Catalysis Today 335 (2019) 20–30

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

A critical review on visible-light-response CeO2-based photocatalysts with T

enhanced photooxidation of organic pollutants
⁎
Ran Maa,1, Sai Zhanga,1, Tao Wena, Pengcheng Gua, Lei Lia, Guixia Zhaoa, , Fenlei Niua,
⁎
Qifei Huangb, Zhenwu Tanga, Xiangke Wanga,
a
College of Environmental Science and Engineering, North China Electric Power University, Beijing, 102206, PR China
b
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, 100012, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Organic pollutants’ treatment in wastewater has attracted extensive attention due to its degradation-resistance
CeO2 and potentially hazardous to human health. Some organic matters such as persistent organic pollutants (POPs)
Photodegradation could exist in environment and resist to decomposition, which may cause chronic intoxication or even cancers.
Organic pollutants Because photocatalytic technique is efficient, nontoxic, and cost-effective to degrade organic pollutants, some
Modification
semiconductors including TiO2 and ZnO as photocatalysts have aroused wide public concern. CeO2 has been
Visible-light-response
reported as an efficient photocatalyst in contrast to TiO2 owing to its high oxygen storage, eco-friendly prop-
erties and photostability. But inefficient utilization of solar energy due to its intrinsic wide bandgap restrains its
further application in real environmental pollutant treatment. In order to improve photocatalytic performances
of CeO2, some modifications have been developed such as doping ions, coupling with semiconductor and con-
struction of CeO2-based solid-solution. The purpose of this review is to introduce these techniques, reveals its
fundamental mechanisms and the recent researches about photodegradation of organic pollutants in wastewater
over CeO2-based photocatalysts. Besides, this review will evaluate the photocatalytic performance for organic
pollutants and outlook the challenges and prospects in the future.

1. Introduction considered as effective methods for the treatment of organic waste-

water. The mechanism of AOPs is to generate reactive species (e.g.,
The development of industry not only facilitate economy boom but hydroxyl radical), which can oxidize organics non-selectively and
also improve the standard of living, and then promote the development quickly [10,11]. As a new AOPs, photocatalytic technique has been
of human society. However, some industrial contaminants in waste- widely applied to degrade organic pollutants due to its advantages such
water effluents are produced in the process of the development, in- as high efficiency, low-cost, green, safety and so on [12].
cluding heavy metals, radioactive nuclides, and organics [1–3]. And Photocatalysis has attracted enormous attention since photoelec-
considerable industrial activities result in the discharge of large trochemistry hydrogen evolution was firstly reported by Fujishima and
amounts of wastewater into the environment, which causes serious Honda by using TiO2 as an electrode catalyst in 1972 [13]. Due to the
environmental pollution. Various organic pollutants such as benzene oil crisis in 1973 and energy crisis in 1979, photocatalytic technology
compounds, phenols, organics dyes, antibiotics and halogenated hy- got further developed and extensively applied [14]. Frank and Bard
drocarbon with high toxicity and degradation-resistant property could successfully appli
not only cause water stink, but also accumulate in aquatic organisms ed this technology to degrade pollutants in aqueous solution in 1976
and along the food chain to human body [4,5]. Hence, the disposal of and laid a theoretical foundation for photocatalytic oxidation tech-
organic pollutants has become one of the most severe environmental nology in wastewater treatment [15]. Afterward, some photocatalysts
problems. A variety of technologies have been used in recent years to such as TiO2 [16], ZnO [17], g-C3N4 [18], CdS [19] and so on have been
decontaminate organic pollutants, including adsorption [6], biode- studied extensively for environmental treatment and energy applica-
gradation [7], chemical oxidation [8] and electrochemical conversion/ tions. Among these photocatalysts, some metal oxide semiconductors
combustion [9] and so on. Advanced oxidation processes (AOPs) are such as TiO2 [16], ZnO [17], and α-Fe2O3 [20] present excellent

⁎
Corresponding authors.
E-mail addresses: [email protected] (G. Zhao), [email protected] (X. Wang).
1
Ran Ma and Sai Zhang contributed equally to this work.

https://doi.org/10.1016/j.cattod.2018.11.016
Received 9 September 2018; Received in revised form 15 October 2018; Accepted 6 November 2018
Available online 29 November 2018
0920-5861/ © 2018 Elsevier B.V. All rights reserved.
R. Ma et al. Catalysis Today 335 (2019) 20–30

photocatalytic performance due to their superior features including responding redox reaction and then produce some reactive oxygen
chemical stability and easy synthesis. As one of the most popular metal species (ROS). For example, the excited e− could react with dissolved
oxide semiconductors, the rare earth oxide ceria (CeO2) is widely ap- oxygen to yield superoxide radical (O2·-, when the redox potential is
plied in many fields, including fuel cells [21], solar cells [22] and more negative than that of E (O2/O2·-) = -0.33 eV vs. NHE), and h+
oxygen sensors [23]. In previous studies, CeO2 was reported as an ef- would like to react with OH− to generate hydroxyl radical (·OH). These
ficient photocatalyst on account of its high oxygen storage capacity chemical forms with strong oxidative property might oxidize organic
with abundant oxygen vacancies (Vo), excellent catalytic property pollutants to nontoxic H2O and CO2. The corresponding reaction
owing to the reversible Ce3+/Ce4+ pairs and its resistance to photo- equations are listed as follows:
corrosion [24,25]. But the n-type CeO2 is a wide bandgap semi- hv
conductor around 2.8–3.1 eV and could only absorb the UV region and CeO2 → CeO2 (e− + h+)
slight in visible region up to ∼400 nm, which is less than 5% of the e− + O2 → O2• −
solar spectrum energy [26]. Therefore, the application of CeO2 is re-
stricted. In order to improve the utilization of sunlight over CeO2, some O2• − + H+ → •OOH
methods come up such as element doping, coupled semiconductor,
noble metal deposition, solid-solution formation and surface photo- 2•OOH → O2 + H2 O2
sensitization have been applied to extend the utilization of visible light. e− + H2 O2 → OH− + •OH
CeO2-based photocatalysts have been fabricated and performed in
water splitting [27], CO2 conversion [28], air purification [29] and e− + H2 O2 → OH− + •OH
organic pollutants degradation, but few people reviewed the CeO2-
h+ + OH− → •OH
based materials as photocatalysts. Motivated by these, herein, we
summarized the CeO2-based photocatalysts for the degradation of or- organic pollutants + resultant radicals → CO2 + H2 O
ganic pollutants. In this paper, we first introduced the mechanism of
+ intermediateproducts
CeO2 semiconductor for the degradation of organic pollutants when it
was exposed to light. In order to enlarge the absorption edge of CeO2 Heterogeneous photocatalytic oxidation organic pollutants can be
and enhance its photocatalytic activity, various modification methods divided into five steps according to Herrmann et al. [38,39], which are
were discussed and the corresponding researches in recent years were described as: 1) the organic molecules in liquid phase transfer to the
summarized. Finally, the future challenges and perspectives of CeO2- surface of CeO2; 2) the organic molecules are adsorbed on CeO2; 3) the
based photocatalysts for the degradation of organic pollutants were adsorbed organic pollutants react with reactive species in the adsorbed
displayed and discussed. phase, where photocatalytic reactions invariably occur once being ex-
cited; 4) the products are desorbed from CeO2 surface; and 5) the
products are removed from the interface region. This review mainly
2. Basic principles of photodegradation over CeO2 photocatalysts
focuses on the third step and summarizes the reaction process on the
surface of CeO2-based semiconductors.
The photodegradation mechanism of organic pollutants by CeO2 is
Unfortunately, the medium band gap of CeO2 is inefficient to utilize
described in Fig. 1. Semiconductor possesses discontinuous energy le-
inexhaustible solar energy and the photo-induce e−-h+ pairs are likely
vels and their photocatalytic capacity is determined by the position of
to recombine and then release useless heat and light, which lead to
the energy band. According to previous studies [30–37], the bottom of
lower photocatalytic performance. In order to resolve these problems,
the conduction band (CB, Ce 4f) of CeO2 is around -0.4 eV vs. normal
some efforts have been made to modify pure CeO2 to improve its
hydrogen electrode (NHE), and the top of the valence band (VB, O 2p)
photocatalytic ability. Therefore, the CeO2-based photocatalysts and its
is ca. 2.5 eV vs. NHE. Generally, the medium energy gap (band gap, Eg)
application in environmental treatment are introduced in Section 3.
of CeO2 between VB and CB is about 2.8–3.1 eV. When the CeO2
semiconductor is illuminated by sunlight, the electron (e−) in VB ab-
3. Modification of CeO2 for improved visible-light photoactivity
sorbs photon (> Eg) and immigrates to CB within femtosecond, and
hence leaves over the same amount of holes (h+) on VB. The photo-
3.1. Metal or nonmetal doped CeO2
generated e− and h+ transfer to the surface of CeO2 and take the

3.1.1. Metal doping

Generally, foreign element doping is often used to decrease the
bandgap of a semiconductor photocatalyst. Metal doping can be divided
into transition metal doping and rare earth metal doping. Doping metal
ions into CeO2 could introduce impurity energy levels in original
bandgap near CB and VB (Fig. 2A). The photo-induced e−/h+ could be
captured by these doped metal ions and then transfer to the surface of
the catalyst to react with organic pollutants. [13,40]
According to previous studies, doping with 3 d-transition metal into
a semiconductor could lead to the formation of lattice defects, which
served as recombination center [41,42]. Theoretically, researches
concerning on the calculation of ab initio band structure reveals that,
with the increase of the atomic number of dopants, the localized 3 d
levels will shift to a lower energy level. Based on the theoretical re-
search, the split 3d state can be mixed with the CB or VB of CeO2, and in
some cases a new bandwidth can be inserted into the original band.
Consequently, the bandgap of CeO2 decreased and absorption edge of
sunlight broadened.
For example, Yue et al. [43] carried out a qualitative study to in-
Fig. 1. Basic mechanism of photodegradation organic pollutants over CeO2. hν vestigate the photocatalytic properties of transition metals (Co, Ti, Fe
represent the energy of irradiate light. and Mn) doped CeO2. The introduction of Co, Ti, Fe and Mn ions to

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R. Ma et al. Catalysis Today 335 (2019) 20–30

Fig. 2. (A) Band structure of metal doped CeO2. (B) UV–vis DRS spectra of various metal ions doped CeO2 nanoparticles [43]; (C) The band structure of Fe-doped
CeO2 and orbital splitting of Fe-3d [44]. (D) The photodegradation mechanism of Fe-doped CeO2 [33]. TEM images of (E) pure CeO2, (F) yttrium doped CeO2. (G)
Plot of F(R)hν1/2 versus hν for the Eg of CeO2 and yttrium doped CeO2. (H) Photodegradation of RhB by as-prepared samples. (E), (F), (G) and (H) reprinted with
permission from Ref. [51].

CeO2 led to the distinct red shift of absorption edge to visible light. Channei et al. [33] synthesized pure CeO2 and Fe-doped CeO2 na-
Finally, the Eg of the as-prepared samples decreased to lower energy. noparticles via a homogeneous precipitation combined with homo-
According to UV–vis diffuse reflectance spectroscopy (DRS) (Fig. 2B), geneous/impregnation method, and the corresponding photocatalyst
the absorption band was broadened to longer wavelength. The red shift films were fabricated by a doctor blade technique to obtain high surface
of absorption band manifested that e− immigrated from O 2p (VB) to and well adhered properties, and thus enhanced its photocatalytic
the unoccupied orbits of transition metals which were lower than Ce 4f performance. Under visible light irradiation, the degradation efficiency
(CB) due to the lower energy requirement. The order of methylene blue of methyl orange (MO) over the optimal Fe-doped CeO2 film was as
(MB) degradation efficiency of metals (Co, Ti, Fe and Mn) doped CeO2 3.88 times good as pure CeO2. Furthermore, the XPS analysis indicated
followed Co > Mn > Ti > Fe. Besides, the photocatalytic perfor- that the presence of Fe3+ may serve as electron acceptor and/or hole
mance of impurity doped CeO2 decreased with the decrease of Vo donor to prolong the separation of photo-generated charge carriers. The
amount, which demonstrated that Vo played an important role in photodegradation mechanism of MO on Fe-doped CeO2 was schemati-
photocatalytic behaviors. In addition, Yang et al. [44] investigated the cally illustrated in Fig. 2D. Additionally, Zhao et al. [45] first reported
origin of the enhancement of photocatalytic activity over transition the using of bio-templates to synthesize Fe-doped CeO2 hollow micro-
metal impurities doped CeO2 by using first-principle calculation. As Fe, spheres. The efficient degradation of acid orange 7 (AO7) could be
Cr or Co atom replaced Ce of CeO2 crystal, the eg and t2g energy level of assigned to the higher specific surface area and more Vo on the hollow
3d orbits emerged intra forbidden gap due to the cubic ligand field. For microspheres of modified CeO2. A visible light response photocatalyst
instance, the band structure of Fe-doped CeO2 was shown in Fig. 2C. As Co-doped CeO2 nanoparticles were fabricated with a coprecipitation
a consequence, the forbidden transition facilitated the enhancement of method [46]. Similarly, the band gap decreased as Co content in-
absorption of visible light and quantum efficiency. However, the Fe, Cr creased. The degradation capacity of pure CeO2, 3% and 6% Co-doped
or Co doping CeO2 without Vo exhibited stronger absorption than that CeO2 NPs were calculated to be 34.7%, 77.1% and 88.9% under visible
with Vo, indicating that the Vo seemed to be detrimental to the im- light, respectively. PL analysis manifested that the introduction of Co
provement of photocatalytic activity of CeO2, which showed different facilitated the formation of Ce3+ and more oxygen vacancies. And the
mechanism with that reported by Yue et al. [43]. dopant Co may suppress the recombination of photo-induced carriers to

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R. Ma et al. Catalysis Today 335 (2019) 20–30

improve the photocatalytic performance of undoped CeO2. enhancement of optical absorption and catalytic performance over N/C
Doping rare-earth metals in CeO2 could also enhance the absorption co-doped CeO2. Calculation analysis showed that the Eg of N-doped
of visible light and change the electronic structure of CeO2 [47,48]. CeO2, C-doped CeO2 and N/C co-doped CeO2 were larger than that of
Extensive researches on rare-earth metal doped CeO2 as an efficient pure CeO2, and the energy band shifted downward owing to the in-
photocatalyst have been carried out to investigate its optical properties. troduce of new anion energy levels.
Shi et al. [49] studied the band structures of rare-earth metals (La, Pr) Electronic structures of the S-doped CeO2 was calculated by using
doping in CeO2 by the hybrid Hartree-Fock (HF)/DFT technique. It was HF combined with DFT technique [58]. The S 3p orbital hybridized
found that doping La element with CeO2 didn’t create impurity level with neighbor O 2p and Ce 4f orbitals and created impurity bands intra
between VB and CB, but the VB (O 2p) of CeO2 was pulled by La 4f and CB and VB, which may lead to enhanced optical absorption and pho-
5p orbitals to Fermi level, which led to p-f hybridize at some extent to tocatalytic activity. The photodegradation activity of S-doped Ceria for
straddle the Fermi level. However, there were three α-spin states and MO degradation was conducted under visible light [59]. The meso-
one β-spin state introduced in the forbidden band when doped CeO2 porous S-CeO2 was fabricated via a solid state reaction method and
with Pr, and all of them were far away from Fermi level whereas close sodium benzene sulfonate (SBS) acted as a template. The XRD analysis
to the bottom of CB. The decreased gap between top of occupied and indicated that S(IV) and S(VI) entered into (111) and (200) crystal face
bottom of unoccupied band led to a visible light absorption and en- of CeO2, and led to the production of oxygen vacancies and the con-
hanced photocatalytic activity. Additionally, Singh et al. [50] synthe- version of Ce4+ to Ce3+. The formation of nonlocalized impurity band
sized La doping CeO2 (LaxCe1-xO2-δ) by co-precipitation method and was owing to the mix of S 2p and Ce 4f orbitals between conduction
investigated the photodegradation efficiency of MB. The resultant ma- band Ce 5d and valence band O 2p, resulting the red shift of absorption
terial present superior photocatalytic efficiency for the degradation of edge to visible light ∼500 nm. The degradation efficiency of MO by S-
organic dyes. CeO2 could reach 98.6%, which was much higher than that of pure
The nitrate-fuel self-sustaining combustion method was performed CeO2 (29.3%) within 80 min visible light irradiation. However, the
to prepare yttrium doped CeO2 by Fakhrabadi et al. [51] According to valence states of S and Ce played an important role in the photo-
the TEM results, the as-prepared CeO2 (Fig. 2E) represented cubic catalytic activity rather than the amount of oxygen vacancy.
fluorite and the structure was almost unchanged after the introduction Besides, Miao et al. [60] prepared F-doped CeO2 by a low-tem-
of yttrium (Fig. 2F), but the specific surface area was enlarged with perature solution combustion process and used the citric acid as fuel.
yttrium doping (from 36 to 52 m2/g). As expected, yttrium doped CeO2 TEM images demonstrated that the doping of F into CeO2 resulted in
could absorb visible light and the bandgap of pure CeO2 was around smaller size and the microstructure changed from nanospheres (CeO2,
3.31 eV and yttrium doped CeO2 was 2.96 eV (Fig. 2G). From Fig. 2H, Fig. 3B) to nanocubes (F-doped CeO2, Fig. 3C), which could be indexed
the degradation rate of Rhodamine B (RhB) under visible light by pure to the etching effect of HF on the surface of CeO2. The band gap of CeO2
CeO2 was negligible due to its inherent large band gap. Notably, the narrowed from 3.16 eV to 2.88 eV after F doping, and the UV–vis DRS
degradation efficiency was obviously improved by yttrium doped CeO2, analysis indicated that the absorbance edge was red shift to slight
which was ascribed to the active electrons and holes produced on the visible light from ∼380 nm to ∼550 nm (F(1/3)–CeO2, Fig. 3D), which
surface of visible-light-driven photocatalyst. means that more solar energy could be utilized by F-doped CeO2. Ac-
cording to Fig. 3E, the optimal photocatalyst was F(1/3)–CeO2. The
3.1.2. Nonmetal doping degradation efficiency of MB over F(1/3)–CeO2 (0.314 min−1) was 9.5
Doping metal ions in a semiconductor could lead to the poor ther- times higher than that of pure CeO2 (0.033 min−1) and 2.2 times higher
modynamic stability of the photocatalyst and metal ions could easily than commercial TiO2 under UV light, whereas the photocatalytic
form recombination centers and then restrain the separation of e−-h+ performance of F(1/3)–CeO2 (0.0896 min−1) was 6.0 times higher than
pairs [52,53]. Therefore, doping of nonmetal ions in CeO2 has attracted that of pure CeO2 (0.0149 min−1) under visible-light irradiation.
extensive attention. Usually, doping of nonmetal ions in a catalyst could
form a new VB over the original one, which was illustrated in Fig. 3A. 3.2. Deposition of noble metal on CeO2
The absorption region of TiO2 presented a red-shift to visible light
after doping nonmetal elements (i.e. N, C, F, S, etc.). The phenomenon As it is well known, the wide band gap and weak visible-light ab-
could be interpreted as the hybridization of the p orbital of nonmetal sorption of CeO2 severely restrained its practical application. The dec-
element with O 2p, which resulted in the upward shift of VB edge and oration of noble metal (e.g., Au and Ag) nanoparticles on CeO2 as
hence decreased the forbidden band [40]. Therefore, it could be in- catalysts is another favorable choice to enhance its photoactivity. The
ferred that doping N might change the density of states near VB edge of fact mainly resulted from localized surface plasmon resonance (LSPR)
CeO2. But Mao et al. [54] found that both VB and CB of N doping CeO2 of noble metal nanoparticles, which led to the extended light response
shifted to lower energies by using density functional theory (DFT) range [61–63]. The detailed electron transfer pathways were depicted
calculation. They employed two cases to investigate the influence of in Fig. 4A. Upon being excited by visible light, photoinduced electrons
nitrogen doping of CeO2, i.e., O was replaced by N or created an O transferred immediately from these metal particles to the CB of CeO2
vacancy in CeO2 crystal, and the overall lowering in transition energy until their Fermi levels were equilibrated. The migrated e− might react
was attributed to the introduction of impurity energy levels. Jorge et al. with dissolved O2 to yield O2•- and other reactive radicals. Meanwhile,
[55] also prepared the N-doped CeO2 porous thin films by sol–gel resultant electron-deficient noble metals would oxide organic pollu-
combining evaporation method, and the nitride CeO2 exhibited an en- tants directly, which were then reduced to their original state. Even-
hanced catalytic capacity for acetaldehyde degradation than pure CeO2. tually, the recombination of e−-h+ pairs was successfully inhibited
And the XPS analysis indicated that the replacement of O by N ac- during photoreaction and thus the photocatalytic performances of na-
companied by the generation of anion vacancies was a reasonable nocomposites were enhanced [64].
mechanism. Another N-doped CeO2 system was reported by Wu et al. For example, Au/CeO2 nanocomposites were successfully prepared
[56] with a low temperature solvothermal method to evaluate the via a facile photodeposition method to degrade organic acid under
photodegradation of rhodamine 6 G (R6 G) under visible light irradia- visible light [65]. An additional absorption peak (Fig. 4B) at ca. 550 nm
tion. Absorption of visible light by N-doped CeO2 was broadened from was revealed in the absorption spectrum of 1 wt.% Au/CeO2, which was
∼360 nm to ∼380 nm with a broad tail from ca. 400 to 800 nm. The derived from the LSPR of supported Au NPs. The CO2 evolution rate,
degradation rate of R6 G was 0.0009 min−1 for pure CeO2 and which represented the mineralization efficiencies of formic acid, in-
0.0114 min−1 for N-doped CeO2 under the reaction conditions. Ren creased until the loaded content of Au on CeO2 was up to 1 wt.%.
et al. [57] utilized the first-principle calculation to understand the Correspondingly, the mineralization rate of formic acid was 2.4 kJ

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R. Ma et al. Catalysis Today 335 (2019) 20–30

Fig. 3. (A) Schematic band structures of nonmetal doped CeO2. TEM images of (B) pure CeO2, (C) F(1/3)–CeO2. (D) UV–vis DRS spectra of pure CeO2 and F(1/
3)–CeO2. (E) Kinetic study of degradation MB by pure CeO2, F–CeO2 and TiO2. (B), (C), (D) and (E) reprinted with permission from Ref. [60].

mol−1 for 1 wt.% Au/CeO2, and oxalic acid and acetic acid could be Au@CeO2 spheres by a combined carbon microsphere template method
completely degraded to CO2. The superior photocatalytic activity was and layer-by-layer strategy. This hybrid consequently exhibited ex-
mainly affected by LSPR of Au NPs and depended on its loading cellent photoactivity and stability for the decolorization of MB.
amount. Besides, the degradation rate of formic acid over different Au Except for Au metal, the Ag NPs@CeO2 (Ag@CeO2) and Ag
NPs deposited nanocomposites ranked in the following sequence of Au/ nanowires@CeO2 (Ag NWs@CeO2) core-shell structure were fabricated
CeO2 > > Au/TiO2 > Au/ZrO2. To provide more active sites and avoid to degrade MB under visible light irradiation [67]. The photodegrada-
the aggregation of Au NPs, Zhou et al. [66] synthesized 3D yolk-shell tion mechanism of NPs@CeO2 and NWs@CeO2 were illustrated in

Fig. 4. (A) Schematic illustration for the degradation mechanism of noble metal-modified CeO2. (B) UV–vis DRS spectra of CeO2 and Au/CeO2 [65]; Photocatalytic
mechanism of (C) Ag NPs@CeO2, (D) Ag nanowires@CeO2. (E) UV–vis DRS spectra of Ag modified CeO2. (F) Kinetic study of degradation MB by as-synthesized
samples. (C), (D), (E) and (F) reprinted with permission from Ref. [67].

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R. Ma et al. Catalysis Today 335 (2019) 20–30

Fig. 4C and D, respectively. Excited e− generated in the Ag cores owing of Y content, the YDC presented increasing amount of Vo. The photo-
to LSPR of noble metal and then transferred to the CB of CeO2. At the catalytic properties of different CeO2 composites were shown in Fig. 5C,
same time, CeO2 shell could absorb photon to produce e−-h+ pairs. and the YDC possessed higher catalytic performance for RhB degrada-
Afterward, the excited charge carriers took a battery of reactions to tion at less than 50% Y doping. The lower band gap than bulk CeO2 at a
yield •OH, which played a dominated role in the degradation of MB. small portion of Y could be interpreted as the production of localized
According to the UV–vis DRS spectra (Fig. 4E), Ag modified CeO2 states between VB and CB owing to Vo and the increase of Ce3+.
presented enhanced visible light absorption capacity. From Fig. 4F, one However, the decline of photocatalytic capacity when the Y content
can see that the degradation efficiency of CeO2 improved after the in- more than 50% was assigned to the Vo clusters microdomains, leading
troduction of Ag, and Ag NWs@CeO2 presented the highest photo- to fast recombination of photoinduced charge carriers.
degradation ability, which could partly be indexed to its high specific Zhang et al. [70] reported ZrO2-CeO2 composites (Zr1-xCexO2) by
surface area. Another high-performance Ag/CeO2 nanohybrids were citrate complexation method to explore the photodegradation activities
synthesized by Saravanakumar et al. via a facile hydrothermal tech- on RhB and 2, 4- dichlorophenol (2, 4-DCP). As shown in Fig. 5D, the
nique [68]. The degradation efficiencies of MB, RhB and crystal violet oxo-bridged bimetallic linkage ZrIV-O-CeIII in Zr1-xCexO2 acting as
by optimized Ag/CeO2 were exceeded 97% in less than or equal to visible-light-driven redox center could improve the photocatalytic ac-
70 min, whereas the photocatalytic capacity of Ag@CeO2 over MB was tivities efficiently. Under visible light irradiation, the metal-to-metal
only 80% within 150 min. The mechanism of enhanced photo- charge transfer (MMCT) occurred owing to the transition of ZrIV-O-CeIII
degradation over Ag/CeO2 could be attributed to the LSPR of Ag and to ZrIII-O-CeIV, and the additional Ce4+ could oxidize organic and the
trapping experiments further showed that •OH radicals took the chief resultant ZrIII could react with dissolved O2 to yield O2·− and thus en-
responsibility for degradation of organic dyes. hance the photocatalytic performance of the homogeneous Zr1-xCexO2
composites. Besides, the degradation efficiencies of Zr0.9Ce0.1O2,
3.3. Construction of CeO2-based solid-solution Zr0.8Ce0.2O2, and Zr0.7Ce0.3O2 were 58%, 74%, and 51% for RhB and
18.2%, 17.8%, and 19.1% for 2, 4-DCP under experimental conditions,
Element doping CeO2 could narrow down Eg by decreasing CB, respectively.
putting upward VB or implementing the both process simultaneously to Tian et al. [71] further investigated different shapes of Ce0.4Zr0.6O2
respond to visible light. However, all the three aforementioned types composites by hydrothermal method for MB photodegradation under
would decrease its redox potential, which reduce the adequate redox visible light, and the nanoparticle Zr-rich phase presented a superior
capability of CeO2. Recently, modification of CeO2 by forming solid- degradation rate of 0.0102 min−1. The optimal photocatalytic property
solution with continuous bandgap (Fig. 5A) has attracted much atten- was ascribed to its appropriate structure for MB molecular absorption
tion in photocatalysis, which could precisely manipulate its position of and motivation and the prompt separation of photo-induced carriers.
energy level in order to realize the balance between effective visible Hao et al. [72] used SBA-15 as template to synthesize Pr-doped meso-
light absorption and strong oxide potential [13]. porous CeO2 (Ce-Pr-O) to decompose RhB under the laboratory natural
The various Y-doped ceria (YDC) solid nanorods were prepared by light. According to characterization analysis, it was found that Ce-Pr-O
Liyanage et al. via a hydrothermal process [69]. According to UV–vis with 2D hexagonal structure possessed abundant oxygen vacancies. The
DRS spectra (Fig. 5B), the band gap of Y-doped CeO2 decreased with the absorption spectra became stronger with the increase of Pr contents and
increase of Y content up to 50%, and then increased. With the increase decreased after Pr contents higher than 45%. Interestingly, the

Fig. 5. (A) Schematic band structures

of CeO2 solid solution. (B) UV–vis DRS
spectra of CeO2 solid solutions with
different Y content [69]. (C) Photo-
degradation of RhB by different CeO2
solid solutions [69] (D) schematically
demonstration the photocatalytic ef-
fects over oxo-bridged ZrIV-O-CeIII
under visible light irradiation [70].

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R. Ma et al. Catalysis Today 335 (2019) 20–30

variation trend of optical edge was consistent with that of Vo, in- heterojunctions, CeO2 are usually decorated by other semiconductors
dicating that the amount of Vo is benefit to absorb visible light. The with low energy gaps or coupled with wider band-gap nanomaterials as
photodegradation efficiency of RhB over mesoporous CeO2 was much light-absorbing medium. Once being coupled with narrower band-gap
better than that of bulk CeO2 (65% > 48%), and this phenomenon was semiconductors (Fig. 6A), both CeO2 and Semiconductor I (SC1) can be
explained in two reasons. Firstly, the increased specific surface area excited when exposed to visible light, and the photo-generated e−
could provide more active sites and improve the separation efficiency of moves from VB to CB and an equal amount of h+ leaves on its VB. In
excited e- and h+. Secondly, the nanosized material allowed the pho- addition, the e− on the CB of SC1 immigrates to that of CeO2, and
toinduced carriers inside the crystal to immigrate to the surface. In meanwhile the remained h+ moves from the VB of CeO2 to that of SC1,
addition, the Ce-Pr-O exhibited much better photodegradation effi- due to the much lower band gap and internal electric field. While, SC2
ciency than mesoporous CeO2, which could be indexed to the formation cannot absorb visible light owing to its large band energy (Fig. 6B).
of Vo after Pr-doping and the positive charged captured reactive e-. Therefore, only one electron transfer route occurs in these hybrids,
Therefore, the separation of photo-driven carriers was enhanced. which is from the CB of CeO2 to that of SC1. The formation of het-
erojunction between different semiconductors accelerates the migration
3.4. Coupling CeO2 with other nanomaterials of e− and h+, and inhibits the recombination of photo-induced charge
carriers.
Recently, fabrication of heterostructures by incorporating CeO2 However, according to the Type II charge transfer pathway, e− and
+
with two or more nanomaterials is deemed as a most promising way to h move to the less negative CB and positive VB of these composites,
realize its more effective photoactivity. The improvement of their de- respectively, indicating an obvious decrease of oxidizability for h+ and
gradation behaviors was originated from synergistic effects between reducibility for e−. The h+ in the VB of SC1 may possess less weak
different nanomaterials, leading to excellent stability, enhanced visible oxidative potential than water oxidation potential (0.82 eV vs. NHE at
light utilization, and efficient charge separation and migration [73,74]. pH 7), which meant the unavailable of O2 evolution. Generally, lots of
oxygen vacancies are formed on the surface of CeO2, which inhibits the
reduction of Ce4+ to Ce3+ by trapping photoinduced e− and improves
3.4.1. Binary hybrid heterostructures its photostability. Besides, the reduction potential of Vo is more positive
In terms of binary CeO2-based composites, the modification of CeO2 than that of O2/O2•- (-0.33 eV vs. NHE), indicating that the production
by combining with other suitable semiconductors is a good strategy. In of O2•- radicals decreases and lead to lower photodegradation perfor-
general, two possible charge transfer pathways are taken into con- mance. However, this mechanism explanation is not consistent with
sideration to elucidate the enhanced photocatalytic activity of visible- most studies. Hence, another Z-scheme mechanism of CeO2-based hy-
light-induced CeO2-based composites, which are namely the typical brids is introduced, as depicted in Fig. 6C. Photogenerated e− from the
type II and Z-scheme mechanisms, as shown in Fig. 6. As for type II

Fig. 6. Schematic illustration of different photodegradation mechanisms: Type II (A) hybridize with SC1; (B) hybridize with SC2. Z-scheme (C); p-n heterojunction
system (D).

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R. Ma et al. Catalysis Today 335 (2019) 20–30

CB of CeO2 transferred to the VB of SC1 to consume h+, and the energy The RhB degradation rate over the optimal BiOBr/CeO2 composite (Ce/
released in the form of heat and futile emission light. While, the left e− Bi molar ratio is 2, denoted as BC-2) reached to 0.1427 min−1, which
and h+ own stronger redox potentials, which contribute to the gen- was 2.8 and 18.8 times higher than that of pure BiOBr (0.0508 min−1)
eration of reactive oxygen species (i.e., O2•-, •OH and so on) and and CeO2 (0.0076 min−1), respectively, under visible light irradiation.
strongly oxidized h+. These reactive species can decompose organic Besides, the degradation efficiencies of MB and phenol on BC-2 were
pollutants directly to CO2, H2O and various intermediate products. 95% for 120 min and 75% for 270 min under visible light irradiation,
A p-n heterojunction system was established by Wang et al. [75] to respectively. On the basis of DRS analysis, the BC-2 exhibited a strong
degrade RhB under the simulated sunlight irradiation by adding hy- optical capability in visible light region, and the Eg value of BC-2 was
drogen peroxide as an electron acceptor. The new technique for the determined to be 2.25 eV according to Kubelka-Munk theory, which
synthesis of p-n type CuO/CeO2 composite was synthesized via a was obviously narrower than that of pure CeO2 (Eg = 2.81 eV) and
ribbon-ignition method. The decomposition rates of RhB were calcu- BiOBr. The photocatalytic mechanism was also investigated by adding
lated as 0.18, 0.12, 0.10 and 0.08 min−1 by CuO/CeO2 composite, CuO, various quenchers (Fig. 7C), and the negative effect on benzoquinone
CeO2 and H2O2 alone under experimental conditions, respectively. The (BQ) and triethanolamine (TEOA) indicated that O2·– and h+ were
enhancement of CuO/CeO2 composite may be ascribed to the visible- important during the photodegradation. Furthermore, the BC-2 showed
light-driven CuO and the intrinsic strong photocatalytic redox cap- a stable degradation performance in cycling tests. Song et al. [36] also
ability of CeO2 as well as the charge transfer channel between CuO and established a three-dimensional (3D) flower-like bismuth oxyhalides
CeO2. (BiOX)/CeO2 p-n heterojunction system by using a hydrothermal
The possible photodegradation mechanism of p-n type heterojunc- method. The 15% CeO2/BiOI exhibited the best photocatalytic perfor-
tion was in agreement with type II mechanism. As shown in Fig. 6D, a mance with a degradation efficiency of 80.29% within 120 min under
local internal electric field was established on the interface of p-n type experimental conditions and had a good efficiency for MO decom-
heterojunction and the orientation was from n-type to p-type semi- position. Moreover, some other Bi-contained semiconductors coupling
conductor. The photo-generated electrons transferred from the con- with CeO2 including Bi4Ti3O12 [80], BiVO4 [81] and CuBiO4 [82] have
duction band of p-type semiconductor to n-type semiconductor and been applied to decompose organic pollutants.
holes migrated in the opposite direction owing to the electrostatic in- Coupling Ag-contained semiconductors was also important to en-
teraction until the equilibrium state was reached. The reverse move- hance the photocatalytic efficiency of CeO2. Lin et al. [83] synthesized
ment of holes and electrons restrained the recombination probability. Ag3PO4/CeO2 heterojunction by ultrasound-assisted method in order to
The separate electrons and holes were likely to produce a chain reaction disperse the CeO2 particles onto the surface of Ag3PO4, so that CeO2
and the resulting active radicals with strong oxidative potential would could expose more surface active sites. Interestingly, the MB degrada-
react with organic pollutants to yield CO2 and H2O or other oxidation tion rates were 0.046, 0.186, 0.223 and 0.218 at the concentration of
products. 0.5, 1.0, 2.0, and 3.0 g/L composites, respectively. The decline of rate
Bi-contained semiconductors such as BiOI, BiOBr, Bi2WO6, Bi2O3 constants at the photocatalyst content of 3.0 g/L was indexed to light
and so on have been studied as efficient photocatalysts, herein, we scattering owing to excessive catalyst. In-situ synthesis of Ag3PO4/CeO2
reviewed the Bi-contained catalysts coupled with CeO2 for organic photocatalyst was reported by Zhang et al. [84] and the obtained
pollutants degradation. Guo et al. [76] fabricated ring-shaped composites presented enhanced photodegradation of RhB than pure
Bi2WO6@CeO2 by solvothermal alcoholysis combining calcination CeO2. High dispersibility of small CeO2 nanoparticles might be bene-
method. The modified CeO2 presented a superior photodegradation of ficial to absorb visible light, and suitable p-n junction structure was
MO and RhB under visible light, and the efficient photocatalytic per- significant to photocatalytic capacity. Wen et al. [31] coupled CeO2
formance was explained that the existence of an internal electric field in with AgI via a deposition–precipitation technique, and the well-mat-
the p-n junction improved the separation of e−-h+ pairs and im- ched band structure facilitated the separation of excited e− and h+. As
migration of interfacial charge. Issarapanacheewin et al. [77] synthe- a result, the degradation efficiency of the optimal AgI/CeO2 was 98%
sized CeO2/Bi2WO6 nanocomposites to degrade RhB and MB. The de- for RhB within 20 min and 94.34% for tetracycline (TC) within 60 min.
gradation efficiency of CeO2/Bi2WO6 is 54.09% for RhB and 15.58% for They also established another Ag-contained/CeO2 system by in-situ
MB within 75 min under visible light irradiation. Trapping experiments loading Ag2CO3 on CeO2 combining thermal decomposition method
indicated that h+ and ·OH played an important role in the degradation [30]. The photodegradation efficiency of enrofloxacin (EFA) was
process. The reasonable photocatalytic mechanism was depicted in 87.11% for optimal Ag2O/CeO2 composite whereas 42.95% for pure
Fig. 7A. The CB of Bi2WO6 (+0.43 eV) was less negative than standard Ag2O within 120 min under visible light irradiation. Moreover, trapping
redox potential of O2, leading to the accumulated e− on the CB of experiments indicated that h+ and O2·- played a dominant role in the
Bi2WO6, which could not react with O2 to generate O2·- and to form degradation process. Besides, AgBr/ CeO2 [85] and Ag2CO3/ CeO2 [86]
·OH. Another CeO2/Bi2WO6 system was reported by Zhang et al. [78] have also been fabricated as efficient photocatalysts to remove organics
by solvothermal method. The optimal composite showed an excellent from wastewater.
tetracycline hydrochloride (TCH) degradation rate of 0.037 min-1, Apart from those, Tian et al. [87] synthesized the CeO2/TiO2 na-
which was much higher than that of pure Bi2WO6 (0.017 min-1). The nobelt heterostructure by the hydrothermal method. It was found that
CeO2/Bi2WO6 microspheres due to couple Bi2WO6 with CeO2 may CeO2/TiO2 composites represented superior photodegradation of MO
improve transference of the charge carriers, which could lead to a under visible light than CeO2, TiO2 and commercial P25 colloids. The
higher photodegradation prosperity of the composite. Bi2O3-modified photocatalytic mechanism could be expressed as a capture–-
CeO2 nanospheres were performed to degrade RhB under visible light photodegradation–release processes. At first, MO molecules were ab-
and exhibited a remarkable photocatalytic activities [79]. The Bi2O3/ sorbed on CeO2 nanoparticles due to its large surface area, and then
CeO2 photocatalysts showed a broad visible light absorption with the were decomposed by reactive species. The degraded molecules were
edge up to ∼700 nm. This might attribute to the suitable ratio of Ce:Bi, released eventually. Zhang et al. [88] prepared a hollow CeO2@TiO2
resulting the sizes of particles and cavities close to the wavelength of composite with a core-shell structure by precipitation combining hy-
light. drothermal method. The optical capacity of CeO2/TiO2 hybrid catalyst
Wen and co-workers [32] fabricated BiOBr/CeO2 nanocomposites showed a visible light absorbance with a band edge ca. 500 nm. Under
through a facile deposition-precipitation process. TEM images and XRD experimental condition, the degradation of RhB by CeO2/TiO2 com-
patterns demonstrated that BiOBr and CeO2 were tightly coupled posites was 75% within 3 h and the enhancement of photocatalytic
without any other impurities. The photodegradation activities of RhB, performance could be attributed to charge carriers transform efficiency
MB and phenol over the as-prepared catalysts were shown in Fig. 7B. facilitated by its core-shell structure. Since it’s a complex process to

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R. Ma et al. Catalysis Today 335 (2019) 20–30

Fig. 7. (A) Schematic photodegradation of CeO2/Bi2WO6 composite. [76] (B) Photocatalytic behaviors of CeO2, BiOBr and their composites for the degradation of
RhB and the optimal composite for the degradation of MB and phenol [32]. (C) Photodegradation of RhB with different scavengers over BC-2 [32].

fabricate hollow structure, Chen et al. [89] reported the synthesis of received increasing attention in virtue of multiple properties, which
CeO2@TiO2 core-shell composites with a facile hydrothermal method. came from the synergistic effects of different individual components
The degradation rate of CeO2@TiO2 catalyst was 0.012 min−1, which and resulted in outstanding photocatalytic behaviors. Numerous efforts
was 3 and 4 times higher than those of bare CeO2 (0.004 min−1) and have been made to modify CeO2 by constructing novel effective ternary
TiO2 (0.003 min−1), respectively. heterostructure. Among these nanocomposites, the incorporation of
For comparison, a summary of photodegradation properties and CeO2 with bismuth containing compounds including Bi2O3, BiVO4 and
preparation methods towards various CeO2-based hybrids were listed in BiOI displayed desirable photocatalytic performance. Zou et al. coupled
Table 1. CeO2 with P25 and Bi2O3 by a facile ball milling and sintering method
[102]. After activity evaluation, the optimal mole ratio of TiO2: CeO2:
Bi2O3 were determined to be 2: 5: 3, which degraded about 55% of RhB
3.4.2. Ternary nanocomposites within 2 h under visible light irradiation. Hezam and co-workers further
Over recent years, construction of CeO2-based ternary systems has

Table 1
Summary of photodegradation properties towards various CeO2-based hybrids.
Photocatalysts Preparation method Application Degradation efficiency Reference

CdS/CeO2 hydrothermal Degradation of RhB 97% in 48 min [90]

CeO2/Ce2O3 liquid phase pulsed laser ablation Degradation of MB 24% in 120 min [91]
CeO2/ZnO precipitation Degradation of direct blue-15 95% in 120 min [92]
CeO2/RGAs sonication-assisted chemical method Degradation of RhB 85% in 120 min [93]
CeO2/Tb2O3 precipitation Degradation of MB 93% in 75 min [94]
rGO-CeO2 in situ hydrothermal method Degradation of MB 72% in 50 min [95]
CeO2/alumina mixing-calcination method Degradation of Congo red (CR) 90% in 120 min [96]
Degradation of MO 92% in 90 min
CeO2/Co3O4 coprecipitation method. Degradation of MB 99.65% in 60 min [97]
Degradation of methyl red (MR) 99.51% in 60 min
CeO2/FACs modified pyrolysis process Degradation of MB 60% in 300 min [98]
CeO2/Nylon solution cast method Degradation of MO 94.32% in 60 min [99]
Degradation of CR 92.51% in 120 min
CeO2–SnO2 coprecipitation Degradation of Direct Black 38 ∼60% in 240 min [100]
process
CeO2/V2O5 thermal decomposition method Degradation of MB 64.2% in 210 min [101]
CeO2/CuO thermal decomposition method Degradation of MB 70.1% in 210 min [101]

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R. Ma et al. Catalysis Today 335 (2019) 20–30

introduced ZnO into Bi2O3-CeO2 nanocomposites via a combined mi- photocatalytic oxidation steps are introduced in this review.
crowave-assisted hydrothermal method and subsequently thermal de- Subsequently, the recent advances in modifications and mechanisms of
composition process [103]. The heterostructure was formed among CeO2-based NPs as effective photocatalysts are summarized in detail.
monoclinic α-Bi2O3, cubic CeO2 and hexagonal ZnO was also verified Besides, this paper also reviewed recent studies about the modified
by PXRD, Raman and FTIR analyses. Enhanced visible-light absorption CeO2 for photodegradation of organic pollutants.
was observed in the range of 400–780 nm. These superior properties led Generally, doping of element in CeO2 could narrow down the for-
to better photodegradation performance for Bi2O3-CeO2-ZnO than pure bidden gap and thus enhance the absorption of visible light. However,
TiO2, CeO2, Bi2O3 and binary systems. In addition, CeO2-BiVO4/FAC doping metal ions into CeO2 tend to be recombination centers, re-
photocatalysts were also prepared by Zhang et al. via a simple im- straining the migration of charge carriers. Therefore, doping nonmetal
pregnation method [104]. For this composites, the p-n heterojunction ions is more effective to expand its absorption edge to visible region.
was formed between BiVO4 and CeO2, and FAC served as supporter to Because of the LSPR of noble metal, depositing noble metals on CeO2
promote their fixation, distribution and recycling. As a result, the en- could also improve its response to visible light. Fabrication of homo-
hanced photocatalytic activity for MB degradation was achieved under geneous CeO2 with continuous bandgaps could manipulate the position
visible light illumination. of CB and VB accurately. In addition, this review explains the two
Silver based compounds were also an important classification of different mechanisms about semiconductor hybridization, which are
candidates to form hybrids with CeO2. Wen et al. firstly prepared Type II and Z-scheme mechanism. Coupled other semiconductor with
Ag2CO3/CeO2 by the in-situ coprecipitation approach and then treated CeO2 could improve the separation of excited e− and h+ and lead to
it by direct hydrobromic acid corrosion for desired ternary Ag2CO3/ high photocatalytic efficiency.
CeO2/AgBr hybrids [105]. A double Z-scheme heterojunctions were In summary, CeO2-based photocatalysts are efficient to dispose or-
fabricated and the visible light absorption was extended due to the ganic pollutants in wastewater, and the modified CeO2 may be a pro-
introduction of Ag2CO3 and AgBr, which led to high removal of levo- mising catalyst for future environment treatment. However, it is urgent
floxacin under λ > 420 nm visible light. Furthermore, coupling CeO2 to dissolve the capacity loss and recovery of photocatalyst in recycle
with Ag NPs and Ag-based semiconductors together has also emerged as use. For some samples, the preparation process is complex and the yield
an attractive modification method to construct visible-light-response is very low. Hence, facile, green and high-yield synthetic strategies is
photocatalysts. As mentioned above, noble metal could contribute to needed to fabricate CeO2-based photocatalysts. Besides, owing to the
the visible-light response and charge separation by fabricating novel easier decomposition of dyes, most of the studies use dyes as research
plasmonic systems. For instance, Wen and co-workers coated Ag/AgCl objects to understand the degradation process of photocatalysis tech-
on CeO2 through a combined in-situ deposition and photoreduction nique. But a few people utilize POPs as model organic pollutants.
approach [106]. It could be discovered that about 91% of norfloxacin Consequently, further understanding of the degradation mechanism
could be removed within 90 min over optimized Ag/AgCl-CeO2 com- and charge transfer pathways is still necessary. Such scientific problems
posites under visible light irradiation, and correspondingly 59.61% was are crucial for the real application of CeO2-based composites in the
mineralized after 150 min. This was mainly attributed to the LSPR of Ag photodegradation of organic pollutants from wastewater.
NPs for better light absorption and formation of effective heterojunc-
tions at interfaces to accelerate the separation of charge carriers. Sub- Acknowledgments
sequently, AgBr was chosen as an analogue to substitute AgCl by
forming ternary CeO2-Ag/AgBr nanocomposites, which was synthesized This work was supported by National Key Research and
by a modified coprecipitation process followed by photoreduction Development Program of China (2017YFA0207002), NSFC (21836001,
[107]. Interestingly, CeO2-Ag/AgBr nanocomposites also revealed the 21607042, 21707033, 21577032), and the Fundamental Research
good heterostructure among individual substances with intimate con- Funds from the Central Universities (2018ZD11, 2017MS045).
tact. This hybrid displayed superior photodegradation activity for ci-
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