journal of environmental sciences 96 (2020) 109–116

Available online at www.sciencedirect.com

www.elsevier.com/locate/jes

Ce-based catalysts used in advanced oxidation

processes for organic wastewater treatment: A
review

Lijun Niu 1,2, Ting Wei 2, Qiangang Li 2, Guangming Zhang 1,∗, Guang Xian 2,
Zeqing Long 2, Zhijun Ren 1
1 School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300130, China
2 School of Environment and Natural Resource, Renmin University of China, Beijing 100872, China

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

Article history: Refractory organic pollutants in water threaten human health and environmental safety,
Received 25 February 2020 and advanced oxidation processes (AOPs) are effective for the degradation of these pollu-
Revised 16 April 2020 tants. Catalysts play vital role in AOPs, and Ce-based catalysts have exhibited excellent per-
Accepted 22 April 2020 formance. Recently, the development and application of Ce-based catalysts in various AOPs
Available online 29 May 2020 have been reported. Our study conducts the first review in this rapid growing field. This pa-
per clarifies the variety and properties of Ce-based catalysts. Their applications in different
Keywords: AOP systems (catalytic ozonation, photodegradation, Fenton-like reactions, sulfate radical-
Ce-based catalysts based AOPs, and catalytic sonochemistry) are discussed. Different Ce-based catalysts suit
Water treatment different reaction systems and produce different active radicals. Finally, future research di-
Redox properties rections of Ce-based catalysts in AOP systems are suggested.
Oxygen vacancies © 2020 The Research Center for Eco-Environmental Sciences, Chinese Academy of
Advanced oxidation processes Sciences. Published by Elsevier B.V.

In a Swiss wastewater treatment plant, large numbers of an-

Introduction
Proper treatment of wastewater is a critical issue in sustain-
able development. Many pollutants, such as pharmaceuticals
and personal care products (PPCPs), pesticides, and industrial
chemicals are toxic, persistent, and endanger human health
and aquatic life (Dong et al., 2019; Sabzehmeidani et al., 2019;
Akpan and Hameed, 2011). Conventional wastewater treat-
ment systems are ineffective for degrading these refractory
and toxic pollutants (Faria et al., 2009; Norzaee et al., 2018;
Zhang et al., 2019). Many of these pollutants are frequently
detected in the effluents of wastewater treatment plants. In
2009, Okuda et al. (2009) reported that 56 compounds were
detected from the primary sludge and 61 compounds were
detected from the excess sludge in Japanese wastewater, and
the concentration ranged between several ng/g to several μg/g.
∗
Corresponding author.
E-mail: zgm@ruc.edu.cn (G. Zhang).
tibiotics and their metabolites were detected. Such as, clar-
ithromycin, roxithromycin, and erythromycin-H2 O. The con-
centrations of clarithromycin varied between 57 and 330 ng/L
(McArdell et al., 2009). Advanced oxidation processes (AOPs)
are promising for the degradation of these pollutants, owing
to their high performance and simplicity (Ribeiro et al., 2019;
Eshaq et al., 2020; Tang and Wang, 2018).
AOPs (Fenton-like reactions, photocatalytic reactions,
ozone oxidation, etc.) aim at generation of highly active radical
species to attack recalcitrant organic pollutants (Tbessi et al.,
2019). For example, ·OH is generated by the activation of H2 O2
in Fenton-like reactions (He et al., 2016). Electrons (e− ) and
holes (h+ ) are generated when a semiconductor absorbs light
photons in photocatalytic process; then, the excited elec-
trons react with electron acceptors, generating O2 ·− and ·OH
(Singh et al., 2019). In catalytic ozonation, ozone can be de-
composed, producing ·OH and O2 ·− (Faria et al., 2008). Recently,
sulfate radical (SO4 ·− )-based AOPs have been widely studied
(Yan et al., 2019). Many technologies have been developed and

https://doi.org/10.1016/j.jes.2020.04.033
1001-0742/© 2020 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.
110 journal of environmental sciences 96 (2020) 109–116
Fig. 1 – Number of Ce-based catalysts in AOPs from 2009 to
2019 (data from Google scholar).
applied for SO4 ·− -based AOPs, such as dewatering of anaero-
bically digested sludge, enhancing production of organics and
nutrients from waste activated sludge and degradation of pol-
lutants in wastewater and soil (Li et al., 2019b; Yang et al., 2019;
Sun et al., 2020). SO4 ·− can be produced via the activation of
persulfate (PS) or peroxymonosulfate. Activation can usually
occur thermally (Ghauch et al., 2012; Ghauch and Tuqan, 2012),
chemically (Naim and Ghauch, 2016; Hakim et al., 2019) and
photolytically (Ghauch et al., 2017; Hakim et al., 2020) with
high reaction stoichiometric efficiency yielding in some cases
more than 50% (Amasha et al., 2018) toward organic contami-
nants degradation. Comparing with these activation methods,
metal catalysts activation has advantages of high efficiency
and low cost (Xian et al., 2019). Therefore, they are the most
widely used persulfate activation method. Clearly, the cata-
lysts are the core of AOPs (Liang et al., 2019a).
Commonly used catalysts include metal catalysts and non-
metal catalysts (such as N-and S-co-doped biomass carbon,
activated carbon and grapheme oxide) (Yang et al., 2011;
Liu et al., 2017). Metal catalysts exhibit high activity in AOPs
owing to their excellent electron transfer capability. Among
them, Ce-based catalysts have attracted considerable atten-
tion recently because of their excellent properties (Li et al.,
2018). Ce, a typical rare earth metal element, is abundant,
inexpensive and non-toxic. Ce-based catalysts have excel-
lent redox properties due to two stable valence states: Ce(Ⅲ)
and Ce(Ⅳ) (Liu et al., 2020). It can interact with other met-
als, promote the production of active metal sites, further ac-
tive oxidants producing active radicals (Kumar et al., 2015).
Guan et al. (2019) reported that the tetracycline removal ef-
ficiency in Co3 O4 /CeO2 /PS system was 80% owing to the in-
teraction between Co and Ce, which was significantly higher
than those of CeO2 /PS and Co2 O3 /PS systems. Additionally, Ce-
based catalysts have excellent oxygen storage/release prop-
erty and high mobility of oxygen species with the formation
of labile oxygen vacancies. This is conducive to the formation
of reactive oxygen species to attack pollutants (Zhang et al.,
2020). Chong et al. (2017a, 2017b) reported that singlet oxygen
(1 O2 ) was the primary reactive species for the degradation of
diclofenac in FeCeOx /ultrasound (US) system, and the produc-
tion of 1 O2 was attributed to the oxygen vacancies of catalysts.
Based on the aforementioned advantages, Ce-based cata-
lysts for AOPs are attracting increasing research attention. As
shown in Fig. 1, the number of reported Ce-based catalysts for
AOPs has increased recently. Therefore, it is necessary to sum-
marize the recent research progress in this field. This is the
first review for Ce-based catalysts in AOPs. We summarize the
varieties, properties, and applications of Ce-based catalysts in
AOPs and propose future research directions. It can not only
give deep insight for the properties and reaction mechanism
of Ce-based catalysts in different AOPs, but also provide guid-
ance for the development of ecofriendly, efficient, and stable
Ce-based catalysts for water treatment.
1. Variety and properties of Ce-based
catalysts
1.1. Variety of Ce-based catalysts
CeO2 is the most basic Ce-based catalyst. Fig. 2a is the scan-
ning electron microscope (SEM) image of CeO2 . CeO2 has low
catalytic activity. Light and electricity can enhance the con-
version of Ce(Ⅲ) and Ce(Ⅳ), thus, improve the activity of CeO2
(Calvache-Muñoz and Rodríguez-Páez, 2019; Tao et al., 2019).
Ren et al. (2018) reported that the efficiency of CeO2 in Fen-
ton system was significantly improved by applying an electric
field. Zang et al. (2018) reported that CeO2 exhibited high per-
formance under visible light for the degradation of salicylic
acid.
Supported Ce-based catalysts (CeO2 /support) have also
been widely studied. Fig. 2b is the SEM image of CeO2 /carbon
xerogel. The commonly used supports are carbon materi-
als, molecular sieves, and metal oxides (Thiruppathi et al.,
2018; Goncalves et al., 2014; Reddy et al., 2009). Support pro-
vides large specific surface area for CeO2 , which makes the
CeO2 evenly dispersed, exposing more metal sites (Bing et al.,
2012; Xiao et al., 2018). Goncalves et al. (2014) reported that
CeO2 /carbon materials exhibited better performance for ery-
thromycin mineralization than carbon materials and CeO2 .
Ce-metal composites also exhibited high activity. Here, Ce
can be used as support, loaded on metal oxides, or mixed with
metal oxides (Rezaei and Yangjeh, 2013; Maddila et al., 2014;
Li et al., 2020b). Fig. 2c and d is the SEM image of FeOx /CeO2
and MnCeOx . Ce can disperse metal active sites and pro-
mote electron transfer of active metals. Additionally, there are
many oxygen vacancies on the surface of Ce-metal compos-
ites, which are conducive to the formation of reactive oxygen
species, enhancing the activity of the catalysts. Gong et al.
(2019) reported that Ru/CeO2 catalyst exhibited high perfor-
mance for N,N-dimethyl formamide degradation due to the
promotion of Ru dispersion and the transfer of active oxy-
gen. Nazari et al. (2019) found that CuFeO2 /CeO2 exhibited ex-
cellent performance and negligible metal leaching in electro-
Fenton system, owing to the strong interaction between active
species and support.
In summary, as shown in Fig. 3, Ce-based catalysts can be
divided into cerium oxide, CeO2 /support, and Ce-metals com-
posite catalysts. All of these Ce-based catalysts play vital role
in AOPs.
1.2. Properties of Ce-based catalysts
Ce-based catalysts have excellent redox and oxygen stor-
age/release properties. Thus, they exhibit high performance
in AOPs. As shown in Fig. 4, the redox property is based on
the cycle of Ce(Ⅲ) and Ce(Ⅳ). Cerium oxide has two stable
valences, Ce3+ and Ce4+ , which are beneficial for improving
the redox cycle to continuously produce low state active sites.
Dong et al. (2019) found that Fe2+ and Ce3+ can be produced
by the redox cycle of Fe/Ce in Fe-Ce oxide catalyst for PS ac-
tivation to degrade phthalate eaters. A similar phenomenon
was observed by Liu et al. (2019) in Cu-Ce tyre catalyst. Ad-
ditionally, it was reported that Ce has a larger lattice radius
 journal of environmental sciences 96 (2020) 109–116 111

Fig. 2 – Scanning electronic microscopy (SEM) of (a) CeO2 (Li et al., 2017), (b) CeO2 /carbon xerogel (Orge et al., 2012), (c)
FeOx /CeO2 (Chong et al., 2017b), and (d) MnCeOx (Niu et al., 2020). Reprinted with permission from Elsevier.

Fig. 3 – Varieties of Ce-based catalysts. AC: activated carbon; MWCNTs: multi-walled carbon nanotubes.
112 journal of environmental sciences 96 (2020) 109–116
Fig. 4 – Redox and O storage/release properties of Ce-based
catalysts.
than many metals and that these metals can be doped into
the lattice of CeO2 to form unique solid solution. The forma-
tion of solid solution is accompanied by lattice defects and
oxygen vacancies. Oxygen vacancies are adsorption sites for
O2 to form reactive O, which can be further activated by active
metals to produce superoxide radicals (O2 ·− ) and 1 O2 to attack
pollutants. Chong et al. (2017a, 2017b) reported that FeCeOx
solid solution was formed (Fig. 5a), and oxygen vacancies ex-
isted which facilitated H2 O2 decomposition and 1 O2 genera-
tion (Fig. 5b).
Ce-based catalysts also have high stability. This is because
CeO2 has a very stable fluorite structure with oxygen vacan-
cies in its crystal cell, in which metal ions can easily be em-
bedded into the cell. The stable Ce-based catalysts have negli-
gible active metal dissolution and can be reused many times.
Liang et al. (2019b) reported that with the addition of CeO2 ,
the leaching of Cu ion in CuO-CeO2 catalyst decreased from
19.1 to 2.1 mg/L. Fe3 O4 -CeO2 could be reused five times in
Fenton-like system at pH of 2.4, while Fe3 O4 -multi walled car-
bon nanotubes (MWCNTs) could only be reused twice at pH of
3.0 (Gogoi et al., 2017; Tolba et al., 2019).
Due to unique structure, excellent redox property and
abundant oxygen vacancies, Ce-based catalysts show high
performance in AOP systems. Reaction stoichiometric effi-
ciency (RSE) is a key parameter to evaluate catalysts perfor-
mance, which is the ratio of the number of moles of con-
taminants degraded over the number of moles of oxidant
used. Gogoi et al. (2017) studied catechol degradation in Fe3 O4 -
CeO2 /H2 O2 system, The RSE were 0.33 and 0.26 for Fe3 O4
and Fe3 O4 -CeO2 , respectively. Xian et al. (2019) reported that
the RSE of Co3 O4 -CeO2 was higher than Co3 O4 for diclofenac
degradation. Thus, Ce-based catalysts have excellent proper-
ties and high performance.
2. Applications of Ce-based catalysts for AOPs
In the past decade, Ce-based catalysts have been increasingly
employed in AOPs. Table 1 presents the applications of Ce-
based catalysts in different AOP systems, e.g., ozone oxida-
tion, photodegradation, Fenton-like reactions, sulfate radical
(SO4 ·− )-based AOPs, and catalytic sonochemistry. Ce plays dif-
ferent roles in different systems. The following table summa-
rizes the types of Ce-based catalysts, free radicals, and organic
pollutants in different AOP systems. This provides guidance
for the selection of suitable Ce-based catalysts and systems
for different organic pollutant
2.1. Catalytic ozonation
Catalytic ozonation aims to degrade organic pollutants (such
as dyes, pesticides, PPCPs, endocrine-disrupting chemicals
(EDCs), polycyclic aromatic hydrocarbons (PAHs), and phtha-
late acid esters (PAEs)) via the transformation of ozone into
more reactive species (Wang and Bai, 2017). Ce-based catalysts
exhibit high activity in catalyst ozone process. They can effec-
tively transform O3 into ·OH and surface oxygenated radical
species (O1 ·− , O2 ·− , O3 ·− ). These free radicals react with almost
all types of substances.
CeO2 /carbon materials (molecular sieves) are the most
widely studied catalysts in catalytic ozonation systems (Xie
et al., 2020). Mesoporous molecular sieves with larger surface
area and larger pore size provide more active sites for reac-
tions. Carbon materials (such as AC, carbon xerogel, graphene
and carbon nanotubes) also have large specific area and fa-
vorable adsorption capacity. Additionally, carbon materials
with delocalized electrons contribute to the formation of Ce3+
species, which promote the decomposition of ozone into ·OH.
Furthermore, Goncalves et al. (2014) found that Ce/AC cata-
lysts can enhance the mineralization of pollutants. As shown
in Table 1, the TOC removal efficiencies were >80% with Ce-
based carbon catalysts. Thus, the carbon materials can not
only disperse CeO2 but also contribute to the formation of
Ce3+ species and enhance the mineralization of pollutants.
Furthermore, Ce-based metal oxides can effectively ac-
tive ozone to degrade pollutants, such as Ce-Zr-loaded
metal oxides, Ce-Ti-Zr ternary oxide, PdO/CeO2 , MnCeOx , and
Ce0.1 Fe0.9 OOH. The presence of multiple metal components
leads to a synergistic effect, producing more low-state metal
sites (Shan et al., 2018). This makes catalysts more effective
for activating O3 to produce free radicals.
2.2. Fenton-like reaction
Heterogeneous Fenton-like reactions can rapidly degrade or-
ganic pollutants (pharmaceutical pollutants and dyes) in the
presence of H2 O2 and catalysts (Alimard, 2019; Ren et al., 2019).
Among the Ce-based catalysts, Ce-Fe oxides (such as FeCeOx ,
Ce-doped Fe3 O4 , Fe0 /CeO2 , Fe3 O4 -CeO2 , and Fe2 O3 -CeO2 ) are
the most widely used in heterogeneous Fenton-like reactions,
and they are presented in Table 1.
Ce-Fe oxides for Fenton-like reactions have the following
advantages: (1) They alleviate the agglomeration of iron ox-
ides; (2) CeO2 with abundant oxygen vacancies benefits the
dissociation of H2 O2 and O2 , which generates ·OH and active
oxygen species (O2 ·− and 1 O2 ) to attack pollutants (Gao et al.,
2019). Chong et al. (2017a, 2017b) reported that the main
free radicals for diclofenac oxidation were ·OH and 1 O2 in
FeCeOx /H2 O2 system. The production of 1 O2 was attributed to
the oxygen vacancies of catalysts (Eqs. (1) and (2)); (3) Ce3+ can
reduce Fe3+ to Fe2+ and promote the Fe2+ /Fe3+ redox cycle;
(4) Doping CeO2 with Fe oxides can reduce the metal leaching
and improve the stability of catalysts. Zhang et al. (2019) re-
ported that tetracycline removal efficiency still reached 90%
with Fe0 /CeO2 after five cycles. Therefore, Ce-Fe oxides are
promising in Fenton-like reactions.
Ovac + O2 − + H+ →1 O2 + · OH (1)
Ce(III ) + Ovac + O2 + H+ → Ce(IV )+1 O2 + · OH (2)
 journal of environmental sciences 96 (2020) 109–116 113

Fig. 5 – (a) Transmission electron microscopy (TEM) image of FeCeOx and (b) roles of oxygen vacancies in FeCeOx (Chong et
al., 2017a). Reprinted with permission from Elsevier.

Table 1 – Applications of Ce-based catalyst in AOPs.

Catalyst Target pollutants Degradation efficiency (%) Active species References

Catalytic ozonation
Ce/AC Dyes Pollutants: 98–100, TOC: 61–83 ·OH, O2 ·− , 1 O2 Faria et al. (2009)
Ce/AC Pyrene and fluoranthene Pollutants: 83–92 ·OH Liu et al. (2012)
Ce-carbon xerogel Oxalic acid and Reactive Blue 5 Pollutants: 100, TOC: 100 ·OH Orge et al. (2012)
Fe3 O4 @SiO2 @CeO2 Acetylsalicylic acid Pollutant: 100, TOC: 44.2 ·OH Dai et al. (2014)
Mn-Ce-O Phenolic acids Pollutant: 100, TOC: 75, COD: 56 Martins and Quinta-Ferreira (2009)
Ce0.1 Fe0.9 OOH Sulfamethazine Pollutant: 100, TOC: 45 ·OH, O2 ·− Bai et al. (2016)
Ce/SBA-15 Dimethyl phthalate Pollutant: 100, TOC: 80 ·OH, O2 ·− Yan et al. (2013)
Ce/red mud Bezafibrate Pollutant: 100 ·OH, O2 ·− Xu et al. (2016)
Ce/MCM-41 p-Chlorobenzoic acid Pollutant: 100, TOC: 80 ·OH, O2 ·− Bing et al. (2012)
PdO/CeO2 Pyruvic acid Pollutant: 100 ·OH, O2 ·− Li et al. (2012)
Fenton-like reactions
Fe/CeO2 Salicylic acid Pollutant: 95, COD: 70 O2 ·− , HO2 · , 1 O2 Wang and Bai (2017)
Fe3 O4 -CeO2 Catechol Pollutant: 98, COD: 89 ·OH, O2 ·− Gogoi et al. (2017)
Fe3 O4 /CeO2 Methylene Blue Pollutant: 100 ·OH Li et al. (2017)
Fe2 O3 -CeO2 Sulfamerazine Pollutant: 100 ·OH Gao et al. (2019)
Fe0 /CeO2 Tetracycline Pollutant: 98 ·OH Zhang et al. (2019)
FeCeOx Diclofenac Pollutant: 83 Chong et al. (2016)
Photodegradation
Ce/MoO3 Methylene Blue Pollutant: 91, TOC: 17 ·OH, O2 ·− Liu et al. (2015)
Ce/TiO2 Diclofenac Pollutant: 100 ·OH, O2 ·− Thiruppathi et al. (2018)
Ce-Ag-ZnO/Fe3 O4 Methylene Blue Pollutant: 100 ·OH, O2 ·− Heshmatpour and Abdikhani (2019)
Ce/ZnO Direct Red-23 dye Pollutant: 100 ·OH, O2 ·− Kumar et al. (2015)
Ce-Mn/TiO2 Diclofenac Pollutant: 94 ·OH, O2 ·− Tbessi et al. (2019)
Ce/BiVO4 Rhodamine B Pollutant: 80 ·OH, O2 ·− Luo et al. (2017)
Ce-TiO2 /diatomite Oxytetracycline Pollutant: 90 O2 ·− Chen et al. (2018)
Sr/Ce/AC Rhodamine B Pollutant: 80, COD: 65, TOC: 70 ·OH, O2 ·− Sharma et al. (2019)
CuO/CeO2 Methyl tertiary butyl ether Pollutant: 100 ·OH, O2 ·− Pal et al. (2018)
CeO2 /CuS Methylene Blue Pollutant: 95 ·OH, O2 ·− Sabzehmeidani et al. (2019)
SO4 ·− -based AOPs
Ce/3D Mn2 O3 2,4-Dichlorophenol Pollutant: 100 SO4 ·− , ·OH, 1 O2 Tian et al. (2019)
1
CuO-CeO2 Dyes Pollutants: 72.84–100 O2 Li et al. (2019a)
Cu-Ce tyre carbon Ofloxacin Pollutant: 85 SO4 ·− , ·OH Liu et al. (2019)
Co3 O4 /CeO2 Tetracycline Pollutant: 79 SO4 ·− , ·OH Guan et al. (2019)
Co3 O4 -CeO2 Diclofenac Pollutant: 100 SO4 ·− , ·OH Xian et al. (2019)
CeO2 -Fe3 O4 Antibiotics and dyes Pollutants: 80–100 ·OH Ghanbari et al. (2019)
Catalytic sonochemistry
MnO2 /CeO2 Methyl Orange Pollutant: 100 ·OH Zhao et al. (2015)
1
FeCeOx Diclofenac Pollutant: 80 O2 Chong et al. (2017b)

AOPs: advanced oxidation processes; TOC: total organic carbon; COD: chemical oxygen demand; AC: activated carbon.
114 journal of environmental sciences 96 (2020) 109–116
where Ovac is oxygen vacancy.
2.3. Photodegradation
Heterogeneous photocatalysis is an effective and ecofriendly
method for pollutant degradation (dyes, pharmaceuti-
cally active compounds (PhACs), and phenolic compounds)
(Thiruppathi et al., 2018; Rostami, 2019; Wang et al., 2018).
Considerable attention is paid to seek semiconductor photo-
catalytic. Traditional semiconductor catalysts (such as TiO2 ,
ZnO, Bi2 O3 , and BiVO4 ) have shortcomings, such as low usabil-
ity of visible light and high recombination rate of electrons
(e− ) and holes (h+ ) (Tang and Wang, 2018; Munoz-Batista et al.,
2018; Zhan et al., 2018).
Doping these semiconductor materials with CeO2 bene-
fits the formation of an intra-band structure between the
valence band (VB) and conduction band (CB), which nar-
rows the band gap of the semiconductor and extends its
light-absorption region (Chen et al., 2018; Maarisetty and
Baral, 2019; Chang et al., 2015). Additionally, Ce, which has an
excellent electron transfer capability, can hinder the recombi-
nation of photo-induced electron–hole pairs and improve the
photo-activity (Dumrongrojthanath et al., 2018). Ce doping can
also influence the texture and surface properties of catalyst.
Xue et al. (2017) reported that La/Ce-codoped Bi2 O3 leads to
the lattice contraction of Bi2 O3 , a reduction in the crystal size,
and an increase in the surface area.
2.4. SO4 ·− -based AOPs
Because of their effectiveness for refractory organics treat-
ment, SO4 ·− -based AOPs have recently attracted increasing at-
tention (Li et al., 2020a). Only a few types of Ce-based catalysts
have been applied in SO4 ·− -based AOPs, such as Co3 O4 /CeO2 ,
CuO-CeO2 , Ce/Mn2 O3 , and iron-cerium oxide. Owing to its ex-
cellent redox property and oxygen mobility, Ce can enhance
the redox cycle of metals to generate active metal sites con-
tinuously. Additionally, Ce3+ can activate O2 to produce O2 ·− ,
which can react with ·OH, producing 1 O2 . Both SO4 ·− and 1 O2
can attack pollutants, in contrast to the situation for other
catalysts, which mainly produce SO4 ·− and ·OH. Niu et al.
(2020) reported that the main free radicals were SO4 ·− , ·OH and
O2 ·− in MnCeOx /PS system for ofloxacin degradation accord-
ing to Eqs. (3)–(6).
− 2−
≡ Mn(III ) − OS2 O−
7 →≡ Mn (IV ) + SO4 + SO4 (3)
− 2−
≡ Mn(II ) − OS2 O−
7 →≡ Mn (III ) + SO4 + SO4 (4)
≡ Ce(III ) + O2 → O−
2
+ ≡ Ce(IV ) (5)
SO·− + 2−
4 + H2 O → ·OH + H + SO4 (6)
2.5. Catalytic sonochemistry
Catalytic ultrasonication (as one of the AOPs) has been used in
the treatment of organic pollutants (such as dyes and PhACs)
(Guo et al., 2017) The cavitation effect and hot spot effect pro-
duced by ultrasound benefit the decomposition of water and
oxygen molecules to produce ·OH and other oxidative species.
Zhao et al. (2015) reported that Methyl Orange removal ef-
ficiency reached 90% in MnO2 /CeO2 catalytic ultrasonic pro-
cess. The main active species was ·OH, which was produced
by the decomposition of H2 O2 by Mn3+ and Ce3+ . Interestingly,
Chong et al. (2017a, 2017b) found that the removal efficiency
of diclofenac using FeCeOx -ultrasound reached 80%; 1 O2 was
the main active species, in contrast to other ultrasonic reac-
tions where ·OH was the main active species. The formation
of 1 O2 may have been related to abundant oxygen vacancies
on FeCeOx surface. The mechanism of free-radicals produc-
tion by Ce-based catalysts in catalytic sonochemistry should
be studied further.
3. Conclusions and prospects
This review introduced Ce-based catalysts in AOPs for
wastewater treatment. The types and properties of Ce-based
catalysts were summarized. Additionally, the typical Ce-based
catalysts and free radicals for different AOP systems were an-
alyzed. The following conclusions are drawn.
(1) Ce-based catalysts include CeO2 , supported CeO2 , and
Ce-metal composites. The activity of CeO2 is relatively
low. Combining CeO2 with light or electrical energy can
enhance the cycle of Ce(Ⅲ) and Ce(Ⅳ). Supported CeO2
catalysts exhibit high performance owing to their large
surface area and dispersed active sites. Ce-based metal
oxide catalysts have high activity owing to the interac-
tion of Ce and other metals, where Ce can act as non-
inert carrier and active component.
(2) Ce-based catalysts have unique structures, excellent re-
dox properties, and abundant oxygen vacancies; thus,
they have high stability, good electron-transfer capac-
ity, and good oxygen storage/release capacity.
(3) CeO2 /carbon materials (molecular sieves) are used to
catalyze ozone degradation of organic pollutants. Ce-
doped semiconductors are used for photodegradation
process. Ce-Fe compounds are often used in Fenton-like
reactions. Ce-metal oxides (Ce-Co, Ce-Cu, and Ce-Mn)
have been used in SO4 ·− -based AOPs. FeCeOx and MnO2 -
CeO2 are used in catalytic sonochemistry.
(4) Reactive oxygen species (O2 ·− and 1 O2 ) are produced
in AOPs catalyzed by Ce-based catalysts owing to the
abundant oxygen vacancies in Ce-based catalysts.
Although studies on Ce-based catalysts in AOPs have in-
creased in recent years, practical applications remain distant.
According to the results of the present study, increased atten-
tions should be paid to the following aspects.
(1) More Ce-based catalysts for AOPs should be developed.
Ce-based catalysts have proven to be effective in AOPs.
However, the varieties of Ce-based catalysts used in
AOPs are limited, particularly in SO4 ·− -based AOPs and
catalytic sonochemistry systems. Thus, more efficient
Ce-based catalysts should be developed for AOP appli-
cations.
(2) The mechanism underlying the production of reactive
oxygen species by Ce-based catalysts should be inves-
tigated in detail. In particular, the relationship between
oxygen vacancies and oxygenated radical species and
the detailed electron-transfer processes should be clar-
ified.
(3) The performance of Ce-based catalysts in combined
AOPs should be investigated. When Ce-based catalysts
are employed in single AOPs, although the removal effi-
ciency for pollutants is high, the TOC removal efficiency
is relatively low. Applying Ce-based catalysts in combi-
nation AOPs can become an active research area.
(4) The performance of Ce-based catalysts in wastewater
should be investigated. At present, the application of
 journal of environmental sciences 96 (2020) 109–116
Ce-based catalysts remains in the laboratory. It is nec-
essary to study the performance of Ce- based catalysts
in actual wastewater, which will lay a foundation for the
industrial application of Ce-based catalysts.
(5) RSE of Ce-based catalyst toward different oxidants, such
as persulfate and hydrogen peroxide, should be studied
and compared. Ce-based catalysts act differently with
different oxidant and show different performance. This
study is beneficial to select suitable oxidant for different
pollutants degradation.
Declaration of competing interest
The submitted work was not carried out in the presence of
any personal, professional or 660 financial relationships that
could potentially be construed as a conflict of interest.
Acknowledgments
This work was supported by National Water Pollution Con-
trol and Treatment Science and Technology Major Project (No.
2018ZX07110003) and the National Natural Science Founda-
tion of China (No. 51779068).
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