position or different light
source types.
Fig. 5. The PCBBR system utilizes macro-porous cellulosic carriers that protect microorganisms from toxic reactants and organic compounds, making intimate coupling possible.
The ESEM image shows the porosity and size of the pores. UV-light illuminated at the lower half of a reactor, increasing the reflection of high intensity light. Adapted from (Marsolek
et al., 2008).
7
Fig. 6a shows a laboratory-scale UPCBBR made of quartz glass
with a volume of 150 mL and suspended circulating carriers on the
rising and falling sides (Li et al., 2011). Except for the 18 cm long
side of the riser, the UPCBBR was covered with aluminum foil to
reflect UV light. Water and carrier circulation was realized through
aeration by an air-lift pump, which also supplied DO at an aeration
rate of 21 mL/min, and the feed water was provided at a rate of 0.4
mL/min. The UPCBBR was illuminated by two UV lamps with an
intensity of 3.0 mWatt/cm2 and located on the exposed part of the
reactor. The total illumination volume was about 41 cm3, ac-
counting for 27% of the total volume of the UPCBBR. Fig. 6b presents
the schematic diagram and photo of UPCBBR, which used a 1 L
quartz glass reactor (Zhang et al., 2016a). Unlike the common
PCBBR, the quartz sleeve was placed in the middle of the reactor,
while the UV lamp was placed in the quartz sleeve. Liquid circu-
lation was realized by aeration at the bottom of the reactor. To in-
crease the light utilization by reflecting light, the outside of UPCBBR
was covered with aluminum foil. The PCBBR was kept at a room
temperature of 12 ± 2  C. The results showed that 100 mg/L of
phenol and 20 mg/L of 2, 4, 5-TCP could be totally degraded by
running the reactor for 3 h and 6 h, respectively.
The two PCBBR systems described above were both operated
under UV light irradiation. Zhou et al. (2015) compared the effect of
UV light and visible light on degrading phenol in PCBBR. As a result,
the removal rate of phenol by the VPCBBR was 99.8%, which was
32.6% higher than that of the UPCBBR. Biofilm was severely shed
due to UV irradiation, resulting in poor removal efficiency of phenol
in UPCBBR. As shown in Fig. 7, Ma et al. (2015) designed a VPCBBR.
The reactor was an internal loop air-driven reactor with a volume of
540 mL, filled with approximately 750 sponge carriers and oper-
ated at 20 ± 2  C. The VPCBBR draft tube is a plexiglass tube with a
diameter of 40 mm, a height of 130 mm and a bottom aerator of
40 mm. The oxygen was provided by an aeration pump with an
aeration rate of 480 g O2 (g phenol
H)1 and a flow rate of 10.6 mm/
s. The VPCBBR was irradiated by visible light from two opposing
LED panels which were placed approximately 10 cm each side of
the reactor. The highest phenol removal efficiency (99.8%) and
mineralization (67.1%) capability was observed within 16 h in
VPCBBR.
Both configurations of PCBBR with suspended or immobilized
photocatalysts have their own characteristics and limitations.
Table 2 briefly summarizes the main advantages and disadvantages
of these two types of PCBBR.
8 M. Yu et al. / Water Research 175 (2020) 115673
a bb
Fig. 6. Schematic diagram of UV-light responsive photocatalytic circulating-bed biofilm reactor (UPCBBR): (a) The UPCBBR was illuminated by two UV lamps located on the exposed
part of the reactor. Adapted from (Li et al., 2011). (b) The UPCBBR was illuminated by the UV lamp placed in the quartz sleeve, while the quartz sleeve was placed in the middle of the
reactor. Adapted from (Zhang et al., 2016).
Fig. 7. Schematic diagram of visible-light responsive photocatalytic circulating-bed
biofilm reactor (VPCBBR). The air was supplied by an aeration pump and the reactor
was illuminated with visible light from the LED panel. Adapted from (Ma et al., 2015).
5. Applications
Wastewater treatment can be more sustainable if it can recycle
energy and other resources while removing recalcitrant organic
pollutants (Li et al., 2015). ARB could conduct electrons to the
cathode, which makes it possible to generate electricity, hydrogen
gas, or other valuable resources (Li et al., 2015; Sharma et al., 2014).
Under the action of photocatalytic reaction and microorganism,
ICPB system can achieve high efficiency and rapid treatment of
UV lamp
Exhaust port
Water outlet
Air bubble
SiO2-TiO2
coated carriers
Quartz sleeve
Water inlet
Intake port
refractory pollutants. It has good practical application prospect in
environmental purification. ICPB has been proven to be suitable for
many bio-recalcitrant organic pollutants, including phenol (Dong
et al., 2016; Zhang et al., 2010), nitrobenzene (Yang et al., 2015a),
quinolone (Yan et al., 2013), dyes (Li et al., 2012a) and so on. Recent
studies on the practical applications of ICPB in the treatment of
wastewater and energy production are summarized in Table 3.
5.1. Degradation of nitrogenous compounds
Quinoline (C9H7N) is a typical nitrogenous heterocyclic com-
pound that is recalcitrant to be biodegraded, which is widely used
in dye, rubber, pharmaceutical, food, and chemical industries
(Felczak et al., 2014). The sequentially and intimately coupling
ability of photolysis and biodegradation were simultaneously
investigated to improve the removal rate of quinoline and the ki-
netics of quinoline mineralization. In the internal loop photo-
biodegradation reactor (ILPBR), the maximum quinoline removal
efficiency (Rmax) increased by 9% and the half-maximum-rate
concentration (KS) decreased by 55% compared to sequentially
coupling. The results showed that the biodegradation rate of
quinoline was about twice of that in the sequentially coupling
system. Both intimate coupling and sequential coupling systems
increased the degree of mineralization by 18% and 5%, respectively.
Therefore, the simultaneous photocatalysis and biodegradation in
ILPBR was superior to sequentially coupling (Yan et al., 2013). 2, 4-
dinitrotoluene (2, 4-DNT), an intermediate in the manufacture of
polyurethanes and dyes, is easy to disperse in soil and groundwater
when not handled properly (Dontsova et al., 2009). Wen et al.
employed ICPB system degrading 2, 4-DNT (Wen et al., 2012).
Although the final degradation efficiency of 2, 4-DNT by ICPB was
similar to that in solo photocatalytic degradation, the results
showed that the conversion ratios of the organic nitrogen to NHþ 4-
N, NO 
2 -N and NO3 -N in ICPB were much higher than the latter.
Therefore, the intermediate products of photocatalysis and photo-
degradation were further destroyed by microorganism, which
promoted the degradation of 2, 4-DNT.
 M. Yu et al. / Water Research 175 (2020) 115673 9

Table 2
Main advantages and disadvantages of PCBBR with suspended/immobilized photocatalysts.

PCBBR with suspended photocatalysts PCBBR with immobilized photocatalysts

Advantages a) Higher photocatalytic efficiency due to enough contact between a) No need to separate the photocatalysts;
photocatalysts and pollutants; b) Pollutants can be simultaneously degraded and mineralized in carrier;
b) Convenient to adjust the photocatalyst concentration to the desired c) The carrier will not be blocked by suspended photocatalysts.
value.

Disadvantages a) Higher operating cost and additional processes to separate a) Lower photocatalytic efficiency due to lower effective specific surface area
photocatalysts; of the photocatalysts;
b) Lower final mineralization rate. b) Not possible to flexibly adjust photocatalyst loading according to
wastewater composition.

Table 3
Applications of ICPB in treatment of wastewater and energy product.

Target pollution Photocatalysts Carriers Main results Ref.

2,4-dinitrotoluene (2,4-DNT) TiO2 The ceramic 2,4-DNT removal: 99% Wen et al. (2012)
The sponge DOC removal: 70%
2,4,5-trichlorophenol (TCP) with P25 TiO2 The cellulose cubes TCP removal: 23.6% Marsolek et al.
acetate Acetate removal: 100% (2008)
Phenol TiO2 The ceramic Phenol removal: 100% Zhang et al. (2010)
COD removal: 92%
2,4,5-trichlorophenol (TCP) TiO2 The sponge TCP removal: 98% Li et al. (2011)
COD removal: 96%
2,4,6-trichlorophenol (TCP) TiO2 The ceramic TCP removal: 100% Zhang et al. (2012b)
COD removal: 95%
3þ
Phenol Er :YAlO3/TiO2 The sponge Phenol removal: 99.8% Zhou et al. (2015)
DOC removal: 63.9%
3þ
Phenol Er :YAlO3/TiO2 The sponge Phenol removal: 99.8% Dong et al. (2016)
MO removal: 94.8%
COD removal: 65.2%
4-chlorophenol (4-CP) NeTiO2 The carbon foam 4-CP removal: 90.5% Zhou et al. (2017)
Current density:0.40A/m2
reactive black 5 (RB5) TiO2 The sponge RB5 removal: 97% Li et al., 2012a
COD removal: 65%
Rhodamine B (RhB) TiO2 The ceramic Octane removal: 98.8% Xing et al. (2014)
RhB removal: 98.6%
Tetracycline Hydrochloride (TCH) Ag/TiO2 The polyurethane TCH removal: 85% Xiong et al. (2017)
sponge COD removal: 66%
TCH with acetate Ag/TiO2 The polyurethane TCH removal: 95% Xiong et al. (2018)
sponge SCOD removal: 95%
Phenanthrene (PHE) Mn3O4/MnO2 The polyurethane PHE removal: 96.2% Cai et al. (2019)
eAg3PO4 sponge TOC removal: 31.93%
Oxytetracycline Bi12O17Cl2 The polyurethane Oxytetracycline removal: 94% Ding et al. (2018)
sponge TOC removal: 26.3%
Na2S (Sacrifice) NeTiO2 The carbon foam Current density: 5.7 A/m2 (100 mM PBS) 3.9 A/m2 (50 mM Zhou et al. (2018)
NaHCO3)

5.2. Degradation of phenolic compounds

Phenolic compounds are typical examples of bio-recalcitrant

toxic contaminants exhibited in the wastewater from various in-
dustries, such as the production of fungicides, herbicides and tex-
tiles (Su et al., 2012; Wu et al., 2012; Yang et al., 2015b). Zhou et al.
(2015) compared the effects of VPCB and UPCB on the degradation
of phenol (Fig. 8). The photocatalyst was doped with both Er3þ and
YAlO3 into TiO2 coated on the sponge carriers. The removal effi-
ciency of phenol in the VPCB reached 99.8%, which was 32.6%
higher than that in the UPCB. The photocatalytic and biodegrada-
tion reactions were tightly coupled in the VPCB, leading to 63.9%
removal of DOC, which further showed the synergistic action of
photocatalysis and biodegradation.
Theoretically, the degradation of chlorophenol can be acceler- Fig. 8. Comparison of the effects of UPCB and VPCB on the degradation of phenol
ated by a co-substrate, or be inhibited by the competition of ROS. under UV light or visible light irradiation. Adapted from (Zhou et al., 2015).
Zhang et al. investigated the effect of phenol and pyrocatechol on
the degradation of 4-CP (Zhang et al., 2017a). The removal rate of 4-
CP was 51%, increasing to 62% after phenol addition. At the same rate of 4-CP to 32%. The difference in the results was due to the
time, the dechlorination efficiency of 4-CP increased from 47 to additional electron donor offered by the photodegradation product
63%. In contrast, the addition of pyrocatechol reduced the removal of phenol to the bacteria, which promoted the degradation of 4-CP,
10 M. Yu et al. / Water Research 175 (2020) 115673
while the pyrocatechol competed with 4-CP for ROS to inhibit its
degradation. In the treatment of phenolic compounds by ICBP,
competition for ROS and co-substrate performances should be
considered.
5.3. Degradation of reactive dyes
Among various pollutants, organic dyes are one of the most
widely used chemicals, mainly from textiles, cosmetics, paper,
leather and other industries (He et al., 2018). ICPB could further
mineralize many reactive dyes, such as reactive dye black 5 (RB5)
(Li et al., 2012a), methyl orange (MO) (Dong et al., 2016) and RhB
(Xing et al., 2014). The degradation and mineralization of RB5 by a
novel bio-recalcitrant-coated biofilm carrier with ICPB were stud-
ied in a PCBBR (Li et al., 2012a). Compared with the low minerali-
zation portion of RB5 in photocatalytic reaction, the removal
efficiency of dyes and COD by the system could reach 97% and 65%,
respectively. Not only was the highly efficient degradation of RB5
realized, but also the intermediate products of photocatalytic re-
action were further mineralized. Photocatalysis was the main cause
of dye loss, but biodegradation led to the most removal of COD. It
was also proved indirectly that the system could run stably under
low pH conditions.
5.4. Degradation of antibiotics
The prevalence of antibiotics in aquatic systems has become an
environmental issue due to that it may result in antibiotic-resistant
pathogens (Zhang et al. 2014a, 2014b). Degradation of tetracycline
hydrochloride (TCH) (Xiong et al. 2017, 2018), oxytetracycline (Ding
et al., 2018) and sulfamethoxazole (SMX) (Yan et al., 2012) have
been studied in ICPB. TCH is one of the most widely used antibiotics
with four aromatic rings and is difficult to biodegrade in traditional
biological treatments (Gao et al., 2012; Wang et al., 2016d; Zhang
et al., 2011b). Xiong et al. (2017) used ICPB to degrade TCH with
visible light. Compared with photocatalytic degradation alone, the
degradation efficiency of TCH was increased by 11% in the first 2 h,
and the removal rate of COD was also increased by more than 20%.
Xiong et al. (2018) tried to further enhance metabolic activity
through adding an easily biodegradable co-substrate that could act
as a carbon source and electron donor to promote bioconversion
and mineralization of TCH. When acetate was added in ICPB, the
TCH removal rate increased by 5% and the mineralization increased
by 20%, and almost all of the photocatalytic imtermediates dis-
appeared. Acetate addition could offer extra electron donors to
Fig. 9. (a) Anode layout for the ICPB-anode electrochemical cell with a schematic detail of the carbon-foam anode. Features of the anode (b) during illumination and (c) after around
7 days’ illumination. Adapted from (Zhou et al., 2017).
enhance more biomass synthesis, inhibit toxicity effects, and
improve photocatalytic oxidation (Bai et al., 2015; Kim et al., 2014;
Muller et al., 2013). Therefore, providing a co-substrate that is easily
biodegradable is an effective way to increase TCH removal and
mineralization in the ICPB system.
5.5. Current generation
The recovery of energy from organic wastewater could be ach-
ieved by the anode-respiring bacteria (ARB), which oxidize electron
donors and transfer the electrons to the anode in ICPB. Zhou et al.
prepared an anode intimately coupled ARB with NeTiO2 on a
porous carbon foam electrode and experiment tested in an elec-
trochemical cell (Zhou et al. 2017, 2018). The configuration of a flat-
plate double-chamber electrolytic cell, made of plexiglass, was
shown in Fig. 9a. A 3 cm  3 cm ICPB-anode was fixed in the anode
chamber, ARB was accumulated in the pores, and the surface was
coated with NeTiO2 as a working electrode. Fig. 9b and c showed
the features of the anode during irradiation and after around 7
days’ irradiation. The corresponding mineralization rate of the
ICPB-anode was the highest and the current generated was 50%
higher than that of bio-anode current. The ICPB anode significantly
enhanced the biodegradation of 4-CP while recovering electrical
current. The large increase in current density in ICPB was due to the
fact that 4-CP photocatalysis produced partially oxidized products
and were biodegraded (Zhou et al., 2017). Combination of the
catalysis by photocatalyst and the biodegradation by biofilm should
be able to degrade bio-refractory contaminants and recover energy
by using the ICPB-anode.
6. Conclusions and future prospects
ICPB technology has shown a huge potential advantage in the
field of water treatment. This review summarizes the mechanisms
involved in ICPB, from the recent advances of photocatalytic ma-
terials, carriers and biofilm, and varied applications. At present, the
study of ICPB for wastewater treatment has just started, and the
mechanism of microscopic action of ICBP is not well understood,
which limits its development of improving the degradation effi-
ciency of pollutants and its practical application. In view of the
existing defects and deficiencies in the field, further research fields
on ICPB are suggested.
There is a lack of detailed information on the degradation
mechanisms, impact of operational variables on pollutants removal
and optimized parameters for reactor design. To optimize the
 M. Yu et al. / Water Research 175 (2020) 115673
structure of the reaction system, various factors (e.g. aeration rate,
coating ratio of photocatalysts) that may affect the reaction process
need to be fully considered. The operating parameters need to be
regulated for a stable photocatalytic operation over a wider pH
range. The mechanism of electron transfer process between pho-
tocatalyst and biofilm remains to be further studied.
To enhance the photocatalytic reaction efficiency in ICPB sys-
tem, novel photocatalytic materials responding to wider solar
spectra and carriers with large loading amount of catalysts need to
be developed, such as g-C3N4, Bi2WO6, three-dimensional graphene
gels and MOFs. The future applications of carriers also rely on the
development of high-strength, bio-based, porous, repeatability and
3D carriers with easy-to-implement synthetic solutions. And to
improve the function of microbial communities, the sources of
microbial inoculation for emerging pollutants should be optimized
for increasing the degradation efficiency of target pollutants. New
genetic engineering knowledge should be introduced to degrade
pollutants with screening and amplification of the most effective
microorganisms, which can shorten the hydraulic residence time
and save the capital cost of the designed reactor.
We note that the current research of ICPB is still in infancy, and
there are still many problems in practical applications such as the
light reflection and occlusion in actual wastewater. The key to over
this problem is that the carrier needs to have a wet density similar
to that of water in order to contact pollutants in the water and
absorb light simultaneously. Moreover, the easy separation of
photocatalyst coated on carrier after wastewater treatment can
help apply ICPB technology in industrial practice. In view of the
current research and trends, there is no doubt that the ICPB system
will play a significant role in many other interesting applications,
including (i) removal of heavy metal ions (Xu et al., 2012); (ii)
practical soil remediation (Wang et al., 2019); (iii) chemical re-
sources production (Sakimoto et al., 2016); and (iv) catalytic
oxidation of volatile organic compounds (VOCs) (He et al., 2019).
These potential applications should be combined with ICPB to
create more widespread applications.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper
Acknowledgments
The study was financially supported by Projects 51579096
supported by National Natural Science Foundation of China, the Key
Research and Development Program of Hunan Province of China
(2017SK2241), the National Innovative Talent Promotion Program
of China (2017RA2088), the Funds for Innovative Province Con-
struction of Hunan Province of China (2019RS3012), and the Na-
tional Program for Support of TopeNotch Young Professionals of
China (2012).
References
Ananpattarachai, J., Kajitvichyanukul, P., Seraphin, S., 2009. Visible light absorption
ability and photocatalytic oxidation activity of various interstitial N-doped TiO2
prepared from different nitrogen dopants. J. Hazard Mater. 168 (1), 253e261.
Bai, Q., Yang, L., Li, R., Chen, B., Zhang, L., Zhang, Y., Rittmann, B.E., 2015. Accelerating
quinoline biodegradation and oxidation with endogenous electron donors.
Environ. Sci. Technol. 49 (19), 11536e11542.
Brosillon, S., Djelal, H., Merienne, N., Amrane, A., 2008. Innovative integrated pro-
cess for the treatment of azo dyes: coupling of photocatalysis and biological
treatment. Desalination 222 (1e3), 331e339.
Cai, H., Sun, L., Wang, Y., Song, T., Bao, M., Yang, X., 2019. Unprecedented efficient
degradation of phenanthrene in water by intimately coupling novel ternary
11
composite Mn3O4/MnO2-Ag3PO4 and functional bacteria under visible light
irradiation. Chem. Eng. J. 369, 1078e1092.
Chalasani, R., Vasudevan, S., 2013. Cyclodextrin-functionalized Fe3O4@TiO2: reus-
able, magnetic nanoparticles for photocatalytic degradation of endocrine-
disrupting chemicals in water supplies. ACS Nano 7 (5), 4093.
Chen, F., Yang, Q., Li, X., Zeng, G., Wang, D., Niu, C., Zhao, J., An, H., Xie, T., Deng, Y.,
2017. Hierarchical assembly of graphene-bridged Ag3PO4/Ag/BiVO4 (040) Z-
scheme photocatalyst: an efficient, sustainable and heterogeneous catalyst with
enhanced visible-light photoactivity towards tetracycline degradation under
visible light irradiation. Appl. Catal. B Environ. 200, 330e342.
Chong, M.N., Jin, B., Chow, C.W., Saint, C., 2010. Recent developments in photo-
catalytic water treatment technology: a review. Water Res. 44 (10), 2997e3027.
Deng, Y., Tang, L., Feng, C., Zeng, G., Chen, Z., Wang, J., Feng, H., Peng, B., Liu, Y.,
Zhou, Y., 2018a. Insight into the dual-channel charge-charrier transfer path for
nonmetal plasmonic tungsten oxide based composites with boosted photo-
catalytic activity under full-spectrum light. Appl. Catal. B Environ. 235,
225e237.
Deng, Y., Tang, L., Feng, C., Zeng, G., Wang, J., Lu, Y., Liu, Y., Yu, J., Chen, S., Zhou, Y.,
2017a. Construction of plasmonic Ag and nitrogen-doped graphene quantum
dots codecorated ultrathin graphitic carbon nitride nanosheet composites with
enhanced photocatalytic activity: full-spectrum response ability and mecha-
nism insight. ACS Appl. Mater. Interfaces 9 (49), 42816e42828.
Deng, Y., Tang, L., Zeng, G., Dong, H., Yan, M., Wang, J., Hu, W., Wang, J., Zhou, Y.,
Tang, J., 2016. Enhanced visible light photocatalytic performance of polyaniline
modified mesoporous single crystal TiO2 microsphere. Appl. Surf. Sci. 387,
882e893.
Deng, Y., Tang, L., Zeng, G., Wang, J., Zhou, Y., Wang, J., Tang, J., Wang, L., Feng, C.,
2018b. Facile fabrication of mediator-free Z-scheme photocatalyst of
phosphorous-doped ultrathin graphitic carbon nitride nanosheets and bismuth
vanadate composites with enhanced tetracycline degradation under visible
light. J. Colloid Interface Sci. 509, 219e234.
Deng, Y., Tang, L., Zeng, G., Zhu, Z., Yan, M., Zhou, Y., Wang, J., Liu, Y., Wang, J., 2017b.
Insight into highly efficient simultaneous photocatalytic removal of Cr(VI) and
2,4-diclorophenol under visible light irradiation by phosphorus doped porous
ultrathin g-C3N4 nanosheets from aqueous media: performance and reaction
mechanism. Appl. Catal. B Environ. 203, 343e354.
Deng, Y., Wei, J., Sun, Z., Zhao, D., 2013. Large-pore ordered mesoporous materials
templated from non-Pluronic amphiphilic block copolymers. Chem. Soc. Rev. 42
(9), 4054e4070.
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 degra-
dation efficiency of oxytetracycline. Water Res. 143, 589e598.
Dong, S., Dong, S., Tian, X., Xu, Z., Ma, D., Cui, B., Ren, N., Rittmann, B.E., 2016. Role of
self-assembly coated Er3þ: YAlO3/TiO2 in intimate coupling of visible-light-
responsive photocatalysis and biodegradation reactions. J. Hazard Mater. 302,
386e394.
Dong, S., Zhang, X., He, F., Dong, S., Zhou, D., Wang, B., 2015. Visible-light photo-
catalytic degradation of methyl orange over spherical activated carbon-
supported and Er3þ:YAlO3-doped TiO2 in a fluidized bed. J. Chem. Technol.
Biotechnol. 90 (5), 880e887.
Dontsova, K.M., Pennington, J.C., Hayes, C., Simunek, J., Williford, C.W., 2009.
Dissolution and transport of 2,4-DNT and 2,6-DNT from M1 propellant in soil.
Chemosphere 77 (4), 597e603.
Er, D., Li, J., Naguib, M., Gogotsi, Y., Shenoy, V.B., 2014. Ti3C2 MXene as a high ca-
pacity electrode material for metal (Li, Na, K, Ca) ion batteries. ACS Appl. Mater.
Interfaces 6 (14), 11173e11179.
Felczak, A., Zawadzka, K., Lisowska, K., 2014. Efficient biodegradation of quinolone
e factors determining the process. Int. Biodeterior. Biodegrad. 96, 127e134.
Feng, C., Deng, Y., Tang, L., Zeng, G., Wang, J., Yu, J., Liu, Y., Peng, B., Feng, H., Wang, J.,
2018. Core-shell Ag2CrO4/N-GQDs@g-C3N4 composites with anti-
photocorrosion performance for enhanced full-spectrum-light photocatalytic
activities. Appl. Catal. B Environ. 239, 525e536.
Fujishima, A., Zhang, X., Tryk, D., 2008. TiO2 photocatalysis and related surface
phenomena. Surf. Sci. Rep. 63 (12), 515e582.
Gao, P., Mao, D., Luo, Y., Wang, L., Xu, B., Xu, L., 2012. Occurrence of sulfonamide and
tetracycline-resistant bacteria and resistance genes in aquaculture environ-
ment. Water Res. 46 (7), 2355e2364.
Geng, H., Xu, Q., Wu, M., Ma, H., Zhang, P., Gao, T., Qu, L., Ma, T., Li, C., 2019. Plant
leaves inspired sunlight-driven purifier for high-efficiency clean water pro-
duction. Nat. Commun. 10.
He, C., Cheng, J., Zhang, X., Douthwaite, M., Pattisson, S., Hao, Z., 2019. Recent ad-
vances in the catalytic oxidation of volatile organic compounds: a review based
on pollutant sorts and sources. Chem. Rev. 119 (7), 4471e4568.
He, K., Chen, G., Zeng, G., Chen, A., Huang, Z., Shi, J., Huang, T., Peng, M., Hu, L., 2018.
Three-dimensional graphene supported catalysts for organic dyes degradation.
Appl. Catal. B Environ. 228, 19e28.
Hong, P.K.A., Zeng, Y., 2002. Degradation of pentachlorophenol by ozonation and
biodegradability of intermediates. Water Res. 36 (17), 4243e4254.
Jiang, Z., Kong, L., Alenazey, F., Qian, Y., France, L., Xiao, T., Edwards, P.P., 2013.
Enhanced visible-light-driven photocatalytic activity of mesoporous TiO2-xNx
derived from the ethylenediamine-based complex. Nanoscale 5 (12),
5396e5402.
Kim, S., Hwang, J., Chung, J., Bae, W., 2014. Enhancing trichloroethylene degradation
using non-aromatic compounds as growth substrates. J. Hazard Mater. 275,
99e106.
12 M. Yu et al. / Water Research 175 (2020) 115673
Li, WenWei, Yu, HanQing, Rittmann, Bruce, E., 2015. Chemistry: reuse water pol-
lutants. Nature 528 (7580), 29e31.
Li, G., Park, S., Kang, D.W., Krajmalnik-Brown, R., Rittmann, B.E., 2011. 2,4,5-
Trichlorophenol degradation using a novel TiO2-coated biofilm carrier: roles
of adsorption, photocatalysis, and biodegradation. Environ. Sci. Technol. 45 (19),
8359e8367.
Li, G., Park, S., Rittmann, B.E., 2012a. Degradation of reactive dyes in a photocatalytic
circulating-bed biofilm reactor. Biotechnol. Bioeng. 109 (4), 884e893.
Li, G., Park, S., Rittmann, B.E., 2012b. Developing an efficient TiO2-coated biofilm
carrier for intimate coupling of photocatalysis and biodegradation. Water Res.
46 (19), 6489e6496.
Li, W., Wu, Z., Wang, J., Elzatahry, A.A., Zhao, D., 2013. A perspective on mesoporous
TiO2 materials. Chem. Mater. 26 (1), 287e298.
Li, Y., Luo, W., Qin, N., Dong, J., Wei, J., Li, W., Feng, S., Chen, J., Xu, J., Elzatahry, A.A.,
Es-Saheb, M.H., Deng, Y., Zhao, D., 2014. Highly ordered mesoporous tungsten
oxides with a large pore size and crystalline framework for H2S sensing. Angew
Chem. Int. Ed. Engl. 53 (34), 9035e9040.
Lim, T.H., Kim, S.D., 2004. Trichloroethylene degradation by photocatalysis in
annular flow and annulus fluidized bed photoreactors. Chemosphere 54 (3),
305e312.
Lin, Y., Ferronato, C., Deng, N., Chovelon, J.-M., 2011. Study of benzylparaben pho-
tocatalytic degradation by TiO2. Appl. Catal. B Environ. 104 (3e4), 353e360.
Litter, M.I., 1999. Heterogeneous photocatalysis : transition metal ions in photo-
catalytic systems. Appl. Catal. B Environ. 23 (2e3), 89e114.
Luo, X., Deng, F., Min, L., Luo, S., Guo, B., Zeng, G., Au, C., 2013. Facile one-step
synthesis of inorganic-framework molecularly imprinted TiO2/WO3 nano-
composite and its molecular recognitive photocatalytic degradation of target
contaminant. Environ. Sci. Technol. 47 (13), 7404e7412.
Ma, D., Zou, D., Zhou, D., Li, T., Dong, S., Xu, Z., Dong, S., 2015. Phenol removal and
biofilm response in coupling of visible-light-driven photocatalysis and
biodegradation: effect of hydrothermal treatment temperature. Int. Biodeterior.
Biodegrad. 104, 178e185.
Machado, L.C.R., Torchia, C.B., Lago, R.M., 2006. Floating photocatalysts based on
TiO2 supported on high surface area exfoliated vermiculite for water decon-
tamination. Catal. Commun. 7 (8), 538e541.
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, 59e69.
Marsolek, M.D., Kirisits, M.J., Rittmann, B.E., 2007. Biodegradation of 2,4,5-
trichlorophenol by aerobic microbial communities: biorecalcitrance, inhibi-
tion, and adaptation. Biodegradation 18 (3), 351e358.
Marsolek, M.D., Rittmann, B.E., 2016. Effect of substrate characteristics on microbial
community structure, function, resistance, and resilience; application to
coupled photocatalytic-biological treatment. Water Res. 90, 1e8.
Marsolek, M.D., Torres, C.I., Hausner, M., Rittmann, B.E., 2008. Intimate coupling of
photocatalysis and biodegradation in a photocatalytic circulating-bed biofilm
reactor. Biotechnol. Bioeng. 101 (1), 83e92.
Monsalvo, V.M., Mohedano, A.F., Casas, J.A., Rodriguez, J.J., 2009. Cometabolic
biodegradation of 4-chlorophenol by sequencing batch reactors at different
temperatures. Bioresour. Technol. 100 (20), 4572e4578.
Muller, E., Schussler, W., Horn, H., Lemmer, H., 2013. Aerobic biodegradation of the
sulfonamide antibiotic sulfamethoxazole by activated sludge applied as co-
substrate and sole carbon and nitrogen source. Chemosphere 92 (8), 969e978.
Ni, M., Leung, M.K.H., Leung, D.Y.C., Sumathy, K., 2007. A review and recent de-
velopments in photocatalytic water-splitting using TiO2 for hydrogen produc-
tion. Renew. Sustain. Energy Rev. 11 (3), 401e425.
Pelaez, M., Nolan, N.T., Pillai, S.C., Seery, M.K., Falaras, P., Kontos, A.G., Dunlop, P.S.M.,
Hamilton, J.W.J., Byrne, J.A., O’Shea, K., Entezari, M.H., Dionysiou, D.D., 2012.
A review on the visible light active titanium dioxide photocatalysts for envi-
ronmental applications. Appl. Catal. B Environ. 125, 331e349.
Qiu, X., Burda, C., 2007. Chemically synthesized nitrogen-doped metal oxide
nanoparticles. Chem. Phys. 339 (1e3), 1e10.
Rittmann, B.E., 2018. Biofilms, active substrata, and me. Water Res. 132, 135e145.
Sakimoto, K.K., Wong, A.B., Yang, P., 2016. Self-photosensitization of non-
photosynthetic bacteria for solar-to-chemical production. Science 351 (6268),
74e77.
Schneider, J., Matsuoka, M., Takeuchi, M., Zhang, J., Horiuchi, Y., Anpo, M.,
Bahnemann, D.W., 2014. Understanding TiO2 photocatalysis: mechanisms and
materials. Chem. Rev. 114 (19), 9919e9986.
Sharma, M., Bajracharya, S., Gildemyn, S., Patil, S.A., Alvarez-Gallego, Y., Pant, D.,
Rabaey, K., Dominguez-Benetton, X., 2014. A critical revisit of the key param-
eters used to describe microbial electrochemical systems. Electrochim. Acta
140, 191e208.
Shi, Y., Hua, C., Li, B., Fang, X., Yao, C., Zhang, Y., Hu, Y.-S., Wang, Z., Chen, L., Zhao, D.,
Stucky, G.D., 2013. Highly ordered mesoporous crystalline MoSe2Material with
efficient visible-light-driven photocatalytic activity and enhanced lithium
storage performance. Adv. Funct. Mater. 23 (14), 1832e1838.
Sirtori, C., Zapata, A., Oller, I., Gernjak, W., Aguera, A., Malato, S., 2009. Decontam-
ination industrial pharmaceutical wastewater by combining solar photo-Fenton
and biological treatment. Water Res. 43 (3), 661e668.
Su, R., Tiruvalam, R., He, Q., Dimitratos, N., Kesavan, L., Hammond, C., Lopez-
Sanchez, J.A., Bechstein, R., Kiely, C.J., Hutchings, G.J., 2012. Promotion of phenol
photodecomposition over TiO2 using Au, Pd, and Au-Pd nanoparticles. ACS
Nano 6 (7), 6284e6292.
Sun, M., Xiong, S., Wu, X., He, C., Li, T., Chu, P.K., 2013. Enhanced photocatalytic
oxygen evolution by crystal cutting. Adv. Mater. 25 (14), 2035e2039.
Tang, L., Deng, Y., Zeng, G., Hu, W., Wang, J., Zhou, Y., Wang, J., Tang, J., Fang, W.,
2016a. CdS/Cu2S co-sensitized TiO2 branched nanorod arrays of enhanced
photoelectrochemical properties by forming nanoscale heterostructure. J. Alloys
Compd. 662, 516e527.
Tang, L., Feng, C., Deng, Y., Zeng, G., Wang, J., Liu, Y., Feng, H., Wang, J., 2018.
Enhanced photocatalytic activity of ternary Ag/g-C3N4/NaTaO3 photocatalysts
under wide spectrum light radiation: the high potential band protection
mechanism. Appl. Catal. B Environ. 230, 102e114.
Tang, L., Wang, J., Zeng, G., Liu, Y., Deng, Y., Zhou, Y., Tang, J., Wang, J., Guo, Z., 2016b.
Enhanced photocatalytic degradation of norfloxacin in aqueous Bi2WO6 dis-
persions containing nonionic surfactant under visible light irradiation. J. Hazard
Mater. 306, 295e304.
Tang, Y., Zhang, G., Liu, C., Luo, S., Xu, X., Chen, L., Wang, B., 2013. Magnetic TiO2-
graphene composite as a high-performance and recyclable platform for efficient
photocatalytic removal of herbicides from water. J. Hazard Mater. 252e253,
115e122.
Teng, W., Li, X., Zhao, Q., Chen, G., 2013. Fabrication of Ag/Ag3PO4/TiO2 hetero-
structure photoelectrodes for efficient decomposition of 2-chlorophenol under
visible light irradiation. J. Mater. Chem. 1 (32), 9060.
van Loosdrecht, M.C.M., Brdjanovic, D., 2014. Anticipating the next century of
wastewater treatment. Science 344 (6191), 1452e1453.
Wang, C., Li, Y., Tan, H., Zhang, A., Xie, Y., Wu, B., Xu, H., 2019. A novel microbe
consortium, nano-visible light photocatalyst and microcapsule system to
degrade PAHs. Chem. Eng. J. 359, 1065e1074.
Wang, J., Tang, L., Zeng, G., Deng, Y., Dong, H., Liu, Y., Wang, L., Peng, B., Zhang, C.,
Chen, F., 2018. 0D/2D interface engineering of carbon quantum dots modified
Bi2WO6 ultrathin nanosheets with enhanced photoactivity for full spectrum
light utilization and mechanism insight. Appl. Catal. B Environ. 222, 115e123.
Wang, J., Tang, L., Zeng, G., Deng, Y., Liu, Y., Wang, L., Zhou, Y., Guo, Z., Wang, J.,
Zhang, C., 2017. Atomic scale g-C3N4/Bi2WO6 2D/2D heterojunction with
enhanced photocatalytic degradation of ibuprofen under visible light irradia-
tion. Appl. Catal. B Environ. 209, 285e294.
Wang, T., Quan, W., Jiang, D., Chen, L., Li, D., Meng, S., Chen, M., 2016d. Synthesis of
redox-mediator-free direct Z-scheme AgI/WO3 nanocomposite photocatalysts
for the degradation of tetracycline with enhanced photocatalytic activity. Chem.
Eng. J. 300, 280e290.
Wang, M., Sun, Z., Yue, Q., Yang, J., Wang, X., Deng, Y., Yu, C., Zhao, D., 2014. An
interface-directed coassembly approach to synthesize uniform large-pore
mesoporous silica spheres. J. Am. Chem. Soc. 136 (5), 1884e1892.
Wang, J., Tang, L., Zeng, G., Liu, Y., Zhou, Y., Deng, Y., Wang, J., Peng, B., 2016a.
Plasmonic Bi metal deposition and g-C3N4 coating on Bi2WO6 microspheres for
efficient visible-light photocatalysis. ACS Sustain. Chem. Eng. 5 (1), 1062e1072.
Wang, L., Liu, Y., Ma, J., Zhao, F., 2016b. Rapid degradation of sulphamethoxazole and
the further transformation of 3-amino-5-methylisoxazole in a microbial fuel
cell. Water Res. 88, 322e328.
Wang, S., Zheng, Y., Yan, W., Chen, L., Dummi Mahadevan, G., Zhao, F., 2016c.
Enhanced bioleaching efficiency of metals from E-wastes driven by biochar.
J. Hazard Mater. 320, 393e400.
Wen, D., Li, G., Xing, R., Park, S., Rittmann, B.E., 2012. 2,4-DNT removal in intimately
coupled photobiocatalysis: the roles of adsorption, photolysis, photocatalysis,
and biotransformation. Appl. Microbiol. Biotechnol. 95 (1), 263e272.
Wu, W.Q., Xu, Y.F., Rao, H.S., Su, C.Y., Kuang, D.B., 2014. Multistack integration of
three-dimensional hyperbranched anatase titania architectures for high-
efficiency dye-sensitized solar cells. J. Am. Chem. Soc. 136 (17), 6437e6445.
Wu, Z., Webley, P.A., Zhao, D., 2012. Post-enrichment of nitrogen in soft-templated
ordered mesoporous carbon materials for highly efficient phenol removal and
CO2 capture. J. Mater. Chem. 22 (22), 11379.
Wu, Z., Yuan, X., Zhang, J., Wang, H., Jiang, L., Zeng, G., 2017. Photocatalytic
decontamination of wastewater containing organic dyes by metal-organic
frameworks and their derivatives. ChemCatChem 9 (1), 41e64.
Xing, Z., Zhou, W., Du, F., Qu, Y., Tian, G., Pan, K., Tian, C., Fu, H., 2014. A floating
macro/mesoporous crystalline anatase TiO2 ceramic with enhanced photo-
catalytic performance for recalcitrant wastewater degradation. Dalton Trans. 43
(2), 790e798.
Xiong, H., Dong, S., Zhang, J., Zhou, D., Rittmann, B.E., 2018. Roles of an easily
biodegradable co-substrate in enhancing tetracycline treatment in an inti-
mately coupled photocatalytic-biological reactor. Water Res. 136, 75e83.
Xiong, H., Zou, D., Zhou, D., Dong, S., Wang, J., Rittmann, B.E., 2017. Enhancing
degradation and mineralization of tetracycline using intimately coupled pho-
tocatalysis and biodegradation (ICPB). Chem. Eng. J. 316, 7e14.
Xiong, Z., Zhao, X.S., 2013. Titanate@TiO2 coreeshell nanobelts with an enhanced
photocatalytic activity. J. Mater. Chem. 1 (26), 7738.
Xu, P., Zeng, G.M., Huang, D.L., Lai, C., Zhao, M.H., Wei, Z., Li, N.J., Huang, C., Xie, G.X.,
2012. Adsorption of Pb(II) by iron oxide nanoparticles immobilized Phaner-
ochaete chrysosporium: equilibrium, kinetic, thermodynamic and mechanisms
analysis. Chem. Eng. J. 203, 423e431.
Yan, N., Chang, L., Gan, L., Zhang, Y., Liu, R., Rittmann, B.E., 2013. UV photolysis for
accelerated quinoline biodegradation and mineralization. Appl. Microbiol.
Biotechnol. 97 (24), 10555e10561.
Yan, N., Xia, S., Xu, L., Zhu, J., Zhang, Y., Rittmann, B.E., 2012. Internal loop photo-
biodegradation reactor (ILPBR) for accelerated degradation of sulfamethoxazole
(SMX). Appl. Microbiol. Biotechnol. 94 (2), 527e535.
 M. Yu et al. / Water Research 175 (2020) 115673
Yan, Q., Xu, M., Lin, C., Hu, J., Liu, Y., Zhang, R., 2016. Efficient photocatalytic
degradation of tetracycline hydrochloride by Ag3PO4 under visible-light irra-
diation. Environ. Sci. Pollut. Res. Int. 23 (14), 14422e14430.
Yang, S.Y., Choi, W., Park, H., 2015b. TiO2 nanotube array photoelectrocatalyst and
Ni-Sb-SnO2 electrocatalyst bifacial electrodes: a new type of bifunctional hybrid
platform for water treatment. ACS Appl. Mater. Interfaces 7 (3), 1907e1914.
Yang, L., Zhang, Y., Bai, Q., Yan, N., Xu, H., Rittmann, B.E., 2015a. Intimately coupling
of photolysis accelerates nitrobenzene biodegradation, but sequential coupling
slows biodegradation. J. Hazard Mater. 287, 252e258.
Yoo, J.E., Lee, K., Altomare, M., Selli, E., Schmuki, P., 2013. Self-organized arrays of
single-metal catalyst particles in TiO2 cavities: a highly efficient photocatalytic
system. Angew Chem. Int. Ed. Engl. 52 (29), 7514e7517.
Zhang, Y.J., Boyd, S.A., Teppen, B.J., Tiedje, J.M., Li, H., 2014a. Organic acids enhance
bioavailability of tetracycline in water to Escherichia coli for uptake and
expression of antibiotic resistance. Water Res. 65, 98e106.
Zhang, Y.M., Chang, L., Yan, N., Tang, Y., Liu, R., Rittmann, B.E., 2014b. UV photolysis
for accelerating pyridine biodegradation. Environ. Sci. Technol. 48 (1), 649e655.
Zhang, J., Du, Y., Zhang, L., Zheng, X., Ma, Y., Dong, S., Zhou, D., 2017b. Preparation of
sponge carrier supported photocatalyst by self-assembly technique for phenol
photodegradation in visible light. Mol. Catal. 432, 1e7.
Zhang, C., Fu, L., Xu, Z., Xiong, H., Zhou, D., Huo, M., 2017a. Contrasting roles of
phenol and pyrocatechol on the degradation of 4-chlorophenol in a
photocatalytic-biological reactor. Environ. Sci. Pollut. Res. Int. 24 (31),
24725e24731.
Zhang, B., Ji, M., Qiu, Z., Liu, H., Wang, J., Li, J., 2011a. Microbial population dynamics
during sludge granulation in an anaerobic-aerobic biological phosphorus
removal system. Bioresour. Technol. 102 (3), 2474e2480.
Zhang, G., Xia, B.Y., Xiao, C., Yu, L., Wang, X., Xie, Y., Lou, X.W., 2013. General for-
mation of complex tubular nanostructures of metal oxides for the oxygen
reduction reaction and lithium-ion batteries. Angew Chem. Int. Ed. Engl. 52
(33), 8643e8647.
Zhang, M., Jiang, W., Liu, D., Wang, J., Liu, Y., Zhu, Y., Zhu, Y., 2016b. Photo-
degradation of phenol via C3N4-agar hybrid hydrogel 3D photocatalysts with
free separation. Appl. Catal. B Environ. 183, 263e268.
13
Zhang, G., Kim, G., Choi, W., 2014a. Visible light driven photocatalysis mediated via
ligand-to-metal charge transfer (LMCT): an alternative approach to solar acti-
vation of titania. Energy Environ. Sci. 7 (3), 954.
Zhang, Y., Pu, X., Fang, M., Zhu, J., Chen, L., Rittmann, B.E., 2012b. 2,4,6-
trichlorophenol (TCP) photobiodegradation and its effect on community
structure. Biodegradation 23 (4), 575e583.
Zhang, L., Song, X., Liu, X., Yang, L., Pan, F., Lv, J., 2011b. Studies on the removal of
tetracycline by multi-walled carbon nanotubes. Chem. Eng. J. 178, 26e33.
Zhang, Y., Tay, J., 2015. Toxic and inhibitory effects of trichloroethylene aerobic co-
metabolism on phenol-grown aerobic granules. J. Hazard Mater. 286, 204e210.
Zhang, Y., Wang, L., Rittmann, B.E., 2010. Integrated photocatalytic-biological
reactor for accelerated phenol mineralization. Appl. Microbiol. Biotechnol. 86
(6), 1977e1985.
Zhang, L., Xing, Z., Zhang, H., Li, Z., Wu, X., Zhang, X., Zhang, Y., Zhou, W., 2016a.
High thermostable ordered mesoporous SiO2eTiO2 coated circulating-bed
biofilm reactor for unpredictable photocatalytic and biocatalytic performance.
Appl. Catal. B Environ. 180, 521e529.
Zhang, G., Zhang, J., Zhang, M., Wang, X., 2012a. Polycondensation of thiourea into
carbon nitride semiconductors as visible light photocatalysts. J. Mater. Chem. 22
(16), 8083.
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, 745e751.
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, 882e889.
Zhou, D., Xu, Z., Dong, S., Huo, M., Dong, S., Tian, X., Cui, B., Xiong, H., Li, T., Ma, D.,
2015. Intimate coupling of photocatalysis and biodegradation for degrading
phenol using different light types: visible light vs UV light. Environ. Sci. Technol.
49 (13), 7776e7783.
Zhou, N., Polavarapu, L., Gao, N., Pan, Y., Yuan, P., Wang, Q., Xu, Q.H., 2013. TiO2
coated Au/Ag nanorods with enhanced photocatalytic activity under visible
light irradiation. Nanoscale 5 (10), 4236e4241.