Structure, Synthesis, and Catalytic Properties of Nanosize Cerium-Zirconium-Based Solid Solutions in Environmental Catalysis

Chinese Journal of Catalysis 40 (2019) 1438–1487
available at www.sciencedirect.com
journal homepage: www.elsevier.com/locate/chnjc
Review
Structure, synthesis, and catalytic properties of nanosize
cerium-zirconium-based solid solutions in environmental catalysis
Jixing Liu a, Zhen Zhao a,b, Chunming Xu a, Jian Liu a,*
a State Key Laboratory of Heavy Oil, China University of Petroleum, Beijing 102249, China
b Institute of Catalysis for Energy and Environment, Shenyang Normal University, Shenyang 110034, Liaoning, China
A R T I C L E I N F O A B S T R A C T
Article history: Nanosize cerium-zirconium solid solution (CZO) with a special fluorite structure has received an
Received 28 May 2019 increasing research interest due to their remarkable advantages such as excellent oxygen storage
Accepted 3 July 2019 capacity and great flexibility in their composition and structure. By partial metal (including rare
Published 5 October 2019 earth, transition, alkaline earth or other metal) doping into CZO, the physicochemical properties of
these catalytic materials can be controllable adjusted for the study of specific reactions. To date,
Keywords: nanosize CZO has been prepared by co-precipitation, sol-gel, surfactant-assisted approach, solution
Cerium-zirconium solid solution combustion, micro-emulsion, high energy mechanical milling, etc. The advent of these methodolo-
Synthesis gies has prompted researchers to construct well-defined networks with customized micromor-
Method phology and functionalities. In this review, we describe not only the basic structure and synthetic
Structure strategies of CZO, but also their relevant applications in environmental catalysis, such as the purifi-
Environmental catalysis cation for CO, nitrogen oxides (NOx), volatile organic compounds (VOC), soot, hydrocarbon (HC), CO2
and solid particulate matters (PM), and some reaction mechanisms are also summarized.
© 2019, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
1. Introduction heterogeneous catalytic reactions [11–18], including methane

combustion, water-gas shift, water steam reforming reaction,
Nowadays, the issue of the environment is receiving ever etc. Moreover, a large number of reports have shown that par-
increasing attention. One of the primary efforts of environ- tial incorporation of zirconium ion (Zr4+) into ceria lattice can
mental protection is concentrated on controlling the emission substantially enhance the redox properties and oxygen storage
of toxic pollutants from combustion of fossil fuels in automotive capacity (OSC) [19–30]. This is an interesting finding, consid-
engines and industrial production [1–3]. Three-way catalysts ered that Zr4+ is isovalent with the host Ce4+ ion and also a fixed
(TWCs) are widely employed to lessen the emissions of carbon valent ion, so that it can not induce the valency change such as
monoxide (CO), nitrogen oxides (NOx), and hydrocarbons (HC) with Pr3+/4+ or creation of charge compensating defects such as
from automobile exhausts [4–6]. Among these catalysts, ceria with Gd3+ [31–35]. Instead, the smaller Zr4+, in comparison with
(CeO2) is a key component, which exhibits cubic fluorite type of Ce4+, prefers a 7-fold coordination, in contrast to the 8-fold
structure and has attracted much attention in recent decades coordination of the fluorite cation, resulting in a driving force to
due to its good redox property and high storage/release oxygen form oxygen vacancies associated with structural relaxation
capacity, associated with the abundant oxygen vacancy and through reduction of the smaller Ce4+ to the bigger Ce3+
facile shift of Ce3+/Ce4+ [7–10]. It has also been used in many [36–39]. Based on the first principle calculations, a Zr dopant
* Corresponding author. Tel: +86-10-89732278; Fax: +86-10-69724721; E-mail: [email protected]

This work was financially supported by the National Natural Science Foundation of China (21673290, U1662103).
DOI: S1872-2067(19)63400-5 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 40, No. 10, October 2019
Jixing Liu et al. / Chinese Journal of Catalysis 40 (2019) 1438–1487 1439
acts as low energy regions for the formation and clustering of first oxygen shell around Ce exhibits the characteristics ex-
oxygen vacancy [40–43]. In addition, the long-term thermal pected for pure CeO2 (fluorite-type crystal structure, one shell
morphology and/or redox stability of pure CeO2 has been en- with 8 oxygen atoms) even if the crystallite phase is t (t′ and t″
hanced by the introduction of Zr [20,28,44,45]. Furthermore, forms) or c. In contrast, the first shell around Zr atoms shows
owing to the special redox ability of Ce-Zr solid solution (CZO), obvious differences from the changes in the crystal structure.
it can be employed to support noble metals and transition met- This means that it splits into two oxygen subshells for the te-
al oxides or to design ternary solid solutions by doping small tragonal forms and displays only one shell for the c phase. In
amounts of other transition or rare earth metals [46–53]. CZO other words, the tetragonal-to-cubic phase transition is closely
has been widely employed in the abatement of CO, NOx and related to a symmetry change of the first oxygen shell around
toxic volatile organic compounds (VOC) and many other heter- Zr atoms, whereas that around Ce atoms remains unchanged.
ogeneous catalysis reactions. This review primarily focuses on The appearance of cubic, t′, and t″ phases in CZO depends
the structure, synthesis, and application of Ce-Zr-based solid strongly on the Zr content. Yashima et al. [54] proposed a phase
solutions in environmental catalysis. The first part of the re- diagram according to XRD and Raman analysis, as shown in Fig.
view presents advances in the structure and synthesis of CZO, 2, and it could be depicted as follows. A cubic fluorite phase c is
and the catalytic properties of CZO are thereafter reviewed in present (group Fm3m) for x > 0.85 at temperature below 1000
the second part. °C. A tetragonal phase t (group P42/nmc) can be produced at
high temperature by solid-state synthesis and then cooling to
2. The structure of nanosize cerium-zirconium-based room temperature for 0.10 < x < 0.30, and it is thermodynam-
solid solutions ical stable. A monoclinic phase (group P21/c) is formed for x <
0.10, while a metastable phase t' is seen for 0.30 < x < 0.65. In
Ceria has a special cubic fluorite structure and is the most the end, t'' or pseudo-cubic phase is intermediate between the c
widely used rare earth oxide. It is also a good catalyst support and t' phases (0.65 < x < 0.85 or 0.5 < x < 0.85 for small parti-
that can promote the uniform distribution of active compo- cles). This is characterized by a cubic cation sublattice, while its
nents and enhance the catalytic activity [17]. However, pure oxygen sublattice is tetragonally distorted (P42/nmc). The
ceria easily aggregates at high temperatures, and Zr doping can phase boundaries should be very approximate. As a matter of
enhance the stability of cerium-based materials. CZO exhibits a fact, in the case of the metastable tetragonal phases, the struc-
main cubic fluorite structure when Zr content is low, as shown ture distortion of CZO should be highly depended on the calci-
in Fig. 1. However, CZO undergoes a cubic to tetragonal fluorite nation temperature and the particle size of the materials.
phase transition with increasing Zr content and ultimately Due to the complexity of the phase diagram, it is difficult to
forms a monoclinic phase at high Zr contents [39,54–56]. The determine the phase homogeneity of CZO, even though a great
bond length ratio of c- to a-axis (c/a) is equal to 1.4 for the te- effort has been made. Small changes in oxygen ion-cation coor-
tragonal phase (t-phase), which is attributed to the P42/nmc
space group and shows two distortions t′ (c/a = 1.01) and t″
(c/a = 1) [57]. One can distinguish between the t′ and t″ phases
from the measurement of lattice parameters, though some sim-
ilarity between the t″ and cubic structures. The phase change
from cubic to t″ would induce an increase in the wavenumber
of Raman vibrational modes and remarkable changes in ionic
bond strength [54,58]. Similar to the cubic to tetragonal distor-
tion in CZO, the relaxation of oxygen atoms away from their
ideal fluorite positions and the formation of ordered domains
have been observed in cubic fluorite and hafnia by electron
diffraction. The structure of CZO materials exhibits some pri-
mary features, which have been reported by Yashima and
Fá bregas et al. [59,60]. One of the important features is that the
Fig. 2. Metastable-stable phase diagram in CexZr1-xO2

tem: c-phase, t''-phase, c'-phase, t'-phase. The dash lines
Fig. 1. Schematic diagram of CexZr1-xO2 lattice structure: O, Zr, represent the metastable phase boundaries. Reprinted from [54] with
and Ce. permission.
1440 Jixing Liu et al. / Chinese Journal of Catalysis 40 (2019) 1438–1487
dination are not always detectable as additional peaks (or peak parison of CZO powders with different particle sizes between
splitting) by XRD. However, Raman and other vibrational spec- ~6 and 80 nm, the phase boundaries exhibit an apparent shift
troscopy methods may be used to distinguish the primary oxy- to slightly higher zirconia contents with the decrease of the
gen ion distortions between the t″ and cubic phases [54]. Ra- particle size and the increase of the solubility of zirconia in each
man spectroscopy can play a critical role in the determination phase [73]. The position of the phase boundaries for CZO can
of all these phases and in the identification of the mechanical only be taken as approximate because t′ and t″ are metastable
stress. In fact, laser-excited Raman spectra are extremely sensi- phases and the degree of distortion of the cubic fluorite struc-
tive to M–O bonds, while powder XRD patterns are essentially ture strongly depends on the synthesis method, particle size,
determined by the arrangement of the lattice cations. Unfortu- morphology, metal doping and supported active phase type
nately, these conventional techniques fail in the investigation of [74].
the low crystallization degree materials, however, which are
very important in heterogeneous catalysis. More advanced 3. Recent advances in the synthesis and morphology of
techniques, such as neutron diffraction and EXAFS, have proved nanosize cerium-zirconium-based solid solutions
to be effectively on determining inhomogeneity and detecting
complementary structural information [36,62–65]. Moreover, It is well known that morphology and microstructure signif-
Montini et al. [66] investigated the potential of luminescence icantly influence the physicochemical properties and the per-
spectroscopy for identifying the homogeneity of CZO materials formances of CZO materials, especially the high surface area,
using Eu(III) ion as a structural probe. This technique provides which can supply a large number of active sites for the pro-
a detailed picture of local environment of the cations in these ceeding of catalytic reactions [75]. Materials with nanosize
materials due to the fact that the luminescence properties of (1~100 nm) will exhibit special properties due to the following
Eu(III) are strongly affected by the local surrounding around effects: a) quantum size effect; b) small size effect; c) surface
the cation ion (Fig. 3). effect; d) macroscopic quantum tunneling effect. Hence, it is
Great efforts to establish a correlation between structure well worthy to pay attention and spare efforts on the study of
and physicochemical properties have been devoted to a lot of the synthesis of nanosize CZO with different morphology and
research concerning CZO materials. The presence of surface catalytic performances.
domains [67,68], formation of ordered defective structures
[69–71], disordered oxygens coordinated around zirconium 3.1. Synthesis methods for nanosize cerium-zirconium-based
[72], and distortion in the oxygen sublattice [38,66–68] have solid solutions
improved redox properties of CZO with respect to CeO2. Com-
A synthesis method is significantly important for nanosize
CZO due to its influence on the size, morphology, structure,
surface state, and oxygen vacancies. It is closely related to the
reducibility of cerium-based composite of the as-prepared ma-
terials [76–80]. The controllable synthesis research is an issue
worthy to concern. To date, various synthetic routes have been
developed for the synthesis of nanosize ceri-
um-zirconium-based solid solutions, such as co-precipitation
(CP), sol-gel (SG), self-assembly, template-assisted approach,
solution combustion (SC), micro-emulsion (ME), high energy
mechanical milling, etc.
3.1.1. Co-precipitation method

CP is one of the most commonly used methods for nanosize
CZO synthesis owing to its simple synthesis process. In general,
it includes room-temperature [81–85], medium-to-high tem-
perature [86–88], surfactant-modified [89,90], and ultra-
sound-induced CP [91]. Precipitants (ammonia water and am-
monium carbonate) are employed to react with the soluble
Fig. 3. Eu(III) emission spectra of the thermodynamically stable cubic components of cerium and zirconium compounds and form
Ce-Zr-EuO2 (CZE) samples with the schematic representation of Eu precipitate in soluble precursors. After a series of process of
surface site located on the stable (111) surface of cubic Ce0.8Zr0.2O2 and separation, washing, drying and calcination, the final products
of the single Eu bulk site in Ce0.8Zr0.2O2 by EXAFS data. The details of are obtained. The reaction is as follows (Eqs. (1)–(4)):
5D→f7 F0 transition are reported for both surface and bulk Eu(III)-doped
Ce 3   3NH 3  H 2 O  Ce(OH ) 3   3NH 4 (1)
materials after different thermal treatments. (a) Surface-doped CZE
calcination at 500 °C for 5 h; (b) Surface-doped CZE calcination at 1000 Zr 4   4 NH 3  H 2 O  Zr(OH ) 4   4 NH 4 (2)
°C for 5 h; (c) Bulk-doped CZE calcination at 500 °C for 5 h; (d) 4Ce(OH) 3  O 2  2H 2 O  4Ce(OH) 4
Bulk-doped CZE calcination at 1000 °C for 5 h. Reprinted from [66] with (3)
permission. Ce(OH) 4  Zr(OH) 4   H 2 O  Ce(OH) 4  Zr(OH) 4   H 2O (4)
This method can make an excellent mixing of the different M-Ce0.7Zr0.3O2 (M = Li, Na, K) using a modified SG method. In
components. The surface area of CZO prepared by this tradi- the synthesis process, a proper amount of citric acid (CA) was
tional CP method is 20–120 m2/g, which would decrease to added to control the hydrolysis of precursors and then calcined
about 20 m2/g after being calcined at 1000 °C. Hsiang et al. [92] at 600 °C for 6 h to obtain the final products. The as-prepared
prepared Ce0.6Zr0.4O2 powders by the CP method and studied materials exhibited a higher catalytic activity for soot combus-
the correlation between the crystallite structure and reductive tion than that prepared by the CP method.
property. The results indicated that Ce0.6Zr0.4O2 decomposed
into Ce-rich (cubic) and Zr-rich (tetragonal) phases from a sin- 3.1.3. Template-assisted method
gle cubic phase after being calcined above 1100 °C. Moreover, The template-assisted method is widely employed for the
the cation diffusion may result in the structural alteration un- preparation of nanostructural CZO due to the advantages of
der reduction/re-oxidation treatment. In this synthesis process, convenience, simplicity and inducing effect of various tem-
because the precursors are made of hydroxides or salts of ce- plates with special structures or morphology. Two types of
rium and zirconium, a calcination process at high temperature templates are available as follows.
is needed to form solid solution. Nevertheless, high tempera- (a) Soft template
ture would lead to the loss of surface area seriously. Further- Surfactants can form micelles with different shape or mor-
more, during the drying process, the particles might aggregate phology when dissolved into water up to a certain concentra-
due to the effect of surface tension of water (or other solvents). tion, and thus the micelles can be used as templates for nano-
Therefore, a lot of improved ways were developed to enhance material synthesis. In recent years, numerous studies have
the property of nanosize CZO. Chen et al. [93] proposed a modi- been reported on the use of cationic, anionic and nonionic sur-
fied CP method with triethylamine assisting to prepare CZO factants as template to synthesize nanosize CZO with mesopo-
with a big surface area and high thermal stability. They found rous structure [96]. The commonly used surfactants are
that the adsorbed surfactant (triethylamine) on the surface of cetyltrimethylammonium bromide (CTAB) and tri-block co-
particles might form a protective layer, which could serve as an polymers Pluronic P123 and F127. Trovarelli et al. [89] pre-
effective barrier to inhibit the grains from aggregating. Conse- pared CZO with high surface area by a soft template-assisted
quently, the added surfactants could remarkably improve the approach. In a typical preparation process, the mixed oxide was
particle dispersion and increase the surface area of CZO. synthesized by adding an aqueous solution of the cationic sur-
factant CTAB to precursor solution made of hydroxides or salts
3.1.2. Sol-gel method of cerium and zirconium. Cationic surfactants effectively in-
The SG method is also widely used for nanosize CZO synthe- corporated into cerium and zirconium hydrous oxides under
sis. Metal compounds are mixed with the highly active coordi- basic conditions. The presence of cerium inhibited al-
nation compounds and undergo hydrolysis and condensation kyl-trimethyl-ammonium salt acting as the template to form
reaction to form sol and then transform to gel with three di- regular pore structure. The removal of surfactants after calci-
mension net-work structure. Final products are obtained after nation gave rise to the formation of fluorite-structured CZO
drying and calcination. Generally, SG synthesis is a suitable with high specific surface area. Yuan et al. [97] demonstrated a
method to prepare CZO with high degree of homogeneity by novel straightforward and reproducible method to prepare a
controlling hydrolysis of alkoxide or similar precursors. How- highly ordered mesoporous CZO with a 2-D hexagonal struc-
ever, when the rates of hydrolysis between the two metals are ture. The general synthesis strategy was based on an SG meth-
quite different, it may be difficult to simultaneously hydrolyze od combined with evaporation-induced self-assembly (EISA) in
both precursors, particularly when Zr(n-C3H7OH)4 is employed ethanol, and P123 was used as the template and ceric nitrate
as a precursor. Therefore, appropriate chemical modifications and zirconium oxide chloride as the precursors. A series of
of the hydrolyzing process are needed to control the rate of mesoporous CZO with different Ce/Zr ratios was obtained un-
hydrolysis. Meeyoo et al. [94] adopted an SG technique to pre- der the optimal temperature and humidity conditions.
pare Ce1-xZrxO2 (x = 0~1.0) mixed oxide catalysts for CO oxida- (b) Hard template
tion. The initial solution was synthesized by mixing 0.4 mol/L The ordinary hard templates contain porous anodic alumina
of urea solution with 0.1 mol/L of metal salt solutions with (AAO), molecular sieves, carbon nanotubes (CNTs) and silica
volumetric ratio equal to 0.5, and the ratio was changed de- nanowires. They can be used as rigid templates for nano-
pending on the desired solid solution. The catalytic activities of material synthesis. Zamani et al. [98] prepared mesoporous
these mixed oxide catalysts were found to be dependent on CZO using mesoporous silica (SBA-15 and KIT-6) as template
Ce/Zr ratio, and Ce0.75Zr0.25O2 exhibited the highest CO conver- agents, which were impregnated with precursor materials.
sion. Kozlov et al. [76] prepared an Al2O3-supported Structural analysis of the products confirmed the formation of
Ce0.45Zr0.55O2 catalyst by a modified SG method. In this prepara- mesostructures, and thermogravimetry measurements showed
tion process, 2-methyl-2,4-pentanediol was added to affect the the remarkable increase of material OSC compared with pure
substitution of the isopropoxy ligand by the diol. As a result, ceria. In the case of Ce0.95Zr0.05O2, response measurements
CZO exhibited a high content of readily reducible Ce4+. Addi- showed the relatively fast and stable response of the sensor to
tionally, the mixed oxide particles still retained small and ho- oxygen-containing atmospheres.
mogeneous single phase even after reduction at 980 °C and Some special structures require specific hard templates. The
reoxidation at 900 °C. Yu et al. [95] synthesized a series of three-dimensional ordered macroporous (3DOM) structure is
prepared via organic polymer templates such as polystyrene green chemistry process due to the very good control of
(PS), polymethyl methacrylate (PMMA), and polysty- volatizing of organic solvents, non-toxic gas releasing. And the
rene-methyl methacrylate-acrylic acid microspheres. Some synthesis can conveniently obtain the nanomaterials with reg-
works have been reported on this aspect [99–104]. Zhao et al. ular shape, size and crystallite phases. Walton et al. [106] re-
[102] prepared a series of 3DOM CZO using PMMA colloidal ported a simple one-step hydrothermal method for preparation
crystal as template agent, as shown in Fig. 4a. In a typical syn- of nanocrystallite CZO, whose redox properties depended cru-
thesis process, the first step was to prepare an ordered colloi- cially on the reaction conditions. Ihm et al. [107] fabricated CZO
dal crystal template (CCT) with monodispersed PMMA spheres by a continuous hydrothermal method in supercritical water.
(444 nm) and PS spheres (454 nm). The second step was to The supercritical synthesis led to CZO with better thermal sta-
synthesize the liquid precursor. The stoichiometric amount of bility and higher OSC than that synthesized by the CP method.
cerium nitrate and zirconium oxide chloride were dissolved in The solvothermal method is a direct and rapid method,
an mixed solvent including ethylene glycol (EG) and methanol which has been used for the synthesis of metal oxide nanopar-
(20–40 vol%) followed by pouring into a volumetric flask. ticles (NPs) for various applications [108,109]. Devaraju et al.
Then, the dried PMMA or PS colloidal crystal was soaked in the [110] adopted the solvothermal method under supercritical
solution for several hours. Excess solution was removed by and high autogenous pressure conditions (400 °C, 40 MPa) for
filtration. Finally, 3DOM CZO was obtained by removing the the direct preparation of nanocrystallite powders CZO, which
template via calcining at 650 °C for 5 h. The as-prepared exhibited a high OSC value.
Ce0.7Zr0.3O2 material exhibited a well-ordered 3DOM structure,
which consisted of interconnected networks of spherical voids 3.1.5. Solution combustion method
through open windows, ca. 120 nm in diameter, as shown in The SC method is simple and fast, and yields high surface
Fig. 4b and 4c. The walls of the macroporous samples were area products with desired composition. It is an attractive syn-
crystallited. thetic route especially for the preparation of multicomponent
oxide materials because the homogeneity of the aqueous solu-
3.1.4. Hydrothermal and solvothermal method tion of the salts is preserved in the combustion residue. The
The hydrothermal method refers to a synthesis route via materials prepared by this method not only possess better ho-
reaction of species in the water media (solvent) under the con- mogeneity and purity, but also have high surface areas. Reddy
dition of certain temperature (100–1000 °C) and pressure et al. [111] reported a single synthesis step of nanosize
(1–100 MPa). It is well known that CP and SG methods can be CeO2-MxOy mixed oxides (MxOy = SiO2, TiO2, ZrO2 and Al2O3) by
used to prepare catalytic materials of high purity. However, the the SC method. Among these samples, CeO2-SiO2 showed the
as-prepared materials usually show amorphous structures. highest surface area compared with other oxides. The decreas-
Hydrothermal synthesis can overcome this drawback and may ing order of specific surface areas was as follows: CeO2-SiO2
be regarded as an effective strategy for synthesis of specific (125 m2/g) > CeO2-TiO2 (79 m2/g) > CeO2-ZrO2 (56 m2/g) >
nanosize catalytic materials in liquid phase. This technique has CeO2-Al2O3 (38 m2/g). Chen et al. [112] prepared mesoporous
attracted more attention since the 1980s when nanoceria was CZO via a salt-assisted combustion method using EG as the fuel
first synthesized via a hydrothermal method by Matijevic et al. and nitrate as the oxidant, and the effect of added salt on the
[105]. In the solvothermal method, organic solvents are em- properties of the products was studied. The presence of salt led
ployed instead of water. The whole process of hydrothermal or to a more than 10-fold increase in the specific surface area of
solvothermal synthesis is controllable and can be regarded as a the products at a given molar ratio of EG/nitrate. It was owing
to that the instant salt in-situ precipitation inhibited the for-
mation of hard agglomerates and sintering of naonocrystallites.
Therefore, this method provided a novel and effective strategy
to tailor the material properties. Zhang et al. [113] synthesized
Ce0.6Zr0.4O2 solid solutions by CP, SG, SC and template-assisted
approaches. The catalytic activities of bulk and γ-Al2O3 sup-
ported Ce0.6Zr0.4O2 solid solutions were investigated for the
oxidation of soluble organic fractions from diesel engine ex-
hausts. Ce0.6Zr0.4O2 mixed oxide was active for lube oxidation.
Among these materials, the sample prepared by the SC method
showed the best catalytic activity due to the reservation of the
high surface area and small particle size.
3.1.6. Micro-emulsion method

Surface and interfacial catalysis plays a key role in the inte-
grated synthesis and construction of functional architectures
Fig. 4. (a) The schematic diagram for the preparation of 3DOM CZO by
the colloidal crystal template method; (b) SEM and (c) TEM images of a particularly for nanosize thin film due to the effect of surface
representative 3DOM Ce0.7Zr0.3O2. Inset: (b) an enlarged area of 3DOM tension and viscosity [114,115]. Zhou et al. [116] prepared five
Ce0.7Zr0.3O2, (c) the corresponding SAED pattern. types of CZO-modified Al2O3 (CZA) by SG, ME, CP with super-
critical drying (CPS), CP with common drying (CPC), and im-

pregnation (IM) methods and investigated the effect of prepa-
ration method on the properties of CZA. The results revealed
that CZA prepared by CPS and ME methods exhibited better
textural and structural properties as well as better reducibility,
which led to the higher catalytic activity and wider air-to-fuel
operation window of the corresponding Pd-only three-way
catalysts. Boutonnet et al. [117] adopted a novel and direct
approach for the preparation of inorganic NPs by an
oil-in-water (o/w) ME method, in contrast to the typical wa-
ter-in-oil ME method. As shown in Fig. 5, the strategy involves
the use of organometallic precursors, which are dissolved in oil
droplets in a nanometer scale (stabilized by surfactant) and
dispersed in a continuous aqueous phase.
3.1.7. Self-assembly method

The self-assembly method refers to structure units such as
molecules or NPs integrating spontaneously via non-covalent
bons to form aggregation with thermodynamically stable
structure. The driving force of this process contains the elec-
trostatic force, hydrogen bond, electronic effect, van der Waals Fig. 5. Strategies for the preparation of inorganic nanosize CZO by the
o/w microemulsion reaction approach. (a) Mixing two microemulsions
force, and space effect of functional groups [118]. The
of identical composition except for reactants A organometallic precur-
self-assembly materials are all with ordered structure and sor and B precipitating/reducing/oxidizing agent; (b) Using a micro-
morphology, and the formation process is according to the emulsion containing reactant A, and then directly adding reactant B.
principle that free energy should be minimized and without Reprinted from [117] with permission.
extra external force. Chane-Ching et al. [119] developed a
two-step self-assembly approach for the preparation of or- Gurav et al. [122] investigated the sonochemical synthesis of
dered 2-D or 3-D nanostructured materials with a large surface nanoporous ceria and CZO with high surface area via
area. Ceria NPs were functionalized by using the CH2CH2O high-intensity ultrasound irradiation. Zhang et al. [123] pre-
groups of the surfactant. According to the cooperative pared nanosize CZO with a very big surface area of 226 m2/g
self-assembly of colloidal NPs, hexagonal arrays of CeO2 were and average size about 3.7 nm by a sonochemical method in the
obtained and the symmetry of the arrays was maintained upon presence of polyethylene glycol (PEG). Moreover, its surface
heating up to 500 °C. Chou et al. [120] facilely synthesized a area and nanosize rarely changed after being calcined at 500 °C.
series of mesoporous CZO nanocrystallite with excellent ther- Recently, Nikitenko et al. [124] prepared Ce0.5Zr0.5O2 nanocrys-
mal stabilities through the EISA strategy. Fig. 6 exhibited the tallite mixed oxide with external mesopores using simultane-
orderedly mesoporous structure for as-prepared different ous sonohydrothermal treatment. The obtained material ex-
Ce/Zr ratio materials. hibited higher surface area than the similar material prepared
by an ultrasonically assisted CP method.
3.1.8. Sonochemical synthesis method
Sonochemical process has proved to be an effective method 3.1.9. Physical method
for the preparation of novel materials with unusual properties
[121]. Moreover, it is an environmentally friendly synthesis 3.1.9.1. High-energy milling
route for functional materials and may be a good approach that The high-energy milling method relies on the high pressure
can be used to synthesize nanoporous transition metal oxide and mechanic force to make particles with high density of lat-
solid solutions. Nevertheless, only a few studies on sonochemi- tice defects, and thus the as-prepared materials possess high
cal synthesis of multicomponent materials have been found. OSC. Trovarelli et al. [125] synthesized nanosize CZO via
Fig. 6. TEM images of Mn-CexZr1-xO2 with different Ce/Zr ratios by calcination at 600 °C. (a) Mn-Ce0.2Zr0.8O2; (b) Mn-Ce0.4Zr0.6O2; (c) Mn-Ce0.5Zr0.5O2.
Reprinted from [121] with permission.
high-energy milling, and ZrO2 was doped into fluorite structural CZO and (Ce0.7Zr0.3O2)x(Al2O3)1-x core-shell nanopowders by
CeO2 lattice when the milling speeds gradually increased. Re- LF-FSP using metallo-organic precursors Ce(O2CCH2CH3)3(OH),
cently, they successfully prepared CZO particles wrapped in a alumatrane N(CH2CH2O)3Al, and Zr(O2CCH2CH3)2(OH)2. The
2-D carbon envelope by high-energy milling of CZO powders as-prepared materials possessed mean particle size below 20
and soot, and the atomic ratio of metal-to-carbon increased nm and specific surface area of 30–50 m2/g and showed good
with more milling time. Consequently, the activation and catalytic activity for HC oxidation and deNOx reaction even
transfer of the oxygen in ceria were shifted to very low tem- without co-catalyst of noble metals.
peratures, which significantly boosted the soot combustion rate In addition, some other methods have also been developed
[126]. for cerium-zirconium based material synthesis, including su-
percritical anti-solvents [131,132], microwave-assisted method
3.1.9.2. Electrospinning method [133–136], electrochemical deposition [137–139], microwave
The electrospinning method is a cost-effective method for method [140], etc.
preparing electrospun fibers with high surface areas and ade-
quately small grain sizes, which are indispensible for good re- 3.1.11. Summary of synthesis methods for nanosize
ducibility and fast low-temperature reoxidation in solar-driven cerium-zirconium-based solid solutions
redox cycles. The high surface area of electrospun structures To date, a great variety of methods have been developed for
can accelerate the reoxidation surface kinetics at low tempera- the synthesis of nanosize CZO, and these methods have a great
ture and inhibit sintering at high reduction temperatures. Da- impact on the properties of materials, such as specific surface
vidson and Jackson prepared a series of CZO fibers with a uni- area, crystal phase, redox, OSC, and thermal stability, as listed
form diameter by a controlled electrospinning method [127]. in Table 1. The preparation of nanosize CZO usually involves
The electrospinning set-up was shown in Fig. 7. These CZO four steps: the synthesis of precursor, the pretreatment of pre-
fibers exhibited remarkable sinter-resistance, which main- cursor, the transformation of precursor into solid solutions,
tained their structure even after 108 redox cycles with reduc- and post-treatment of solid solutions. At present, the primary
tion at 1400 °C and oxidation with CO2 at 800 °C. It was higher preparation methods for nanosize CZO are CP, SG, surfac-
than those observed for other ceria-based materials conducting tant-assisted template, hydrothermal, SC, and ME methods, and
under similarly high temperature conditions. each of them possesses its feature and certain deficiencies.
The high energy ball milling method is highly costly and
3.1.10. Other methods time consuming, and the material prepared by this method
Liquid-feed flame spray pyrolysis (LF-FSP) is a facile meth- exhibits low specific surface area and OSC value. Thus, this
od which was developed in recent years for material synthesis. method is rarely employed to prepare nanosize CZO. Generally,
In this synthesis strategy, organometallic alcohol solutions are SG synthesis is a suitable method to prepare CZO with high
usually used and are aerosolized with oxygen and ignited. The degree of homogeneity by controlling the hydrolytic process of
combustion process produces flames up to 1500–2000 °C. If the precursor like alkoxide. However, it should be taken into
the combustion process derived metal oxide ions are quenched account that when the rates of hydrolysis between the two
rapidly enough, e.g., 1000 °C/ms, it is possible to prepare a metals are quite different, it may be difficult to simultaneously
large variety of unaggregated (easily dispersed) nanopowders hydrolyze the both precursors. Consequently, CZO prepared by
whose compositions are almost completely determined by the this method often exists split phase. But the homogeneity of
precursors in solution [128–130]. Kim et al. [128] synthesized CZO can be improved via suitable chemical modification or
adding certain solvent to control the hydrolysis rate of the both
precursors. The SC method is usually used to prepare
nanostructural CZO by burning Ce(NO3)3, ZrO(NO3)2, oxalyl
dihydrazide, and carbohydrazide. Its advantage is that the
samples possess high specific surface area, and the disad-
vantages are high cost, waste gas producing, and low OSC value.
The hydrothermal method is employed to prepare CeO2 and
ZrO2-containing materials, and CZO prepared by this method
under supercritical conditions shows good homogeneity, high
OSC value, and excellent thermal stability. However, its produc-
tion amount is very little. In general, the hydrothermal method
is used in laboratory and not industrialized yet. The CP method
is one of the common methods to prepare CZO. It uses a precip-
itant to transform soluble components into complex com-
Fig. 7. Fiber production via electrospinning set-up. (a) Wire coil spin-
pounds and the corresponding solid solution is obtained by
neret rotating through a bath of spinning solution, fibers on a rotating
wire drum collector; (b) Removal of the collected fibers from the wire separation, washing, drying, and roasting. Currently, the CP
drum, leaving a non-woven mat of polymer and ceramic precursor method is convenient for industrial production due to its sim-
fibers; (c) SEM image of the ceramic + precursor fibers. Reproduced ple process, controllable condition, cheap raw materials, and
from [127] with permission from the PCCP Owner Societies. low preparation cost. Nevertheless, high temperature calcina-
Table 1
Main characteristics of different synthesis methods for nanosize CZO materials.
Synthesis method Characteristics of the method Characteristics of the materials
Co-precipitation method Simple synthesis process, controllable condition, cheap raw An excellent mixing of the different components,
materials, and low preparation cost surface area 20–120 m2/g
Sol-gel method Mild synthetic conditions, but time consuming Existing split phase, but high surface area
Template-assisted method Convenience, simplicity and inducing effect of various tem- Controllable size, morphology and structure as well
plates with special structures or morphology as high surface area
Hydrothermal and solvothermal Direct and rapid, high temperature (100–1000 °C), high Homogeneous, high OSC and good thermal stability
method pressure (1–100 MPa)
Solution combustion method Simple, fast, but high cost and waste gas producing Uniform crystalline particle size and high surface
area but low OSC
Micro-emulsion method Especially for nanosize thin film Better textural and structural properties as well as
better redox behavior
Self-assembly method Cheap, fast, simple and convenient, but difficult to prepare Ordered structure and morphology
materials with complex structure
Sonochemical synthesis method Useful technique in the synthesis of novel materials with Remarkably high surface area
unusual properties and environmentally friendly synthesis
route for functional materials
High energy ball milling method High cost and time consuming Low surface area and OSC
Electrospinning method Cost-effective High surface areas and adequately small grain sizes
tion can induce a serious decrease of specific surface area of ising material in both fundamental research and application
solid solution. Moreover, when precipitation is performed in development due to its special properties. Especially, CZO na-
water, the particles size would aggregate and grow up in the nopowders have attracted much attention in recent years
process of drying owing to the effect of surface tension. There- [143,144]. They are synthesized mainly via CP, hydrothermal,
fore, the various preparation technologies for nanosize CZO and SG methods. Despite of many studies on the synthesis
material synthesis still need to be improved. technique of CZO nanopowders, it is still a tough issue to obtain
products with high stability and uniform size.
3.2. Morphology for nanosize cerium-zirconium-based solid To prepare nanopowders with high stability, surfactants are
solutions employed in synthesis processes to promote the dispersion of
precursors. PVP (polyvinylpyrrolidone) can be used in different
As is known to all, properties and functions of CZO materials dispersion systems as a stabilizer agent for preventing reaction
highly depend on their morphology and size. Hence, the con- product aggregation. Si et al. [145] used Ce(NO3)3·6H2O as
trollable synthesis of CZO with unique morphology is signifi- precursor and PVP as stabilizing agent in alcohol solution to
cantly important [141,142]. Meanwhile, CZO with nanometer prepare CeO2 colloidal particles with sizes of ca. 4 nm. Du et al.
size usually possesses high OSC value and specific surface are- [146] used CTAB as template to induce the assembly of
as, which can greatly enhance the catalytic activity. Nanopow- Ce0.7Zr0.3O2 nanopowders via the CP method. Under the condi-
ders and one-dimensional (1-D) nanostructure nowadays have tion of plenitudinous reaction and aging time, CZO with a pure
been the most popular realm of synthesis of ceri- crystal phase was obtained. The as-prepared material pos-
um-zirconium-based materials, including nanowires, nanobelts, sessed an average size of 15 nm, pore diameter of 2–4 nm, and
nanorods, and nanotubes. Moreover, nanoplates, nanodisks, specific surface area of 179 m2/g and showed high stability. Liu
linearly-mesoporous structure (two-dimensional, 2-D), and et al. [147] prepared a series of Ce-Zr-Pr nanopowder oxide
nanocages, or 3-D mesoporous or macroporous structure catalysts via uniting solution-combustion and rotating evapo-
(three-dimensional, 3-D) and various specific morphology of ration techniques. The catalysts exhibited a cubic fluorite
CZO have also arouse the interests of researchers. CZO can be structure with particle sizes in the range of 6–8 nm. Darr et al.
divided into five categories according to the different mor- [143] prepared La- and Y- doped nanosize CZO with different
phology: nanopowders, 1-D, 2-D, 3-D, and other morphology compositions by a hydrothermal method. Both samples
such as core-shell structure, as shown in Table 2. showed an average particle size of 4.5 nm. For nanopowder
synthesis, the raw material utilization is usually inefficient and
3.2.1. Nanopowders the process of preparation may also be not environmentally
Nanopowder is an important part of the nanomaterial fami- friendly. Thus, seeking for the efficient and comfortable synthe-
ly, which is composed of NPs with the size of 1–100 nm. Na- sis of CZO nanopowders of regular morphology with high sta-
nopowder is a transition state between atoms (or molecules) bility and activity is an imperative issue.
and macroscopic objects. The quantitative change of NPs may
lead to the remarkable change of material properties. In fact, 3.2.2. 1-D cerium-zirconium-based solid solutions
the crystal symmetry, space lattice, defects, dislocations, and
crystal boundaries of macroscopic objects have been deeply 3.2.2.1. Nanowires, nanobelts, and nanofibers
and systematically investigated. Nanopowders may be a prom- Nanowires, nanobelts, and nanofibers are 1-D nanostuc-
Table 2
Main characteristics and synthesis methods of nanosize CZO materials with the different morphology.
Morphology Synthesis method Characteristics
0-D nanomaterials Nanopowders Co-precipitation, hydrothermal and sol-gel method Particle sizes of 1–100 nm
1-D nanomaterials Nanowires Sol-gel, hydrothermal method Ultrasmall diameter of ~1 nm and a length of 70 nm
Nanobelts Electrochemical deposition Ultrathin
Nanofibers Electrospinning, hydrothermal, co-precipitation, Uniform size from 300–400 nm in length
Nanorods Template-assisted method hydrothermal (sol- 10–40 nm in diameter and 30 nm to 2 μm in length
vothermal), ME, template-assisted method
Nanotubes Template-assisted and hydrothermal method; ~15 nm in wall thicknesses and 100 nm to 8 μm in
length, high surface areas
2-D nanomaterials Thin film One-step, sol-gel, template assisted hydrothermal Highly thermal stability
method
3-D nanomaterials Nanocages Hydrolysis process Controlled shapes, sizes and high surface areas
Mesoporous materials Self-assembly, co-precipitation, hydrothermal High surface area and special porous structure
synthesis and hard template method
Macroporous materialsTemplate-assisted method Ordered macroporous materials with controlled pore
size
Hierarchically porous Dual-template assisted colloidal crystal templating High surface area, controllable composition, thermal
materials method and chemical stability, high porosity
Other nanomaterials Flower-like Electrodepositon and template-assisted hydro- Flexibility in controlling the sizes, shapes, and com-
nanostructures thermal method positions
Core-shell structure Sol-gel and chemical deposition method
tures, but studies on the morphology of CZO materials are not Shen et al. [152] prepared Ce1-xZrxO2 (0 ≤ x ≤ 0.2) nanorods with
sufficient compared with nanopowders. Despite of this, some an average length of ~40 nm and a mean diameter of ~8 nm by
work has been reported. Song et al. [148] prepared CZO nano- an aqueous-phase CP method. The reaction was under the con-
fibers via an electrospinning technique. In this process, P123 ditions of 95 °C in the solvent media and lasted for 8 h. Lee et al.
and polyethylene oxide (PEO) were used as co-template agents [153] employed a two-step route under hydrothermal condi-
and ceric nitrate and zirconium nitrate as precursors. P123 and tions and prepared CZO nanorods with average diameter and
PEO mixture allowed the formation of microphase domains length in a range from 20–30 to 100–200 nm, respectively. Shi
during the electrospinning process. A handful of PVP was also and Zhang et al. [154] designed the synthesis of MnOm/CZO
introduced to control the viscosity of the composite solutions nanomaterials and investigated the effect of the morphology of
for better electrospinning. The as-prepared material has a uni- CZO on the catalytic activity of MnOm/CZO for the SCR of NO
form size of 300–400 nm in length. Li et al. [149] synthesized with NH3. Three different shapes of CZO nanomaterials such as
ceria-based nanobelts by electrochemical deposition on Cu nanorods, nanocubes, and nanopolyhedra were prepared by a
substrates. The surface morphology was highly dependent on hydrothermal method and the temperature was maintained at
the additive and current density of electrochemical deposition, 100 °C for nanorods. Zhang et al. [155] prepared
and this method could be applied to prepare other nanosize Ce0.9Zr0.1O2-supported manganese oxides (MnOm) nanorods
rare earth oxide materials. Hyeon et al. [150] fabricated ceria through a hydrothermal method with the reactants at 100 °C
nanowires with a length of 71 nm and an ultrasmall diameter of for 24 h. TEM images in Fig. 8 showed Ce0.9Zr0.1O2 nanorods
1.2 nm by a nonhydrolytic sol-gel method. During the thermol- with a length range of 15–90 nm and a uniform diameter (11 ±
ysis of the precursor complexes, the selective adsorption of 3 nm).
capping ligand onto particular crystallographic facets was im- Many metal-doped CZO samples were also investigated by
portant for the formation of ultrathin nanowires, whose lengths researchers. Dai et al. [156] prepared Ce0.6Zr0.3Y0.1O2 (CZY)
were tunable by altering the amount of oleylamine. This strat- solid solution nanorods with cubic fluorite structure by adopt-
egy is effective in adjusting the length/diameter ratio of nan- ing the strategy of CTAB-assisted hydrothermal treatment at
owires. 120 and 160 °C for 72 h. Fig. 9 shows that both samples exhib-
ited a rodlike shape with length variation from 30 nm to 2 μm
3.2.2.2. Nanorods and uniform diameters of ~10 nm, and the samples contained
A number of pure CeO2 nanorods have been synthesized via some irregular NPs. Yan et al. [157] synthesized monodisperse
hydrothermal (solvothermal), ME, template-assisted, and and large-scale Pr-doped ceria nanorods by combination of
chemical vapor deposition methods. However, compared with low-temperature aging and high-temperature precipitation
the synthesis of CeO2 nanorods, CZO nanorods are more diffi- without further sintering. The morphology of the products was
cult to fabricate. Du et al. [151] synthesized nanorod-like 400 nm in length and 30 nm in diameter, and Pr-doped ceria
Ce0.7Zr0.3O2 solid solutions by a sodium dodecyl sulfate-assisted nanorods exhibited relatively high specific surface area (153
precipitation method. Typical Ce0.7Zr0.3O2 nanorods were 450 m2/g).
nm in length and 40 nm in average diameter, with specific sur-
face area and OSC of 194 m2/g and 374 μmol/g, respectively. 3.2.2.3. Nanotubes
Fig. 8. TEM images of (a) Ce0.9Zr0.1O2 and (b) MnOm/Ce0.9Zr0.1O2 nano- Fig. 10. SEM images of (a, b) Ce0.5Zr0.5O2, (c–f) Ce0.7Zr0.3O2, and (g–i)
rods. HRTEM image (c) and EDS pattern (d) of MnOm/Ce0.9Zr0.1O2 na- Ce0.9Zr0.1O2 at low magnification, showing the high yield of nanotubes;
norods. Reprinted from [155] with permission. at intermediate magnification, showing the structure of individual
nanotubes, including several tubes viewed end-on; and at high magni-
fication, showing the nanoparticulate nature of the nanotube walls.
Reprinted from [161] with permission.
m2/g in specific surface area. Moreover, the nanotubes pos-

sessed inner diameter ranging from 30 to 50 nm, and wall
thickness was about 15 nm.
3.2.3. 2-D cerium-zirconium-based solid solutions

Sanchez et al. [163] prepared a highly linearly mesoporous
CZO thin film with 2–4 nm pores by a one-step method. This
Fig. 9. SEM (a,d) and HRTEM (b,c,e,f) images as well as their SAED pat- kind of material exhibited highly thermal stability, which still
terns (insets) of (a–c) CZY-CTAB-120 and (d–f) CZY-CTAB-160. Re- retained their structural integrity even after crystallization and
printed from [156] with permission. thermal treatment at 700 °C. Niklasson et al. [164] fabricated
CZO films by the SG method. Cerium nitrite together with zir-
Nanotube research has become a hot spot in the material conium oxychloride was dissolved in ethanol to prepare pre-
science field because of several reasons [158–160]. First of all, cursor solutions. Veszelei et al. [165] prepared CZO films by
nanotubes with sufficient small dimensions possess high spe- reactive direct current magnetron cosputtering. The films could
cific surface areas, good atomic efficiencies, rapid response to remain completely transparent under repeated Li+ and electron
reaction conditions, and high activities in catalyst systems. insertion/extraction and were, therefore, of much interest as
Secondly, the tubular nanostructure may endow itself addi- counter electrodes in transparent optoionic devices such as
tional advantages, such as high thermal and chemical and smart window. Brezesinski et al. [166] synthesized mesostruc-
structural stability. Finally, these structures may lead to com- tural thin films of CZO using a novel type of amphiphilic block
pletely new applications in nanotechnology, for example, if the copolymer as template, and the films possessed highly crystal-
nanotubes can be aligned. CZO nanotubes can be prepared via lited pore walls and ordered arrays of mesopores. Zelcer et al.
template (CNTs, polycarbonate, etc.)-assisted and hydrother- [167] adopted a straightforward and reproducible way to pre-
mal methods. Fuentes and Baker et al. [161] synthesized CZO pare CexZr1-xO2 (0 ≤ x ≤ 0.5) thin films with linearly mesoporous
nanotubes with CeO2 contents of 50 mol%, 70 mol%, and 90 structure. Zr(PrO)4 and CeCl3·7H2O were used as the inorganic
mol% using polycarbonate membrane with pore diameter of sources, acetylacetone as stabilizing agent, and F127 as pore
800 nm as template. The obtained nanotubes were 1–8 μm in template. Janek et al. [168] reported a series of ordered meso-
length, 500 nm in diameter, and 20 nm in wall thicknesses, as porous thin films of CZO with 17 nm diameter pores and nano-
shown in Fig. 10. Lee et al. [162] prepared zirconium-doped crystallite walls. The mesoporous oxide films were thermally
ceria nanotubes by mixing Ce(NO3)3·6H2O and zirconium diox- stable and still kept their structure up to 600 °C.
ide powder in NaOH solution under hydrothermal conditions. Dai et al. [156] synthesized a bowknot-like Ce0.6Zr0.3Y0.1O2
The influence of zirconium on the growth of ceria nanotubes entity, consisting of a variety of nano- and microslices with 2–6
was also investigated, and the Kirkendall effect would affect the µm in width and 5–10 µm in length, by adopting the strategy of
formation of nanotube structure. They reported a straightfor- P123-assisted hydrothermal treatment. These nano- and mi-
ward synthesis method of CZO nanotubes with high yield, sev- croslices were aligned along the reverse orientation of the cen-
eral hundred nm in length, ~52 nm in average pore size, and 76 ter of the microbowknot, forming rather coarse surfaces of the
ends of a microbowknot. area after calcination at 500 °C was in the range of 78–113
m2/g. Other nanocasting techniques have also been reported
3.2.4. 3-D cerium-zirconium-based solid solutions that siliceous KIT-6 was employed as the template [177]. As
expected, relatively high surface area was achieved (> 163
3.2.4.1. Nanocages m2/g) despite of high calcination temperatures for example
CZO nanocages may exhibit excellent catalytic performance 550 °C. And the aging temperature of the siliceous template
owing to the special morphology and may be also employed as was of importance because it was directly related to both the
novel nanoreactors due to the hollow structure. Li et al. [169] pore size and specific surface area of the target materials. The
fabricated monodisperse CeO2 spheres via a hydrolysis process, as-prepared 3-D mesoporous CZO was used for the complete
which then were employed as precursors and reacted with oxidation of naphthalene and exhibited higher catalytic activity
zirconium(IV) to prepare CZO nanocages with controlled com- than CeO2. Additionally, these mesoporous CZO oxides also
positions, sizes, and shapes according to a modified Kirkendall demonstrated a high stability. Lu et al. [178] synthesized mes-
effect. Fig. 11 exhibited that the materials showed a special oporous Ce0.6Zr0.4O2 solid solution via combining CP and
nanocage morphology which possessed high surface areas of self-assembly methods. Thereupon, the solid solution consisted
142 m2/g for nearly cubic nanocages, and 183 m2/g for spheri- of homogeneous nanocrystals with uniform mesopores of ca. 4
cal nanocages, respectively. Xu and Huang et al. [170] prepared nm and showed highly thermal stability. Moreover, different
the uniform monodisperse CZO nanocages with an apparent surfactants had little influence on the mesoporous structures.
interior void. The diameters of the nanocages were about Although many methods are developed, further research is still
80–100 nm. needed, which should be concentrated on how to improve the
mesopore regularity and raise the tolerated maximum temper-
3.2.4.2. 3-D mesoporous cerium-zirconium-based solid solutions ature.
Nanocrystallite structured materials are desired in the prac-
tical applications due to their high surface area and special 3.2.4.3. Macroporous cerium-zirconium-based solid solutions
porous structure. 3-D mesoporous materials with high specific 3DOM materials have attracted much attention because of
surface area, highly ordered channels, and narrow pore size their peculiar structure and wide application in photonic crys-
distribution have provoked intensive interest, thus widespread tal, catalysis, and separation science. To date, the main tech-
application on catalysis. 3-D mesoporous Ce-based materials nique for 3DOM material synthesis is the template-assisted
were reported in the 1990s. This material shows a broad ar- method. Colloidal crystals are usually used to prepare ordered
rangement of mesopores in the region of 2–8 nm with an opti- macroporous materials with controlled pore size. Li et al.
mal value at around 3.5–4.0 nm, and surfactants are signifi- [179,180] employed PS microspheres as templates and CA as
cantly important to obtain high surface area mesoporous ceria complexing agent to prepare 3DOM CeO2 via the SG method and
because they can lower the surface tension of water in the reported the synthesis of 3DOM ZrO2 by two steps. They pre-
pores during drying [171]. Many methods were developed to pared 3DOM carbon framework by using SiO2 as templates, and
synthesize mesoporous ceria and CZO with crystallite frame- then ZrOCl2 was impregnated on the carbon framework. The
work, including self-assembly [97,172], direct hydrothermal final 3DOM product was obtained after the removal of carbon
synthesis [173], and hard-template assisted method [174,175]. framework under a high-temperature condition.
Deshpande et al. [176] synthesized a series of CZO beads via Zhao et al. [99–102,181–184] carried out research on CZO
a nanocasting approach by employing commercially available with 3DOM morphology. 3DOM CZO was synthesized by the
PS beads as templates. The as-prepared materials offered ad- CCT method using EG-methanol solution of Ce(NO3)3·6H2O and
vantages of ease of handling and recovery and good flow prop- ZrOCl2·8H2O as precursor solution. To obtain 3DOM metal ox-
erties. Moreover, the materials retained a high compositional ides, the solidification of these salts was necessary before the
homogeneity even after thermal treatment, and the surface removal of PMMA. The heteropolynuclear complex containing
cerium and zirconium ions using EG-methanol solution as sol-
vent was formed at low temperature during the dry process,
indicating that the solidification of the two salts occurred. The
inorganic precursors were introduced to CCT and permeated
the voids between the close-packed spheres, and condensed
into a hard inorganic framework upon drying. After removal of
excessive liquid, drying at room temperature for 12 h, and cal-
cination at 550 °C for 5 h, a 3DOM CZO material possessing
perfect crystal phase was obtained.
3.2.4.4. Hierarchically porous cerium-zirconium-based solid

solutions
Fig. 11. (a-c) TEM images of spherical CZO nanocages with different Arandiyan et al. [185] reported a facile dual-template syn-
magnifications, (d-f) TEM images of nearly cubic-like CZO nanocages thesis of Pt NPs supported on 3DOM-structured Ce0.6Zr0.3Y0.1O2
with different magnifications. Reprinted from [169] with permission. (3DOM CZY) with nanovoid-like or mesoporous skeletons. It
was based on the use of a CTAB-assisted gas bubbling reduc-

tion route with H2PtCl6/NaBH4 and P123 as soft template and
well-arrayed colloidal crystal PMMA microspheres as hard
template to generate a 3DOM structure, as shown in Fig. 12.
Pt/3DOM CZY catalysts possessed great utility because of their
high surface area, diverse composition, crystallinity, thermal
and chemical stability, high porosity, and uniform pore size
distribution as well as their excellent catalytic performance for
CH4 combustion. Huang et al. [186] synthesized hierarchical
CZO nanospheres with an outer diameter of about 90 nm by a
modified approach (Kirkendall effect). The nanospheres Fig. 13. SEM images of CZO flower-like nanostructures prepared in
solution of 0.02 mol/L Ce(NO3)3 + 0.005 mol/L Zr(NO3)4 + 0.1 mol/L
showed uniform and monodisperse characteristic, which could
NH4NO3 with current density of 2 mA/cm2. Reprinted from [189] with
be employed as effective adsorbents for arsenic removal. Yu et permission.
al. [187] developed a series of high-efficiency Pd/CexZr1-xO2 (x =
0.2–0.8) catalysts with mesoporous structures and macro-
channels by a combined surfactant and CCT method. The products included rods, spheres, bowknot-like shape, and oc-
non-interconnected macrochannels have a length of 20–60 mm tahedral shape.
and diameter of 1–2 mm. The high-magnification SEM images Core-shell structure nanosize CZO is a good material for ion
revealed that the walls of these macro-channels derived from conductivity. In order to introduce more conductive interfaces,
the packing of fine particles. The intraparticle spacing was re- Li et al. [190] synthesized the doped CZO core-shell nanocom-
lated well to the mesopores in the product and hence both posites via a simple and cost-saving SG method. Nitrates, CA,
macro and meso-textural structures coexisted in the system. and PEG were used as the starting materials, and the composi-
Wei et al. [188] innovatively fabricated a series of 3-D ordered tions of the core and the shell parts were Ce0.9Gd0.1O1.95 and 8
meso-macroporous PdCo/CZO catalysts by a combined CCT mol% Sc2O3-doped ZrO2, respectively. The grain size of core
and EISA method, in which F127 and PMMA were used as and shell was 6 and 8 nm, respectively. The core-shell
mesopore and macropore templates, respectively. The result- nanostructure contained about 60 nm diameter core and about
ing catalysts show ~240 nm in macropore diameter and ~5 nm 20 nm thick shell. Ozawa et al. [191] prepared core-shell type
in mesopore. CZO support by precipitation of CeO2 NPs followed by heat
treatment at 800 °C on pure zirconia surface. Li et al. [169]
3.2.5. Other morphology prepared CeO2@CZO nanocages with different morphology by
The other special morphology has been successfully synthe- Kirkendall effect using the colloid ceria clusters as both chemi-
sized and studied, such as flower-like, bowknot-like, core-shell cal precursors and physical templates. This approach showed
and so on. This greatly broadened the application area of na- great flexibility in controlling the compositions, shapes, and
nosize CZO materials. Li et al. [189] synthesized CZO flower-like sizes of the solid solution.
nanostructures via the electrochemical deposition technique.
By tailoring the electrodepositon conditions, various CZO flow- 3.2.6. Summary of cerium-zirconium-based material with
er-like structures were readily prepared, as shown in Fig. 13. different morphology
CZO may be greatly influenced by different surfactants used. To date, nanosize cerium-zirconium-based materials with
Zhang et al. [156] prepared a series of CZY with different mor- ordered space morphology have attracted much attention due
phology via hydrothermal treatment, in which P123 or CTAB to their special and remarkable physicochemical properties in
surfactants were employed and the reaction time and temper- different areas. The ordered morphology includes nanopow-
ature were regulated. The morphology of the as-prepared ders, 1-D nanorods, nanotubes, nanobelts, nanowires and 2-D
nanofilms, nanomembranes, nanopaltes and 3-D nanocages,
3-D mesoporous, macroporous and hierarchical pores. In addi-
tion, many other special morphologies have been reported, and
the synthesis routes and techniques are also different. Based on
the nanosize morphology, space ordered structures for CZO
materials have been developed for different applications. CZO
materials have been widely used in heterogeneous catalysis
because of their remarkable redox properties. However, as for
the research of CZO materials with different morphology, some
work should be still improved: (a) stability and mechanic
strength of the as-synthesized materials; (b) environmentally
friendly synthesis route exploring; (c) morphology dependence
Fig. 12. SEM images of 3DOM CZY support and y% Pt/3DOM CZY and
Bulk CZY catalysts. (a) PMMA colloidal crystal; (b) 3DOM CZY; (c) factors, such as reaction time, temperature, pH value, concen-
3DOM CZY; (d) 0.6% Pt/3DOM CZY; (e) 0.6% Pt/3DOM CZY; (f) 0.6% tration of cerium and zirconium source, raw material configu-
Pt/3DOM CZY. Reprinted from [185] with permission. ration, metal doping, etc; (d) physicochemical properties of
CZO nanomaterials with different morphologies; (e) correlation [197–200]. Therefore, a great amount of work has been devot-
among structures, morphologies, and catalytic performance of ed to this aspect, as summarized in Table 3.
CZO nanomaterials.
4.1.1.1. Effect of the material composition
4. Cerium-zirconium-based solid solutions for The different Ce/Zr ratios markedly affect the catalytic ac-
heterogeneous catalytic reactions tivity of CO oxidation over CZO catalysts. Meeyoo et al. [94]
found that CO oxidation activity was strongly dependent on
4.1. Cerium-zirconium-based solid solutions for catalytic Ce/Zr ratio because of the difference in phase compositions of
oxidation of environmental pollutants the mixed oxides. The cubic fluorite structure mainly existed in
Ce1-xZrxO2 (where x < 0.5) and tetragonal phase was found in
CZO is a common active component used for the prepara- Ce1-xZrxO2 (where x > 0.5). The former phase could be reduced
tion of automotive exhaust TWCs catalysts for oxidation and easily than the latter one. Trovarelli et al. [201] proposed that
reduction of combustion byproducts. CO, NOx, and uncombust- the catalytic activities of CZO were dependent on textural
ed HC can be transformed into environmentally friendly forms properties and composition of samples. The rate of CO2 for-
by tailoring their oxidation states. CZO serves as an ‘oxygen mation under stationary conditions was almost proportional to
reservoir’ in which concurrent oxidation/reduction reactions the amount of ceria, whereas, under cyclic feed stream condi-
take place, either removing oxygen to create oxygen vacancies tions the rate reached a maximum when CeO2 was within the
or storing it to fill the vacancies in the solid material. In most range of 50 mol%–80 mol%. Zhao et al. [202] reported that the
cases, CZO porous solid is supported with metal NPs (Cu, Ag, zirconium-doped CeO2-supported cobalt catalysts were more
Au, Pt, Pd), which can promote oxygen transport into and out of active than the pure CeO2 and ZrO2-supported cobalt ones
the ‘reservoir’. For CZO-supported metal catalysts, factors such (Co3O4/CeO2 and Co3O4/ZrO2). When the ratio was 0.85–0.95,
as metal type, CZO particle size, Ce/Zr ratio, pretreatment con- especially 0.85, the Co3O4/Ce0.85Zr0.15O2 catalyst exhibited much
ditions, preparation method, dopants, and choice of the support higher catalytic activity than the others.
may affect the catalytic activities of the final catalysts Reddy et al. [203] investigated the effect of Tb, Pr, and Hf
[192–196]. dopant cations on the structure and catalytic properties of na-
nosize CZO-supported Pd catalysts for CO oxidation. They
4.1.1. CO oxidation found that CO oxidation activity strongly relied on the nature of
Although CO oxidation is a conceptually simple reaction, it is the dopant cations, and Pr cation incorporating CZO exhibited
very important to meet the rigorous environmental regula- the best activity when being calcined at 800 °C. The catalytic
tions. It is also a vital reaction occurring in the preferential oxi- activity was closely related to the redox couples Pr4+/Pr3+ and
dation of CO (CO-PROX) in a hydrogen purification system calcination temperature.
connected to polymer electrolyte membrane fuel cells Ayastuy et al. [204] investigated CexZr1-xO2 (x = 0–1.0) sup-
Table 3
Catalytic activities of nanosize CZO materials for CO oxidation.
Catalyst Particle size (nm) BET area (m2/g) Reaction conditions T50 (°C) Ref.
CeO2 — 10 2.0% O2 + 4.0% CO (100 mL/min, 0.08 g sample) 311 [201]
Ce0.5Zr0.5O2 4.7 84 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 421 [203]
Ce0.75Zr0.25O2 9–10 9.6 1.0% O2 + 1.0% CO (50 mL/min, 0.1 g sample) 355 [103]
Ce0.5Zr0.3Hf0.2O2 3.3 86 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 384 [203]
Ce0.5Zr0.3Pr0.2O2 3.5 88 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 364 [203]
Ce0.5Zr0.3Tb0.2O2 3.2 92 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 355 [203]
Ce0.67Zr0.33O2-Al2O3 4.0 146 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 387 [206]
Ce0.67Zr0.33O2-TiO2 3.7 105 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 392 [206]
Ce0.67Zr0.33O2-SiO2 3.1 172 10.2% O2 + 9.98% CO (50 mL/min, 0.1 g sample) 507 [206]
7% CuO/CeO2 6–7.9 150 1.0% O2 + 1.0% CO (200 mL/min, 0.1 g sample) 88 [204]
5% CuO/Ce0.5Zr0.5O2 6–8 169 3.3% O2 + 2.0% CO + 50% H2 (30 mL/min, 0.1 g sample) 89 [207]
7% CuO/Ce0.8Zr0.2O2 6–7.9 90 1.0% O2 + 1.0% CO (200 mL/min, 0.1 g sample) 102 [204]
7% CuO/Ce0.9Zr0.1O2 — 78 1.0% O2 + 1.0% CO + 50% H2 (30 mL/min, 0.1 g sample) 62 [205]
8% Co3O4/Ce0.85Zr0.15O2 5.4–6.1 1.0% O2 + 1.0% CO + 50% H2 (50 mL/min, 0.2 g sample) 135 [202]
16% Co3O4/Ce0.85Zr0.15O2 5.4–6.1 1.0% O2 + 1.0% CO + 50% H2 (50 mL/min, 0.2 g sample) 119 [205]
20% Co3O4/meso-Ce0.85Zr0.15O2 6.8 85 1.0% O2 + 1.0% CO + 50% H2 (50 mL/min, 0.1 g sample) 108 [208]
0.8% Pd/meso-macro-Ce0.6Zr0.4O2 7.6 69 20% O2 + 1.0% CO + 50% H2 (50 mL/min, 0.2 g sample) 65 [187]
T50 is denoted as temperature corresponding to 50% CO conversion.
ported copper oxide catalysts for CO oxidation and found that structural defects, larger surface area (181 m2/g) and better
the catalytic activity of this system depended on the amount of chemical homogeneity. Zhang et al. [208] prepared a series of
active sites located at the copper-ceria interface, which de- Co3O4/meso-CexZr1-xO2 (x = 0.75–1.0) catalysts using cationic
creased with increasing of ZrO2 loading amounts particularly surfactant CTAB and anionic surfactant ammonium do-
for ZrO2 > 50%. The optimum activity in CO oxidation was ob- decylbenzenesulfonate as structure-directing agent.
served for the CuO/CeO2 catalyst. Linear correlations were Co3O4/meso-Ce0.85Zr0.15O2 catalysts showed an outstanding
found for ceria-containing catalysts between pre-exponential catalytic activity for CO-PROX reaction. Moreover, compared to
factor and surface Ce/Cu ratio, and a compensation effect also the conventional Co3O4/CZO catalysts with the same composi-
exhibited between pre-exponential factor and Ea, as displayed tion [202], Co3O4/meso-CZO with orderly mesoporous archi-
in Fig. 14. Chen et al. [205] prepared a series of CuO/CexZr1-xO2 tecture displayed higher CO oxidation activity and CO2 selectiv-
(x = 0.1–0.5) catalysts for CO oxidation. The catalytic activity for ity, which should be due to the presence of mesoporous struc-
CO oxidation increased with the decrease of the amount of in- ture affecting the cobalt oxide dispersion and redox behavior of
corporating Zr4+, and 7% CuO/Ce0.9Zr0.1O2 exhibited the best catalyst. Yu et al. [187] reported a series of meso- and
catalytic activity. macroporous Pd/CexZr1-xO2 (x = 0.2–0.8) catalysts using the
It is reported that the catalytic activity of CZO is strongly in- surfactant template-assisted method. The me-
fluenced by the crystal structure, defects and Ce content, the so-macrostructural Pd/CexZr1-xO2 showed a higher CO oxida-
degree of reducibility, and the mobility of oxygen in the bulk. tion activity than that with mesochannel structures and the one
Despite all these implications, inadequate textural/structural prepared by the CP method due to the high homogeneity of
stability and mechanical strength and fall of specific surface crystal phase, more oxygen vacancies available, and large spe-
area at high temperatures are some problems encountered in cific surface area.
the case of unsupported CZO, because many applications re-
quire high temperatures. Stabilization of CZO on an inert sup- 4.1.1.3. Mechanism of CO oxidation over ceria-zirconium-based
port to form stable and active catalysts is an effective way to solid solutions
overcome these drawbacks. Reddy et al. [206] synthesized CZO Liu et al. [209] reported that Zr was not effective for CO ox-
dispersed over Al2O3, SiO2, and TiO2 by the CP method and idation reaction. Yang et al. [210] and Tang et al. [211] revealed
studied the influence of various supports on the thermal stabil- that Zr had almost no influence on the electronic structure of
ity, OSC, and CO oxidation activity. Al2O3-supported CZO ceria. Therefore, CeO2 has been widely used to represent CZO
showed the best performance, followed by TiO2- and for simplicity to investigate the reaction mechanism that CO
SiO2-supported systems. The OSC properties exhibited a strong oxidation involved. A detailed CO oxidation mechanism over
influence on the catalytic performances of ceria-based nano- CZO was proposed by Trovarelli et al. [212]. It is supposed that
composite oxides for CO oxidation. CO2 chemisorption should be statistically favored on CeO2 ra-
ther than on CZO mixed oxides due to its more Ce3+ sites. In
4.1.1.2. Effect of the pore structure fact, ZrO2 can only weakly adsorb CO or CO2 and usually is not
The different pore structure of CZO affects the dispersion of capable of forming stable carbonates. Moreover, preferential
active species of reactant molecules and the diffusion. Luo et al. adsorption on pure CeO2 could also be dependent on the prop-
[207] synthesized a series of mesoporous CuO/CZO catalysts to erties of the adsorption sites. Furthermore, it was reported that
be investigated for CO oxidation. Mesoporous CuO/CZO was the most stable surface for polycrystallite high surface area
much more active than non-mesoporous CuO/CZO in CO oxida- ceria was (111) among the three low index surfaces, namely
tion because of its higher oxygen vacancy concentration and CeO2 (111), (110), and (100). After reduction this surface re-
Fig. 14. (A) Linear dependency of lnA0 with catalyst composition (Ce/Cu ratio); (B) Constable-Cremer plot for CO oxidation over CuO/CexZr1−xO2 cata-
lysts. Reprinted from [204] with permission.
laxed with a vacancy association mechanism. This mechanism applications where NO oxidation to NO2 must be accomplished
could account for highly unsaturated sites onto which CO2 [215].
would be preferentially adsorbed. Vacancy association had
lower probability to occur in CZO due to the higher mobility 4.1.2.1. Effect of the support composition
resulting from the addition of a smaller cation in the lattice. Among the various physicochemical properties, the surface
Finally, zirconia could stabilize other surfaces with reactivity composition appears to be the most relevant one influencing
characteristics different from those of the (111) plane. The the NO oxidation capacity of CZO. García-García et al. [216]
following five steps were proposed to account for CO oxidation prepared two CZO with a ceria-rich and zirconia-rich surface,
reaction (Eqs. (5) –(9)): respectively. They found that the phase composition seemed
CO (g )  2CeO 2  CO 2(g )  2CeO1.5 not to be the direct factor affecting the catalytic activity for NO
(5)
CO ( g )  2CeO 2  CO 2(s)   2CeO1.5 oxidation (as shown in Fig. 15), and that the formation of a
(6)
proper solid solution prevented important surface segregation
O 2(g )  CeO1.5  (O 2 ) ads  CeO1.5
(7) of Zr upon calcination at high temperature.
(O 2 ) ads  2O ads
(8) Zhong et al. [217] reported Cr/CZO NPs with nonuniform
CO 2(S)  2O ads  4CeO1.5  CO 2(g )  4CeO 2 dopant concentration of Ce and Cr enriched on the surface as
(9)
Among which, the initial two steps accounted for CO oxida- NO oxidizing catalysts. Nonuniform dopant concentration
tion. In Eq. (5), CO2 entered gas phase, while Eq. (6) accounted promoted the utilization of Ce and Cr, and the strong polar abil-
for the adsorption of CO2 as carbonate-like species. The rate of ity of Zr in the aqueous solution made it become the nucleation
the two competing steps determined the intensity and the ratio site in the hydrolysis process, resulting in Ce enriched on the
of the two peaks, which were strongly dependent on the com- surface. The adsorption of Cr by the porous structure of CZO
position and specific surface area of the oxide. Eqs. (7)–(9) ex- during the impregnation resulted in nonuniform. Zr-rich sam-
pressed the phenomena observed during the second half of the ple with tetragonal structure was favorable for the increasing
cycle: oxygen adsorption during the second half cycle was ex- of surface area and the decreasing of particle size and led to a
pressed in Eqs. (7) and (8), and reaction (9) was the reoxida- higher adsorption capacity of NO and O2 than Ce-rich sample.
tion step. Moreover, it was assumed that Eq. (8) was the
rate-limiting step in the oxygen dissociative adsorption pro- 4.1.2.2. Effect of the different preparation conditions
cess, while Eq. (7) was instantaneous. Thus, the rates of Eqs. (7) Zhong et al. [218] prepared the rigid ben-
and (9) determined the observed time lag between oxygen zene-muti-carboxylate ligand-modified Cr/CZO for NO oxida-
consumption and CO2 release. tion. The catalyst prepared with cinnamic acid as precipitant
exhibited a larger specific surface area, a lower band gap, and a
4.1.2. NO oxidation stronger ability to adsorb reactant gas. By contrast, Cr/CZO
NO oxidation to NO2 under O2-rich condition is attracting synthesized with terephthalic and trimesic acid was unbenefi-
more and more attention as it is involved in many diesel cial for the preparation of CZO owing to the long distance be-
de-pollution processes such as: (a) NSR strategy, where a noble tween the carboxyl groups. Subsequently, they studied the ef-
metal/alkaline-earth oxide component accomplishes NOx stor- fect of precursor solution of cinnamic acid as complex ligand
age and the subsequent reduction to N2 by adding a reducing for the preparation of Cr-doped Ce0.2Zr0.8O2 on the oxidation
gas in the exhaust [213]; (b) NO2-assisted soot combustion, activity of NO [219,220]. The solvent with appropriate polarity
where NO2 initiates and continues along with O2 to promote could decrease the band gap of the catalysts and benefit for
soot oxidation even under loose contact between catalyst and more generation of Ce3+ and Cr6+ on the catalyst surface, which
soot [214]; and (c) SCR of NOx, where NOx are selectively re- was beneficial to the adsorption of NO and O2. Moreover, Zhong
duced in an O2-rich environment. CZO showed extremely at- et al. [221] synthesized Co/CZO using citrate acid as complex-
tractive as possible substitutes of noble metals for catalytic ing agent and by an impregnation method. The sample pre-
Fig. 15. NO2 production profiles during TPR experiments for NO + 1/2O2 reaction. (a) Ceria-rich catalysts; (b) Zirconia-rich catalysts. Double arrow
(as symbol): NO2. Reprinted from [216] with permission.
pared by the former method showed better catalytic perfor- and finally miscellaneous compounds will be successively re-
mance for NO oxidation than that synthesized by the latter one viewed below, and the results are listed in Table 4.
due to its lower crystallite size, higher content of Ce3+, and eas-
ier reducibility. 4.1.3.1. Alkanes
4.1.3. Volatile organic compounds (voc) elimination 4.1.3.1.1. CH4 oxidation

VOC emitted from a large diversity of sources, such as Catalytic combustion of CH4 is an important technology for
transport and industrial processes as well as household prod- energy production and environmental pollution abatement.
ucts, are identified as main contributors to air pollution either CZO-supported noble metals and transition metals have been
through their toxic nature and/or as precursors of ozone and widely investigated for CH4 oxidation [48,225,226].
photochemical smog [2,222]. Catalytic oxidation is one of the (a) Effect of different Ce/Zr ratio
most useful and economically feasible techniques for the oxida- Meeyoo et al. [227] prepared highly uniform Ce1-xZrxO2 (x =
tion of VOC into CO2, H2O, and other less harmful compounds 0–1.0) materials via urea hydrolysis for CH4 combustion. The
[223,224]. Compared to CO, NO, and CH4 oxidation, fewer stud- incorporation of Zr into CeO2 lattice promoted the reductive
ies were devoted to VOC elimination over CZO. It is rather sur- behavior. The CH4 combustion activity of the mixed oxides was
prising if one considers their very good activity in oxidation closely related to the Ce/Zr ratio, and Ce0.75Zr0.25O2 showed the
reactions. The performance of CZO in eliminating hydrocarbons highest activity for CH4 combustion with T50 about 540 °C. Luo
(alkanes, alkenes, aromatics), alcohols and other oxygenates, et al. prepared CexZr1-xO2-supported PdO catalysts (x = 0–1.0)
Table 4
Catalytic activities of VOCs combustion over nanosize CZO materials.
Catalyst BET area (m2/g) Reaction conditions T50 (°C) Ref.
Ce0.75Zr0.25O2 108 2.0% CH4 + 21% O2 (100 mL/min, 0.1 g sample) 540 [227]
Ce0.6Zr0.3Y0.1O2 69 2.0% CH4 + 20% O2 (125 mL/min, 0.25 g sample) 671 [185]
3DOM Ce0.6Zr0.3Y0.1O2 94 2.0% CH4 + 20% O2 (125 mL/min, 0.25 g sample) 590 [185]
7% Mn/Ce0.67Zr0.33O2 62 1.0% CH4 + 4% O2 (100 mL/min, 0.5 g sample) 525 [234]
8.0% Fe2O3/Ce0.67Zr0.33O2-Al2O3 164 1.0% CH4 + 4% O2 (50 mL/min, 0. 2 g sample) 520 [232]
30% Co3O4/Ce0.6Zr0.4O2 172 0.3% CH4 + 4.8% O2 (50 mL/min, 0. 25 g sample) 380 [233]
0.25% Pd/Ce0.25Zr0.75O2-SiO2 — 2.0% CH4 + 21% O2 (10 mL/min, 0.1 g sample) 355 [229]
2.0% Pd/Ce0.67Zr0.33O2 77 2.0% CH4 + 20% O2 (100 mL/min, 0. 5 g sample) 400 [229]
2.0% Pt/Ce0.67Zr0.33O2 79 2.0% CH4 + 20% O2 (100 mL/min, 0. 5 g sample) 417 [229]
1.6% Pt/Ce0.67Zr0.33O2 69 1.0% CH4 + 4% O2 (100 mL/min, 0.5 g sample) 335 [234]
1.2% Pt/Ce0.6Zr0.3Y0.1O2 71 2.0% CH4 + 20% O2 (125 mL/min, 0.25 g sample) 558 [185]
3DOM 1.1% Pt/Ce0.6Zr0.3Y0.1O2 84 1.0% CH4 + 4% O2 (125 mL/min, 0.25 g sample) 434 [185]
0.2% Au/Ce0.6Zr0.3Y0.1O2 88 5.0% CH4 + 8% O2 (10 mL/min, 0.1 g sample) 600 [230]
Ce0.75Zr0.25O2 100 0.6% C3H6 + 21% O2 (100 mL/min, 0.1 g sample) 330 [242]
1.5% Ru/Ce0.75Zr0.25O2 42 0.6% C3H6 + 21% O2 (100 mL/min, 0.1 g sample) 212 [242]
1.5% Pd/Ce0.33Zr0.67O2-Al2O3 60 0.2% C3H8 + 2% O2 (500 mL/min, 0.1 g sample) 400 [235]
2% Pd/Ce0.2Zr0.78Y0.02O2-Al2O3 62 0.3% C3H8 + 3% O2 (300 mL/min, 0.6 g sample) 324 [236]
2% Pd/Ce0.2Zr0.78Ca0.02O2-Al2O3 68 0.3% C3H8 + 3% O2 (300 mL/min, 0.6 g sample) 327 [236]
2% Pd/Ce0.2Zr0.78Ba0.02O2-Al2O3 82 0.3% C3H8 + 3% O2 (300 mL/min, 0.6 g sample) 348 [236]
2% Pd/Ce0.2Zr0.75Y0.05O2-Al2O3 65 0.3% C3H8 + 3% O2 (300 mL/min, 0.6 g sample) 310 [237]
0.5% Pt/3%Ni/Ce0.4Zr0.6O2 65 0.2% C3H8 + 1% O2 (30 mL/min, 0.1 g sample) 330 [238]
8% CuO/Ce0.8Zr0.2O2 163 0.44% C7H8 + 21% O2 (55 mL/min, 0.1 g sample) 212 [248]
1.5% Ru/Ce0. 5Zr0.5O2 163 0.1% C6H6 + 2% O2 (320 mL/min, 0.2 g sample) 220 [243]
1.0% Pt/Ce0. 5Zr0.5O2 43 0.07% C7H8 + 2% O2 (130 mL/min, 0.4 g sample) 171 [244]
4.7% Au/Ce0.6Zr0.3Y0.1O2 79 0.1% C7H8 + 40% O2 (16.7 mL/min, 0.05 g sample) 218 [246]
0.9% Au1Pd2/Ce0.6Zr0.3Y0.1O2 76 0.1% C7H8 + 40% O2 (16.7 mL/min, 0.05 g sample) 190 [247]
17% Pd/Ce0.8Zr0.2O2 113 40% CH3OH (50 mL/min, 0.3 g sample) 200 [251]
Ce0.6Zr0.3Mn0.1Ox 55 1.5% C2H5OH + 21% O2 (30 mL/min, 0.25 g sample) 280 [252]
Ce0.24Zr0.4Mn0.36O2 163 0.08% C4H9OH + 21% O2 (100 mL/min, 0.2 g sample) 145 [255]
5% CuO/CeO2-ZrO2-TiO2 16 0.2% C4H8O2 + 21% O2 (100 mL/min, 0.2 g sample) 220 [257]
4% CuCe0.75Zr0.25Oy/ZSM-5 339 0.2% C4H8O2 + 21% O2 (400 mL/min, 0.8 g sample) 200 [258]
Ce0.5Zr0.5O2 99 0.1% 1,2-C2H4Cl2 + 21% O2 (500 mL/min, 0.85 g sample) 300 [260]
sulphated-Ce0. 5Zr0.5O2 98 0.1% 1,2-C2H4Cl2 + 21% O2 (500 mL/min, 0.85 g sample) 212 [262]
1.5% Pt/Ce0. 5Zr0.5O2 41 0.1% C2H4Cl2 + 21% O2 (1030 mL/min, 0.87 g sample) 412 [261]
0.3% Au/Ce0. 5Zr0.5O2 39 0.1% C2H4Cl2 + 21% O2 (1030 mL/min, 0.87 g sample) 417 [261]
Ce0.1 5Zr0.85O2 86 0.1% C2HCl3 + 21% O2 (500 mL/min, 0.85 g sample) 385 [265]
T50 is denoted as temperature corresponding to 50% VOC conversion.
and investigated the effect of Ce/Zr ratio on the catalytic activi- low-temperature combustion activity by dispersing the active
ty for CH4 oxidation [228]. PdO/ZrO2 was more active than phase Co3O4. Primet et al. [234] investigated the thermal stabil-
PdO/CeO2, and the activity of PdO/Ce0.1Zr0.9O2 was similar to ity of Ce1-xZrxO2 (0 < x < 0.53) materials. After being aged at
that of PdO/ZrO2. However, the activity of PdO/Ce0.2Zr0.8O2 1000 °C under oxygen and steam, the Ce0.67Zr0.33O2 solid solu-
catalyst decreased remarkably. As the content of Ce increased tion exhibited the highest thermal stability, and the
again (x = 0.3–1.0), the catalytic activity increased, and Pt/Ce0.67Zr0.33O2 catalyst exhibited a higher activity for CH4
PdO/Ce0.5Zr0.5O2 was the most active for CH4 oxidation in all combustion than Pt/Al2O3. However, a deactivation on stream
catalysts. Fu et al. [229] reported a series of y% was observed under isothermal conditions in the range of
Pd/CexZr1-xO2/SiO2 (x = 0–1.0, y = 0.1–1.0) catalysts for catalytic 200–500 °C. After being aged at 1000 °C, the positive effect of
CH4 combustion. The Ce/Zr ratio played an important role in Ce0.67Zr0.33O2 support was no longer observed.
the catalytic activity of Pd/CexZr1-xO2/SiO2. 0.5%
Pd/Ce0.25Zr0.75O2/SiO2 exhibited the most active for CH4 oxida- 4.1.3.1.2. Light hydrocarbons oxidation
tion in all catalysts, and T50 was obviously lower than the other Cerium-zirconium-based solid solutions were also used for
catalysts. oxidation of other light alkanes, especially for oxidation of C3H8.
(b) Effect of CZO-supported different nobel metals Weng et al. [235] reported C3H8 oxidation over Ce0.33Zr0.67O2
Dai et al. [230] fabricated a series of nanosize polycrystal- and Al2O3 supports and investigated the effects of the supports
line y% AuOm/Ce0.6Zr0.3Y0.1O2 (y = 0.2–10.0) using an in-situ on the catalytic performance of Pd-based catalysts for C3H8
reduction procedure with HAuCl4 as Au source, NaBH4 as reoxidation. The enlargement of the interface between Pd and
ductant, and PVP as surfactant. The redox property of y% support during thermal aging might lead to different
AuOm/CZY catalysts was significantly improved by the intro- Pd-support interaction. Furthermore, the light-off temperature
duction of Au, and AuOm/CZY catalysts with 0.2% Au exhibited for C3H8 oxidation over co-aged Pd/Ce0.33Zr0.67O2 and Al2O3 was
the highest catalytic activity for CH4 combustion, which may be lower than that over the mixture of aged Pd/Ce0.33Zr0.67O2 and
ascribed to the synergistic effect between the nanosize Au and Al2O3. Meng et al. [236] prepared a series of Pd/CZO-M/Al2O3
CZY nanocrystalline. Moreover, they reported a series of 3DOM (M = Y, Ca or Ba) closed-coupled catalysts by an ultrason-
Ce0.6Zr0.3Y0.1O2-supported high-dispersion Pt NPs (y% ic-assisted successive impregnation method for the total oxida-
Pt/3DOM CZY, y = 0.6–1.7) with high surface area (84–94 tion of C3H8. The introduction of Y greatly enhanced the cata-
m2/g) and highly dispersed Pt NPs (2.6–4.2 nm). 1.1% lytic activity of the catalysts for C3H8 total oxidation because of
Pt/3DOM CZY exhibited the best catalytic performance with the improved dispersion of Pd species and interaction between
90% CH4 conversion at 598 °C (GHSV = 30000 mL/(g∙h)) for Pd species and support, which endows Pd species with higher
CH4 combustion. The apparent activation energy (Ea) was 64 oxidation state. They further investigated the effect of Y loading
kJ/mol for 1.1% Pt/3DOM CZY, which was much lower than amounts (0%, 2%, 5%, 10%) on the catalysts for C3H8 combus-
that of 95 kJ/mol over Bulk CZY [188]. Bozo et al. [231] pre- tion [237]. The introduction of 5% Y greatly improved the dis-
pared a Ce0.67Zr0.33O2-supported Pt or Pd catalyst for CH4 total persion of Pd species and promoted the catalytic performance
oxidation. Deposition of Pt or Pd on this support resulted in a for C3H8 oxidation. However, further increasing the amount of Y
strong increase in activity, and CH4 oxidation took place at low led to the decrease of Pd-support interaction, resulting in a
temperature (200–500 °C). The Pd/Ce0.67Zr0.33O2 catalyst was slight decrease of Pd 3d5/2 binding energy. Therefore, the
more active than Pt/Ce0.67Zr0.33O2. chemical state of Pd species could be influenced by Y and its
(c) Effect of CZO-supported different transitional metal ox- amount, and the catalytic activity for C3H8 oxidation was also
ides affected. Wei et al. [238] investigated the effect of nickel on the
Fe2O3/Ce0.67Zr0.33O2-A12O3 for CH4 combustion was report- Pt/Ce0.4Zr0.6O2 catalyst for C3H8 oxidation and sulfur resistance.
ed by Gong et al. [232]. The optimal loading amount of Fe2O3 on The addition of nickel not only increased the specific surface
Ce0.67Zr0.33O2-A12O3 for catalytic combustion of CH4 was 8%, area of the catalyst, but also enhanced its redox property. As a
and the catalyst held the highest activity and the best thermal result, the nickel doping catalyst was more active in C3H8 com-
stability. The complete-conversion temperature of CH4 for fresh plete oxidation. Furthermore, the introduction of nickel to the
and aged samples was 515 and 565 °C, respectively. Liotta et al. catalyst was capable of enhancing the desorption amount of
[233] synthesized Co3O4/CZO containing 30% Co3O4 and inves- sulfur species under reducing atmosphere. Thereby the sulfur
tigated its catalytic activity on CH4 combustion. The results resistance of the Pt/Ce0.4Zr0.6O2 catalyst was improved. De Lei-
indicated that Co3O4/CZO exhibited a slightly lower CH4 con- tenburg et al. [239] reported a series of CZO doped with Mn
version than Co3O4/CeO2. and Cu solid solutions for the total oxidation of light hydrocar-
(d) Effect of Pretreatment temperatures bons. Both MnOm and CuO at low loading amount were dis-
Liotta et al. [233] investigated the effect of pretreatment solved into CZO lattice, which significantly influenced the re-
temperature and oxygen concentration on the light-off temper- ductive behavior of the catalysts by increasing the oxygen mo-
ature of CH4 combustion over a Co3O4/CeO2-ZrO2 catalyst. The bility, and then the catalytic activity for the total oxidation of
thermal stability of the catalyst depended on the size of the light HC was promoted.
cobalt oxide crystallites and the oxygen contents. Moreover, the
ceria and ceria-zirconia played a key role in inhibiting Co3O4 4.1.3.2. Alkenes
decomposition into CoO and maintaining a good Alkene combustion was exclusively performed with C3H6 as
model compound. D’Itri et al. [240] investigated the effect of mL/(g∙h), and T50 was 32 °C for CO oxidation and 218 °C for
sulfation on the structural, morphological, and catalytic prop- toluene oxidation, respectively. It should be attributed to its
erties of Ce0.75Zr0.25O2 solid solution. When Ce0.75Zr0.25O2 was higher oxygen adspecies concentration, superior
exposed to gaseous mixtures containing 20–40 ppm SO2 at 600 low-temperature reducibility, and better Au NPs dispersion.
°C, the crystallite grain size grew accompanied by the loss of Deactivation by water vapor addition was reversible due to the
surface area. Additionally, the introduction of 20 ppm SO2 into competitive adsorption of H2O and toluene as well as oxygen on
the 1100 ppm C3H6 + 2% O2 + N2 reaction mixture resulted in a the catalyst surface. Ea values (39–53 kJ/mol) obtained over y%
promoting effect on the catalytic activity of C3H6 oxidation over Au/CZY were much lower than that (88 kJ/mol) over CZY for
CeO2 due to the presence of acid-base interaction between sur- toluene oxidation. Subsequently, they prepared CZY nanorods
face hydroxysulfate species and C3H6. and supported Au and Pd alloy NPs [247]. 0.9% Au1Pd2/CZY
A Ce0.25Zr0.75O2-supported Pd catalyst was prepared for C3H6 exhibited the best catalytic activity, and T50 was 190 °C at a
oxidation reaction [241]. The catalytic activity of Pd/CZO was space velocity of 20000 mL/(g∙h). The active sites might be the
strongly influenced by the pretreatment conditions such as surface oxygen vacancies on CZY, oxidized noble metal NPs,
oxidative or reductive atmosphere. The initial activity of the and/or interfaces between noble metal NPs and CZY. Ea values
Pd/CZO catalyst under the insufficient oxygen condition was (37–43 kJ/mol) over 0.90%–0.93% AumPd/CZY were much
equivalent to the activity under the stoichiometric condition lower than that (88 kJ/mol) over CZY for toluene oxidation.
because of the property of high OSC. The CZO support promot- Yuan et al. [248] prepared mesoporous CZO using the surfac-
ed the dispersion of Pd oxide particles and their OSC property, tant template-assisted method, and then it was used as support
which assisted the C3H6 oxidation reaction. of CuO NPs for catalytic total oxidation of toluene. CuO/CZO
Aouad et al. [242] studied the catalytic behavior of CZO and catalysts exhibited a wormhole-like mesoporous structure with
Ru/CZO calcined at 500 and 600 °C for C3H6 oxidation. The high specific surface area and uniform pore diameter, and CuO
reactivity at both temperatures increased with increasing ce- NPs were highly dispersive on the CZO surface. 8%
rium content, and the introduction of Ru greatly enhanced the CuO/Ce0.8Zr0.2O2 calcined at 400 °C showed the best catalytic
reactivity of the two solids. The both specific surface area and activity due to the interfacial interaction between CuO and CZO
reductive behavior of the solids affected the catalytic reactivity. support and highly dispersive CuO NPs as well as the nature of
However, the reducibilities were the determinant factor in the the support.
catalytic behavior where easily reducible solids were more
reactive. Ru/CeO2 showed the optimal catalytic performance 4.1.3.4. Alcohols and other oxygenates
due to its high specific surface area and amount of Ru-O-Ce Methanol combustion was investigated by Ziolek et al. [249]
species. RuO2 clusters were formed with increasing Zr contents, over CeO2, ZrO2, and mixed CZO mesoporous oxides-supported
leading to a decrease in their catalytic activities. When the ce- Au and Cu. The electronic state of Au and the mobility of metals
rium content increased in the support, a more efficient interac- and oxygen from the support played a vital role in the combus-
tion was observed between cerium and ruthenium oxides. This tion of methanol at low temperature. In addition, the activation
interaction hindered the formation of RuO2 agglomerates and temperature strongly affected the mobility of surface oxygen
led to a better dispersion of ruthenium oxides and therefore a and the oxidation states of the cationic components, which
better catalytic performance. played the role of Lewis acid sites and thereby strongly influ-
enced the activity and selectivity of methanol oxidation. More-
4.1.3.3. Aromatics over, the catalytic decomposition of methanol to H2 and CO was
Except for the report of Zhu et al. [243], which deals with another efficient route. Chen and Liu et al. [250,251] reported
benzene oxidation, all authors have chosen toluene as a model catalytic decomposition of methanol to CO and H2 over
compound of aromatic hydrocarbons. The effect of Pt loading Pd/Ce0.65Zr0.30La0.05O2 and Pd/CexZr1-xO2 (x = 0–0.5). All
amounts (0.09–1.00%) on the catalytic performance of Pd-containing catalysts exhibited high selectivity to synthesis
CZO-supported catalysts in the total oxidation of toluene in air gas, among which the methanol conversion achieved 100% at
was investigated by Topka et al. [244]. The introduction of Pt 220 °C over Pd/Ce0.65Zr0.30La0.05O2.
facilitated the reduction of surface cerium and decreased the The ethanol complete oxidation over Mn0.1Ce0.9Ox and
acidity of the catalysts. The catalysts with 0.59% Pt showed the Mn0.1Ce0.6Zr0.3Ox complex compounds was studied by Wang et
best catalytic activity because of the presence of highly disper- al. [252]. T50 was lower over Mn0.1Ce0.9Ox (247 °C) than that
sive Pt NPs. Zhao et al. [245] investigated a over Mn0.1Ce0.6Zr0.3Ox (280 °C) for the fresh samples. For the
Pd/Ce0.4Zr0.602/substrate washcoat catalyst for toluene com- aged samples, however, T50 over Mn0.1Ce0.6Zr0.3Ox was lower
bustion. The Pd/Ce0.4Zr0.602/substrate monolithic catalyst after than that over Mn0.1Ce0.9Ox solid solution. The addition of Zr to
being calcited at 400 °C displated good thermal stability and Mn0.1Ce0.9Ox significantly improved its thermal stability, there-
highly catalytic activity, and the conversion of toluene was up fore, retaining its catalytic activity for the ethanol oxidation
to 95% at 210 °C. Dai et al. [246] prepared y% reaction. The effect of dopants (M = Mn, Y, La) on
Au/Ce0.6Zr0.3Y0.1O2 (y% Au/CZY, y = 0.4–4.7) using the MnOm/Al2O3/Ce0.45Zr0.45M0.10Oy for the catalytic combustion of
CTAB-assisted hydrothermal and PVP-protected reduction ethanol was investigated by Chen et al. [253]. The catalytic ac-
methods for the oxidation of toluene. 4.7% Au/CZY exhibited tivity of the MnOm/Al2O3/Ce0.50Zr0.50O2 monolithic catalyst was
the best catalytic performance at a space velocity of 20000 promoted by doping Mn, Y, and La into Ce0.50Zr0.50O2.
MnOm/Al2O3/Ce0.45Zr0.45Y0.10O1.95 exhibited the best catalytic  y-z y-z

C x H y Cl z   x   O2  xCO 2  H 2 O  zHCl
performance with 100% ethanol conversion temperature at  4  2 (10)
230 °C. The catalytic activity of Au versus Pt on CZO in oxida-  y y z
Cx H y Cl z   x   O2  xCO2  H2O  Cl2
tion of ethanol was compared by Gaálová et al. [254]. Pt cata-  4 2 2 (11)
lysts were more active in ethanol oxidation than Au catalysts The ratio between HCl and Cl2 can be controlled by the
due to their better reductive behavior and higher amount of Deacon equilibrium (Eq. (12)):
basic centers. On the other hand, the Au catalysts exhibited the 2HCl  1 O2  H2O  Cl2
2 (12)
better selectivity in ethanol oxidation.
This is an exothermic reaction (ΔrH° = 58.4 kJ/mol at 350
Ce0.6−xZr0.4MnxO2 solid solutions were used for the butanol
°C). Chlorine is produced in higher concentration at low tem-
total oxidation [255]. The textural and redox properties were
perature. For environmental reasons, it is preferable to orien-
improved when Mn content increased in the material, espe-
tate the reaction toward HCl, more easily eliminated by soda
cially for x = 0.36, which was the most active in the butanol
washing. Whatever the product, HCl or Cl2, the oxidation cata-
oxidation because of its high surface Mn4+ concentration and
lyst has to work under severe conditions, generally leading to
oxygen mobility.
rapid deactivation. Catalyst stability is an essential parameter
Pagadala et al. [256] reported a versatile reusable hetero-
for VOC oxidation processes involving chlorinated hydrocar-
geneous CZO/SiO2 catalyst synthesized by a very practical C–C
bons. CZO plays a key role in the abatement of chloroorganics.
and C–O bond forming reaction. This catalyst was superb for
Gutierrez-Ortiz et al. [260] studied the chlorinated hydro-
benzyl alcohols oxidation under the solvent-free liquid-phase
carbons (1,2-dichloroethane and trichloroethylene) oxidation
condition and was reusable with no loss of catalytic activity
over a series of CZO and found that the surface acidity and lat-
even after multiple cycles.
tice oxygen of the catalyst were responsible for the chlorohy-
Oxidations of esters were studied over non-noble metal cat-
drocarbons oxidation. The optimum performances were
alysts. Xu et al. [257] reported a series of CeO2 and/or
achieved over the zirconia-rich system. Matějová et al. [261]
ZrO2-TiO2-supported copper oxide catalysts for catalytic ethyl
prepared Ce0.5Zr0.5O2-supported Pt and Au catalysts for the
acetate combustion. CZO-promoted TiO2 greatly improved the
total oxidation of dichloromethane. The introduction of Pt and
dispersion of CuO phase, which then enhanced the catalytic
Au on the Ce0.5Zr0.5O2 support significantly promoted the redox
activity and prevented the formation of by-products. The com-
behavior of surface ceria particular for Pt-based catalysts, but it
plete combustion of ethyl acetate was observed at 270 °C over a
led to the loss of catalyst acidity. As a result, the noble metal
5% CuO/CZO-TiO2 catalyst. A series of CuCexZr1-xOy/ZSM-5 (x =
catalysts exhibited lower catalytic performance than
0‒1.0) catalysts were reported by Dou et al. [258], and their
Ce0.5Zr0.5O2 in dichloromethane total oxidation due to the de-
catalytic performance was tested for ethyl acetate abatement.
creases of acid sites for chlorinated compounds. Moreover,
The optimal performance was obtained with the
Pt-based catalysts showed considerably high CO2 selectivity
CuCe0.75Zr0.25Oy/ZSM-5 catalyst, which achieved total combus-
compared with the Ce0.5Zr0.5O2 support.
tion of ethyl acetate at 270 °C and the onset temperature as low
Gutiérrez-Ortiz et al. [262] prepared a series of sulphated
as 110 °C. Moreover, this catalyst exhibited remarkable stabil-
CZO using sulphuric acid and nitric acid for the oxidative de-
ity, and no deactivation phenomenon was noted after a
composition of dichloroethane. The catalyst showed a superior
long-term catalytic reaction for 60 h at 270 °C. Apart from
catalytic activity at a reaction temperature of dichloroethane
Cu-based CZO catalysts, doping other metals (Mn, Y) into CZO
decomposition as low as 80 °C. The increased acidity of CZO
affected the activity for ethyl acetate catalytic combustion
was responsible for its excellent activity. Li et al. [263] investi-
[259]. The Mn doping greatly increased the OSC of the oxy-
gated the catalytic oxidation of 2-chlorophenol over a Ru/CZO
gen-storage materials (OSMs), whereas doping Y decreased the
catalyst. The mobility of the lattice oxygen was significantly
reduction temperature of catalysts. The doping of Mn and Y
promoted by the addition of Ru, which greatly enhanced the
combined the advantages of Mn and Y.
catalytic activity of the catalyst. González-Velasco et al. [264]
MnOm/Ce0.40Zr0.40Mn0.10Y0.10Oy/Al2O3 gave the best catalytic
studied the catalytic oxidation of dichloroethane and trichloro-
performance, which achieved complete conversion of ethyl
ethylene over CZO in the presence and absence of n-hexane.
acetate at 240 °C, and the temperature range between the ini-
The catalytic activity of the catalyst for the chlorinated organics
tial conversion and complete conversion was the smallest. Mn
oxidation was dependent on the Ce/Zr molar ratio, surface
and Y entered the lattice of CZO, which modified their textural
acidity, and OSC of CZO. CZO exhibited higher activity than pure
properties and greatly improved the dispersion of MnOm active
CeO2 in the elimination of chlorohydrocarbons in the absence
phase on the support surface.
of n-hexane. In the presence of n-hexane, however, an increase
in the ignition temperature was observed over CZO. Further-
4.1.3.5. Chlorinated VOC and other Cl-containing compounds
more, the introduction of n-hexane led to the formation of H2O
Chlorohydrocarbon is one of the primary air pollutants,
in its combustion process, which was responsible for the in-
which has superior stability and toxicity and is emitted from
creased selectivity to HCl.
various sources. Therefore, great efforts have been made to
Rivas et al. [265] investigated trichloroethylene oxidation
eliminate these compounds. Oxidation of chlorinated hydro-
over CZO prepared by the CP method. The catalyst with the
carbons (CHC) can produce HCl (Eq. (10)) or Cl2 (Eq. (11)):
most acidity displayed the highest activity. A mechanism for the
dechlorination reaction was also proposed, in which the ad- cars in Europe since 2009, and in China since 2018). It has im-
sorption of trichloroethylene onto catalyst surface is the posed the utilization of catalytic technologies to satisfy the re-
rate-limiting step, in agreement with that reported by Fei- quired standards [269,270]. Among the different alternatives,
jen-Jeurissen et al. [266]. Gutierrez-Ortiz et al. [267] investi- the entrapment of particulate from exhaust gases by diesel
gated 1,2-dichloroethane decomposition over CrxZr1-xO2 (x = particulate filter (DPF) has attracted much attention in recent
0–1.0), and the catalytic activity changed with the zirconia years [271–278]. The soot particulates can be burnt off above
content for the samples. Ce0.5Zr0.5O2 exhibited the best perfor- 600 °C, however, typical engine exhaust temperatures fall
mance. A reaction mechanism was proposed based on the within the 180–400 °C range [277–279]. In order to overcome
in-situ FT-IR spectra. It involved 1,2-dichloroethane dehydro- the limitation of alternative regeneration of DPF and prevent
chlorination on the acidic sites of the catalyst to form vinyl from the deposition of particles, oxidation catalysts are devel-
chloride and HCl. Then the vinyl chloride got protonation from oped to improve the combustion activity of soot over DPF.
the basic species (OH) of catalyst surface, which led to the for- Among which, CZO is efficiently used due to their high mobility
mation of carbonium ions. Subsequently, these ions were of reactive oxygen species and thermal stability [273,280,281].
trapped by the nucleophilic oxygen from the catalyst to form It is now accepted that it exhibits much higher soot oxidation
chlorinated alkoxide compound and then it decomposed to rate in the presence of O2 + NO2 than that in O2 alone. In this
acetaldehyde. Finally, CO2 and trace amounts of CO were section, soot combustion over Ce-Zr-based catalysts is re-
formed by the conversion of acetaldehyde. viewed, as shown in Table 5.
4.1.4. Soot combustion 4.1.4.1. Effect of support composition

Soot emitted from diesel engine outlets is a main constituent The effects of specific surface area and OSC of CZO on soot
of air pollution. It is closely related to respiratory and cardio- combustion were investigated by Trovarelli et al. [280]. The
vascular diseases as well as skin cell alterations [268]. There- surface oxygen linked to ceria played a vital role for the cata-
fore, stringent legislation has been implemented to limit soot lytic combustion of soot, while OSC could be important when
content from vehicles (e.g., 0.005 g/km for soot from passenger oxidation of soot particles was carried out in the absence or
Table 5
Catalytic activities of nanosize CZO materials in soot combustion.
Catalyst Reaction conditions T50/Tm (°C) Ref.
Ce0.5Zr0.5O2 20% O2 (100 mL/min)/(Cat./soot = 4, tight) 522 [285]
Ce0.69Zr0.31O2 20% O2 (100 mL/min)/(Cat./soot = 4, tight) 458 [275]
Ce0.8Zr0.2O2 10% O2 (100 mL/min)/50 mg sample (Cat./soot = 9, tight) 469 [282]
Ce0.9Zr0.1O2-NP 10% O2 (100 mL/min)/50 mg sample (Cat./soot = 9, tight) 435 [283]
3DOM Ce0.7Zr0.3O2 0.2% NO + 10% O2 (100 mL/min) (Cat./soot = 10, loose) 388 [102]
HP Ce0.5Zr0.5O2 20% O2 (100 mL/min) (Cat./soot = 4, tight) 415 [289]
K/Ce0.5Zr0.5O2 10% O2 (500 mL/min)/110 mg sample (Cat./soot = 10, tight) 340 [187]
Ru/K/Ce0.8Zr0.2O2 10% O2 (500 mL/min)/20 mg sample (Cat./soot = 20, loose) 385 [306]
Ru/K/Ce0.8Zr0.2O2 0.05% NO + 10% O2 (500 mL/min)/ 20 mg sample (Cat./soot = 20, loose) 393 [306]
Ru/Ba/Ce0.8Zr0.2O2 10% O2 (500 mL/min)/20 mg sample (Cat./soot = 20, loose) 585 [306]
Ru/Ba/Ce0.8Zr0.2O2 0.05% NO + 10% O2 (500 mL/min)/20 mg sample (Cat./soot = 20, loose) 495 [306]
Ce0.48Zr0.5La0.02O1.99 6% O2 (400 mL/min)/25 mg sample (Cat./soot = 20, tight) 414 [284]
Ce0.84Zr0.15Y0.01O2 20% O2 (100 mL/min) (Cat./soot = 4, tight) 456 [405]
Ce0.8Zr0.1Pr0.1O2 10% O2 (100 mL/min)/50 mg sample (Cat./soot = 9, tight) 444 [282]
Ce0.4Zr0.5Pr0.1O2 0.2% NO + 5% O2 (100 mL/min) (Cat./soot = 10, tight) 361 [274]
Ce0.48Zr0.5Pr0.02O1.99 6% O2 (400 mL/min)/25 mg sample (Cat./soot = 20, tight) 410 [284]
Ce0.48Zr0.5Tb0.02O1.99 6% O2 (400 mL/min)/25 mg sample (Cat./soot = 20, tight) 414 [284]
Ce0.48Zr0.5Sm0.02O1.99 6% O2 (400 mL/min)/25 mg sample (Cat./soot = 20, tight) 411 [284]
3DOM Ce0.6Zr0.3Pr0.1O2 0.2% NO + 5% O2 (100 mL/min)/110 mg sample (Cat./soot = 10, loose) 361 [103]
Ce0.5Zr0.2Fe0.3O2 10% O2 (500 mL/min)/165 mg sample (Cat./soot = 10, loose) 310 [287]
3DOM Ce0.8Zr0.1Fe0.1O2 0.1% NO + 0.1% NH3 + 3% O2 (100 mL/min)/110 mg sample (Cat./soot = 10, loose) 375 [182]
3DOM Ce0.8Zr0.1Mn0.1O2 0.1% NO + 0.1% NH3 + 3% O2 (100 mL/min)/110 mg sample (Cat./soot = 10, loose) 402 [184]
3DOM Ce0.8Zr0.1Co0.1O2 0.1% NO + 0.1% NH3 + 3% O2 (100 mL/min)/110 mg sample (Cat./soot = 10, loose) 433 [184]
3DOM Ce0.8Zr0.1Ni0.1O2 0.1% NO + 0.1% NH3 + 3% O2 (100 mL/min)/110 mg sample (Cat./soot = 10, loose) 429 [184]
Ru/Ce0.4Zr0.6O2 20% O2 (75 mL/min)/11.67 mg sample (Cat./soot = 9, loose) 360 [294]
3DOM Au/Ce0.7Zr0.3O2 0.2% NO + 5% O2 (50 mL/min)/110 mg sample (Cat./soot = 10, loose) 375 [101]
Cu/Ce0.55Zr0.45O2 9.5% O2 (500 mL/min)/110 mg sample(Cat./soot = 10, tight) 365 [296]
Co/Ce0.5Zr0.5O2 15% O2 (35 mL/min)/100 mg sample(Cat./soot = 10, tight) 386 [298]
Ni/Ce0.5Zr0.5O2 20% O2 (60 mL/min)/100 mg sample (Cat./soot = 4, tight) 463 [299]
Ag/Ce0.75Zr0.25O2 5% H2O + 4.8% O2 (50 mL/min)/200 mg sample (Cat./soot = 19, loose) 286 [295]
Ag/Ce0.75Zr0.25O2 5% H2O + 0.1% NO + 4.8% O2 (50 mL/min)/200 mg sample (Cat./soot = 19, loose) 279 [295]
CuO-CoO/Ce0.5Zr0.5O2 20% O2 (60 mL/min)/100 mg sample (Cat./soot = 4, tight) 363 [299]
CuO-NiO/Ce0.5Zr0.5O2 20% O2 (60 mL/min)/100 mg sample (Cat./soot = 4, tight) 388 [299]
T50 and Tm are denoted as temperature corresponding to 50% soot conversion and temperature at the maximum CO2 concentration in the process of
soot combustion, respectively. Loose or tight is referred to that the contact condition between catalyst and soot is loose contact or tight contact.
defect of gaseous oxygen. The effects of Ce/Zr ratios on the tion, the yttrium doping and loading had a minor or null effect
phase composition and catalytic activities of CZO and Pr/CZO on the activity, and the stabilizing effect of the specific surface
samples for soot combustion were investigated by Bensaid et area due to zirconium doping prevailed.
al. [282], as displayed in Table 5. The role of Zr in stabilizing
surface area of ceria was also important when evaluating the 4.1.4.2. Effect of preparation method
effect of composition on soot combustion activity. Fino et al. The catalytic performances of CZO-based materials for soot
[283] prepared a series of nanostructured CZO with different combustion were influenced by the preparation method. Sang
Zr contents and structural features for soot combustion. The et al. [287] reported a series of Ce0.5Fe0.30Zr0.20O2 catalysts pre-
optimally catalytic performance was obtained for the pared by different methods (CP, SG, physical mixed, impregna-
nano-polyhedra Ce0.9Zr0.1O2 catalyst due to its higher mobility tion, and hydrothermal method). Fe3+ and Zr4+ were incorpo-
of the lattice oxygen and easier reducibility compared with rated into ceria lattice to form a homogeneous Ce-Fe-Zr-O solid
other catalysts. The substitution of some Zr4+ ions into Ce4+ was solution by the CP method, but two kinds of Fe phases existed
favorable for the generation of defects in the ceria lattice, in Ce-Fe-Zr-O catalysts prepared by other methods: dispersed
thereby leading to a distortion of the oxygen sublattice. Never- Fe2O3 clusters and Fe3+ incorporated into CeO2 lattice. The free
theless, the amount of redox Ce species decreased with in- Fe2O3 clusters could promote the activity of catalysts for soot
creasing Zr contents. Therefore, it seemed that the substitution combustion comparing with Ce-Fe-Zr-O solid solution owing to
of Zr for Ce did not have a direct promotion effect on the oxida- the synergetic effect between free Fe2O3 and surface oxygen
tion activity of catalysts. vacancies. In addition, the activity of catalysts considerably
The effect of the rare earth elements-modified CZO on the relied on the surface reducibility of free Fe2O3 particles. The
catalytic combustion of soot was investigated. Aneggi et al. hydrothermal Ce0.5Fe0.3Zr0.2O2 catalyst displayed the minimum
[284] studied the effect of rare earth elements (La, Pr, Sm, Tb) ignition temperature (251 °C) and maximum oxidation rate
on the textural and structural characteristics of CeO2 and CZO temperature (Tm = 310 °C) for the combustion of soot in tight
for soot combustion. CeO2 doped with these rare earth ele- contact between soot and catalysts. This was due to the both
ments exhibited more active activities due to the increased abundant free Fe2O3 particles and high oxygen vacancy con-
oxygen storage, which could provide an alternative route for centration. Even after being aged at 800 °C for 10 h, Tm still
the oxidation of big soot particles in contact with ceria. Howev- displayed a low value at 361 °C.
er, CZO modified with rare earth elements did not achieve low-
er combustion temperature, which was comparable to CeO2 4.1.4.3. Effect of pore structure
and CZO. The role of Pr as dopant for ceria-based catalysts was It is well known that the conventional ce-
studied in CO and soot oxidation by Zhao et al. [103]. It ap- ria-zirconium-based catalysts have smaller pore sizes (< 10
peared that the incorporation of Pr species into CZO framework nm) than soot particles (> 20 nm). Therefore, soot particles are
improved the oxidation activity for CO, while this positive effect difficult to enter the inner pores of these catalysts to access
was less prominent for soot combustion due to the effect of active sites. So how to effectively make use of the inner surface
catalyst morphology. The phase compositions of Pr-modified for increasing the contact area between catalysts and soot par-
CZO were similar to those of corresponding CZO samples, and ticles is a key factor to enhance the catalytic activity for the
cubic and tetragonal phases coexisted in the samples with removal of soot. Fino et al. [283] investigated the soot combus-
moderate zirconia content, which was beneficial to soot com- tion over microporous and mesoporous Ce0.9Zr0.1O2 oxides.
bustion. Additionally, the effects of thermal and hydrothermal Lower soot conversion was achieved for both microporous and
treatments on the catalytic activities of 3DOM CeO2, Ce0.7Zr0.3O2, mesoporous Ce0.9Zr0.1O2 with similar Ce/Zr ratio. Ce0.9Zr0.1O2
and Ce0.6Zr0.3Pr0.1O2 for soot oxidation were comparatively particle catalyst showed the worse activity than the porous
studied. Compared with 3DOM CeO2, 3DOM Ce-Zr-based solid materials, which confirmed the important role of the textural
solutions, especially Pr-modified Ce0.6Zr0.3Pr0.1O2 solid solution, properties for soot combustion. 3DOM CZO contains periodic
showed the highest stability due to its lowest lattice oxygen arrays of interconnected macropores [102]. The open, inter-
mobility among the three samples. The relative efficacy of the connected macroporous structure is a desirable feature for
La promoter in CZO was investigated systematically for soot diesel soot combustion. Compared with that of disordered
oxidation at low temperature [285]. The addition of La3+ to macroporous (DM) catalysts, 3DOM samples facilitate the con-
ceria promoted the oxidation rate of soot compared with pure tact between soot and catalysts and promote the catalytic ac-
ceria and Zr4+-doped ceria. This should be due to the more activity for soot combustion. T50 of 3DOM samples could be low-
tive oxygen provoked by defective structure of ceria, which was ered by 51 °C at most, as shown in Fig. 16. Then, 3DOM
induced by the presence of La3+. The effect of Y doping and CZO-supported Au NPs catalysts were prepared via the gas
loading on the physicochemical properties and soot combus- bubbling-assisted membrane reduction method [288]. This
tion activity of CZO was investigated by Bueno-López et al. kind of catalysts combined both advantages of good contact
[286]. In tight contact, Ce0.85-xZr0.15YxO2 mixed oxides on the between diesel soot and catalyst by 3DOM supports and the
catalytic activity with respect to yttrium. And in loose contact, highly active sites for the activation of O2 by Au clusters with
the catalytic activity was dependent on their specific surface suitable nanosize, and they exhibited good catalytic perfor-
area, and catalysts Ce0.85-xZr0.15YxO2 (10–13 m2/g) were more mances for the oxidation of soot. 3DOM Au/Ce0.7Zr0.3O2 catalyst
active than Ce1-xYxO2 (2–3 m2/g). In this loose contact condi- showed T50 as low as 375 °C. In addition, Pr-modified 3DOM
the ceria surface, which might lower the activation energy of

soot combustion. Reddy et al. [297] reported CZO-supported Cu
catalysts for soot combustion. The introduction of Cu2+ into
CZO was benefited to the formation of more structural defects,
which accelerated the oxygen diffusion and induced the pro-
duction of more surface-active oxygen species. It was responsi-
ble for the improved low-temperature activity of soot combus-
tion. Chen et al. [298] investigated the effect of Co addition on
catalytic performance of Ce0.5Zr0.5O2 mixed oxide for soot com-
bustion. The catalytic activity of the catalyst was effectively
improved by the addition of Co with soot due to the existence
of synergistic effect between Co and Ce. CZO-based monometal-
lic (CoO/CZO and NiO/CZO) and bimetallic (CuO-CoO/CZO and
CuO-NiO/CZO) catalysts were prepared by Reddy et al. [299]
Fig. 16. T50 of Ce1-xZrxO2 catalysts with different macroporous struc-
and used for soot oxidation. The bimetallic CuO-CoO/CZO cata-
tures versus Zr molar fraction for soot combustion. Reprinted from
[102] with permission. lyst exhibited the best catalytic activity (T50 = 363 °C) and
nearly 100% CO2 selectivity due to the formation of facile re-
duction and abundant oxygen vacancies as well as the small
CZO was prepared by a CCT method [103]. It was used for the size of the metal particles and the high specific surface area.
removal of soot and exhibited higher catalytic activities com- Escribano et al. [300] found that the Mn/CZO catalyst showed
pared with DM ones. This was due to the improved contact high activity for soot combustion, producing CO2 and CO as a
efficiency between soot and ordered macroporous structure. by-product in the temperature range of 152–452 °C, and the
Zaletova et al. [289] reported that hierarchical porous (HP) amount of CO decreased significantly with increasing O2 con-
CZO was prepared using small-size fraction of wood as tem- centration in the feed gases.
plate for oxidation of diesel soot particulate. HP CZO exhibited Adding low melting point metal salts can improve the cata-
higher soot conversion over regular CZO due to its larger sur- lytic activity [301], and alkali metals have been reported as a
face area, higher amount of mobile lattice oxygen and lower molten salt to promote catalyst-soot contact by increasing sur-
temperature of oxygen release. face mobility [102,302,303]. Neyertz et al. [279] reported that
the introduction of K promoted the catalytic performances of
4.1.4.4. Effect of active phase K/CeO2/cordierite and K/Ce0.65Zr0.35O2/cordierite for soot
Ru is established as a successful catalytic system in oxida- combustion. However, the K/CeO2/cordierite catalyst was
tion reactions [290–293]. Nascimento et al. [294] reported the more active due to the distribution of Zr on the surface of
soot combustion over Ru-doped Ce0.4Zr0.6O2 nanopowders in Ce0.65Zr0.35O2, which decreased the catalytic activity. Zhu et al.
the temperature range of 220–500 °C. Ce0.4Zr0.6O2 showed good [304] investigated the effect of KNO3 loading on Ce0.5Zr0.5O2 for
tolerance to water as well as excellent thermal stability. The catalytic soot combustion. KNO3 loading on Ce0.5Zr0.5O2 resulted
addition of Ru NPs (8–10 nm) to Ce0.4Zr0.6O2 greatly boosted in an distinct enhancement in the catalytic activity due to that
the reactivity of the mixed binary catalyst due to the increased KNO3 favored the formation of chemisorbed oxygen and car-
active oxygen species. Chen and Zheng [295] prepared a mes- bonate species (C-O-K), which could react with soot to yield
oporous Ag/CZO catalyst with Ag/Ce structure by the CP CO2, and the reduced state C-M was reoxidized by O* to reform
method using a mixture of NH3∙H2O and KOH as precipitant. C-O-K. In addition, Wu and Weng et al. [305] studied the role of
The Ag-Ce interaction led to the increase of Ag+ species, which CZO in diesel soot oxidation and thermal stability of a potassi-
was favorable for the activation of oxygen species. In addition, um catalyst, and they believed KNO3 to be the key factor affect-
it was found that Ag0 species surrounding with Ag+ species was ing soot catalytic combustion due to that the nitrate can act as
more beneficial to activating the oxygen. While Ag-Ce interface an oxidant of soot being transformed into reduced nitrite spe-
brought about Ag+ species, which would be more effective in cies.
transferring the activated oxygen species. Thus, the Ag-based Castoldi et al. [306] investigated K- and Ba-doped Ru sup-
catalyst with optimal Ag-Ce interaction exhibited excellent ported catalysts for the removal of soot in the presence of NOx.
performance for soot oxidation even in the loose contact mode 1 wt% Ru-10 wt% AM/MO (AM = Ba or K; MO = Ce0.8Zr0.2O2,
and in the absence of NOx. And its activity could keep stable for ZrO2, Al2O3) catalysts promoted the soot particulate combus-
several runs, which was attributed to Ag-Ce interaction along tion in the presence of NO/O2. The promotion effect for K-based
with different distribution of Ag species. catalysts seemed to be not dependent on the nature of the
Transition metals, such as Co, Cu and, Mn, are widely used in support, and it appeared to be closely related to the synergic
commercial soot removal systems. Wu et al. [296] investigated interaction between Ru and K that boosted the combustion of
the soot catalytic oxidation over Cu doping CeO2/CZO catalysts. soot at low temperature. K-containing catalysts exhibited very
Cu modification improved the activity and selectivity of CeO2 low onset temperature, in the range 220–235 °C. In addition, all
and CZO for the catalytic oxidation of soot attributing to the Ru-based samples were able to simultaneously remove NOx and
well dispersed copper oxide species strongly interacting with soot when operating under isothermal cycling conditions, i.e.,
alternating lean-rich phases based on the typical diesel engine fered/spilled over to the soot and the catalyst was reduced. In
NOx reduction strategy. In particular, the materials showed a the third step, the SOC decomposed to yield CO or CO2.
NOx storage capacity comparable to that of model Pt-based
catalysts. NOx storage capacity increased over Ru-based sys- 4.2. Nanosize cerium-zirconium-based solid solutions for selec-
tems in the presence of soot particulate, while for model tive oxidation of NH3
Pt-containing catalysts a detrimental effect of soot was found.
Among all the developed formulations, K-based materials ex- The removal of NH3 from waste streams is becoming an
hibited higher NOx storage capacity and higher soot oxidation important issue due to ever increasing environmental concerns
activity compared to Ba-containing samples. [309]. In order to control the NH3 slip, several different tech-
niques have been used for the elimination of NH3, such as ad-
4.1.4.5. Mechanisms of soot combustion over nanosize sorption, chemical treatment, catalytic decomposition, and
ceria-zirconium-based solid solutions selective catalytic oxidation (SCO) [310–314]. Among which,
The combustion of soot over ceria mainly relies on the re- SCO of NH3 to N2 from oxygen-containing waste gases over CZO
dox couple. Ce3+/Ce4+ with its ability shifts between Ce2O3 and is becoming a hot issue in recent years.
CeO2, which is associated with the OSC of ceria. The surface
oxygen of pure ceria is used for the soot oxidation and the con- 4.2.1. Effect of material composition
secutive vacant site is quickly refilled by gaseous/subsurface Qu et al. [315] investigated SCO over Ce1-xZrxO2 (0.2 ≤ x ≤
oxygen. Doped ceria can create more structural defects com- 0.8) mixed oxides. Compared with pure CeO2 and ZrO2, CZO
pared to pure ceria. So, these defects facilitate either more gas- exhibited more acid sites and higher catalytic activity. Espe-
eous oxygen to adsorb onto the surface or diffusion of subsur- cially, the Ce0.4Zr0.6O2 catalyst displayed the highest NH3 con-
face lattice oxygen onto the surface, thereby enhancing the version and the lowest total conversion temperature up to 360
formation of active oxygen species. It was reported that the rate °C, which was associated with the partial phase segregations of
of this active oxygen transfer to soot is much faster than that of ZrO2 in Ce0.2Zr0.8O2. Additionally, zirconium-rich samples (x >
both gas phase oxygen transfer to soot. It is self recombination 0.4) showed the higher N2 selectivity (~100%), and the for-
to give O2, hence plays a crucial role in the soot oxidation. The mation of N2O was the main reason resulting in the low N2 se-
reaction mechanism for soot combustion in the presence of lectivity for these catalysts (x ≤ 0.4). They further studied
O2/NO over 3DOM Au/Ce1-xZrxO2 catalysts was investigated by Al-promoted Ce0.4Zr0.6O2 mixed oxides in the SCO of NH3 to N2
Zhao et al. [101], and they proposed a reaction pathway for [316]. The addition of Al to Ce0.4Zr0.6O2 greatly improved the
soot combustion, as shown in Fig. 17. The synergic effect be- oxidation activity of NH3. Particularly, the 3% Al-Ce0.4Zr0.6O2
tween Au particle and Ce1-xZrxO2 support played an important catalyst exhibited higher NH3 conversion (12.7%) than the
role for soot combustion. So far, the accepted mechanism Ce0.4Zr0.6O2 catalyst due to the improved oxygen mobility, re-
[285,307,308] for the catalytic oxidation of soot over ceri- ducibility, and oxygen vacancies. Among these, oxygen vacancy
um-zirconium-based solid solutions involved the following was thought to be the essential oxygen adsorption and activa-
steps: tion sites. Therefore, more oxygen vacancies facilitated NH3
Mred  gas  O  Mox  O oxidation reaction.
(13)
Mox  O  Cf  M red  SOC (14)
SOC  CO or CO 2 4.2.2. Effect of active phase types and reaction condition
(15)
Qu and Wang et al. [317] prepared a series of Cu/CZO mate-
where Mred and Mox-O represented the reduced and oxidized
rials by the incipient-wetness impregnation, CA-SG, and homo-
states of the catalyst, respectively. Gas-O stood for the oxidant
geneous precipitation methods. Cu/CZO prepared by the CA-SG
gas (O2, CO2, H2O, etc.), Cf denoted a carbon active site or free
method exhibited the best NH3-SCO activity owing to its better
site on the soot surface, and SOC represented a surface car-
adsorption capacity, more isolated Cu2+, and active oxygen ad-
bon-oxygen complex. In the first step, the catalyst “captured”
species. The influence of Ni loading (0, 5%, and 10%), oxygen
oxygen from the gas-phase molecules and was itself oxidized.
amounts (λ = 0.25, 0.5), and gas hourly space velocity (50000,
In the second step, the active oxygen on the catalyst trans-
100000, and 150000 h−1) on catalysts for NH3-SCO was inves-
tigated by Nassos et al. [318]. 10% Ni/Ce0.9La0.1O2 showed the
optimally catalytic activity with 65% and 97% N2 yield at 500
and 750 °C, respectively. Increasing λ and lowering the gas
hourly space velocity led to considerably improved N2 yield at
500 °C. Qu and Yan et al. [319] synthesized Ru-modified
Ce1-xZrxO2 for NH3-SCO. The 0.2% Ru-modified Ce0.6Zr0.4O2 cat-
alyst displayed excellent performance for the SCO of slip NH3,
and SO2 could enhance the removal of slip NH3 in the presence
of NOx but also slightly supressed NH3 oxidation and signifi-
Fig. 17. Mechanism illustration of soot combustion over 3DOM cantly improved N2 selectivity to 100% in the absence of NOx,
Au/Ce1-xZrxO2 catalysts at different temperatures in the presence of O2 as shown in Fig. 18.
and NO. Reprinted from [101] with permission.
Fig. 18. (a) NH3-SCO efficiency over various catalysts at 350 °C; (b) N2 selectivity of NH3-SCO with or without SO2 over various catalysts. GHSV = ~3 ×
105 h−1, temperature = 350 °C, 30 ppm of NH3, 30 ppm of NO, 500 ppm of SO2, the other gas including 4% O2 and N2. Reprinted from [319] with per-
mission.
NOx produced from the combustion of fossil fuels such as

4.2.3. Mechanisms of NH3 oxidation over nanosize coke in the electrical power plants or petroleum in the engines
ceria-zirconium-based solid solutions of vehicles brought about ecological and health hazards [321].
Qu and co-worker [317] proposed that the mechanism of The nitrous oxide N2O, not submitted to drastic regulations as
NH3-SCO with lattice oxygen was different from that of gaseous NOx, is considered as a nontoxic greenhouse gas. However, its
oxygen, which was much less active than gaseous oxygen at low global warming potential is 310 times as that of CO2, and its
temperature. They suggested that the reaction mechanism of abatement is often considered as a priority to avoid erratic
NH3-SCO over Ru/Ce0.6Zr0.4O2 should follow an internal SCR climate changes in the next decades [322,323]. Therefore, great
mechanism [319], as shown in Fig. 19, which was in accordance efforts were devoted to the development of highly efficient
with the results of Breen et al. [320] The adsorbed NH3 was catalysts for the elimination of NOx including N2O [324–326].
irst activated and reacted with lattice oxygen to form a −HNO CZO has drawn ever increasing attention due to its specific
intermediate. Subsequently, −HNO reacted with O2 to generate properties. NOx can be reduced or decomposed to N2 by direct
NO. Meanwhile, the formed NO interacted with −NH2 to pro- decomposition or by chemical reduction using reductants such
duce N2, and N2O as the byproduct. as NH3, H2, HC, etc.
NH 3  NH 2  H
(16) 4.3.1. NH3-SCR
NH 2  NH  H
(17) NH3-SCR is regarded as an effective method for the removal
NH  O  HNO (18) of NOx from stationary and mobile sources, and the catalytic
O 2  2O (19) efficiency of this technique is significantly affected by the com-
HNO  O  NO  OH (20) position of CZO supported catalysts, as show in Table 6.
NH2  NO  N2  H2O
(21)
NH  NO  N 2O  H 4.3.1.1. Effect of support composition
(22)
Zhang et al. [327] studied the catalytic activity of the 3DOM
H  OH  H 2 O
(23) CZO catalyst doped by metal M (Mn, Fe, Cu and Co) for NH3-SCR
4NH3  3O2  2N2  6H2O
(24) of NOx. Those dopants were well incorporated into Ce lattice,
except for Cu, and the introduction of those additives to CZO
4.3. Nanosize cerium-zirconium-based solid solutions for enhanced the active oxygen species, surface reducibility and
selective reduction of NOx acidity of the catalysts. Therefore, these doped catalysts dis-
played better catalytic activity than CZO at low temperature.
Among them, the Co-modified catalyst showed the optimum
catalytic activity attributed to its highest Oα/(Oα + Oβ) ratio and
reducibility, as well as the strongest NH3 adsorption ability. In
addition, Fe and Mn dopants effectively broadened the activa-
tion temperature window.
The effect of nickel- and sulfate- modified CZO for NH3-SCR
of NO in the presence of excess O2 was investigated by Weng et
al. [328]. The addition of Ni increased the strength of Lewis
acid sites of the catalyst, which was viewed as the essential
Fig. 19. Mechanism of NH3-SCO and the effect of SO2. Reprinted from active sites for low-temperature NH3-SCR reaction. Additional-
[319] with permission.
ly, the sulfate modification induced the formation of Brønsted
Table 6
Catalytic activities of nanosize CZO materials in NH3-SCR of NOx.
Catalyst Reaction conditions XNO (%) Tr (°C) SN2 (%) Ref.
Ce0.75Zr0.25O2 NO/NH3/H2O/O2 = 0.05:0.05:5:5/300000 h−1 77 300–350 — [346]
3DOM Ce0.8Zr0.2O2 NO/NH3/SO2/O2 = 0.05:0.05:0.02:3/20000 h−1 >90 275–425 — [327]
3DOM Ce0.75Zr0.2M0.05O2-δ (M = Fe, Cu, Mn, Co) NO/NH3/SO2/O2 = 0.05:0.05:0.02:3/20000 h−1 >90 225–450 — [327]
Ni0.04Ce0.81Zr0.15O2 NO/NH3/H2O/CO2/O2 = 0.05:0.05:10:14:14/160000 h−1 40–50 275–375 81 [328]
Ni0.04Ce0.81Zr0.09S0.06O2 NO/NH3/H2O/CO2/O2 = 0.05:0.05:10:14:14/160000 h−1 >80 275–425 — [328]
Mo0.5CeZr2Ox NO/NH3/O2 = 0.05:0.05:5/50000 h−1 >90 220–425 — [338]
10% P/Ce0.75Zr0.25O2 NO/NH3/H2O/O2 = 0.05:0.05:5:5/300000 h−1 >80 300–500 — [346]
10% P/Ce0.75Zr0.25O2 NO/NH3/O2 = 0.05:0.05:5/30000 h−1 >80 250–450 — [347]
ZP/Ce0.75Zr0.25O2 NO/NH3/H2O/O2 = 0.05:0.05:5:5/300000 h−1 >80 240–470 — [346]
F/Ce0.5Zr0.5O2/TiO2 NO/NH3/O2 = 0.06:0.06:6/71400 h−1 >80 290–450 — [330]
9.1% WO3/CexZr1-xO2 (x = 0.58, 0.4) NO/NH3/H2O/CO2/O2 = 0.05:0.05:10:10:10/160000 h−1 >90 275–500 100 [335]
5% Mo/Ce-ZrO2 NO/NH3/O2 = 0.05:0.05:5/98000 h−1 >90 250–400 — [338]
10% WO3/Ce0.68Zr0.32O2 NO/NH3/O2 = 0.05:0.05:5/30000 h−1 >80 213–470 >97 [331]
10% WO3/20%Ti-Ce0.68Zr0.32O2 NO/NH3/O2 = 0.05:0.05:5/30000 h−1 >80 190–500 >99 [331]
15% WO3/ZrO2-Ce0.6Zr0.4O2 NO/NH3/H2O/O2 = 0.1:0.1:5:10/50000 h−1 >80 275–500 87 [334]
Ce1−xZrxVO4 (x = 0.1–0.8) NO/NH3/O2 = 0.05:0.05:5/26000 h−1 >80 150–390 100 [333]
5% V2O5/Ce0.7Zr0.3O2 NO/NH3/O2 = 0.1:0.1:5/70000 h−1 90 200 ~100 [342]
FeW1.1/Ce0.68Zr0.32O2 NO/NH3/O2 = 0.1:0.1:5/30000 h−1 >90 245–455 ~100 [337]
MnOm/Ce0.5Zr0.5O2 NO/NH3/H2O/SO2/O2 = 0.06:0.06:3:0.01:3/30000 h−1 >90 100–220 >85 [340]
MnOm(0.4)/Co0.1Ce0.45Zr0.45O2 NO/NH3/H2O/SO2/O2 = 0.06:0.066:3:0.01:6/45000 h−1 >90 110–250 >85 [341]
15% Nb2O5/Ce0.75Zr0.25O2 NO/NH3/H2O/CO2/O2 = 0.05:0.05:5:12:5/300000 h−1 >90 300–500 ~100 [344]
XNOx, SN2 and Tr are denoted as NOx conversion, N2 selectivity, and reaction temperature range of NO complete conversion, respectively.
acid sites, which weakened the strong oxidation of NH3 but activity and sulfur/water vapor tolerance than W/CZO.
enhanced the NH3 adsorption capacity of catalyst. Therefore, Zhang and Huang et al. [333] developed a series of
the catalytic activity of the catalysts at high temperature was Ce1-xZrxVO4 solid solutions for NH3-SCR of NOx. The introduc-
improved. Moreover, the introduction of sulfates to NiO/CZO tion of Zr into CeVO4 considerably enhanced the specific sur-
led to high NH3-SCR activity and N2 selectivity. The addition of face area, redox property, active oxygen species as well as sur-
sulfates not only promoted the mobility of lattice oxygen by the face acidity of the catalysts, which were favorable for the im-
formation of Nin+-O-Sn+ bond in CZO, but also inhibited NH3 provement of SCR performance. The catalyst Ce0.85Zr0.15VO4
oxidation by reducing the amount of surface active oxygen exhibited the best low-temperature NH3-SCR performance. T50
[329]. was as low as 125 °C for above 80% NO conversion, and almost
Shen and Zhu et al. [330] studied the effect of fluorine addi- 100% N2 selectivity was obtained in the range of 150–375 °C.
tive on CeO2-ZrO2-TiO2 (CZT) for NH3-SCR. A series of CZT cat- Furthermore, the catalysts also showed excellent H2O/SO2 du-
alysts with different fluorine additives were synthesized by an rability and good performance at high GHSV of 400000 h−1.
impregnation method. The (001) facets were exposed on the
catalyst surface with the modulation of HF. The grain size of 4.3.1.2. Effect of active phase types
TiO2 increased and the specific surface area reduced after add- Kröcher et al. [334] prepared a 15% WO3/ZrO2-Ce0.6Zr0.4O2
ing HF. However, the OSC of catalyst could be also enhanced catalyst by the SC method. The catalyst showed more than 90%
with the modulation of HF. In addition, the synergy of (101) NOx reduction efficiency between 300 and 500 °C, and it re-
and (001) facets and the increase of surface chemisorbed oxy- mained almost unchange over the entire temperature range
gen and Ce3+ concentrations were beneficial to the improve- even after being aged at 700 °C. In addition, sulfur poisoning
ment of catalytic activity. CZT-10F exhibited excellent catalytic promoted the reduction efficiency of NOx at high temperatures
performance for NH3-SCR and more than 96% NO conversion at the cost of a decreased low-temperature activity, but the
at 360 °C under GHSV of 71400 h−1. catalyst could be fully recovered by heating in O2 at 650 °C. Can
Wang and Chen et al. [331,332] investigated the effect of ti- et al. [335] investigated the catalytic performance of
tanium additive on a W/CZO monolithic catalyst for NH3-SCR of CZO-supported WO3 catalysts for NH3-SCR of NOx. The addition
NOx. The doping of TiO2 led to the formation of ceri- of WO3 on CZO induced a loss of the basic properties, the oxy-
um-zirconium-titanium solid solution with large surface area. gen mobility, and the oxidation capacity of NO to NO2, but it
The interactions among metal oxides promoted the reductive also led to a significant enhancement of NH3 storage capacity,
behavior of the catalyst, which was helpful to enhance the which seemed to play a significant role in NH3-SCR reaction at
NH3-SCR activity at low temperature. Moreover, the addition of high temperatures [336]. The changes in acid-base properties
TiO2 to CZO improved the adsorption and activation of NH3 and resulted in the enhancement of NH3-SCR performance. All
increased the reactivity of adsorbed nitrate species with NH3 WO3/CZO materials exhibited more than 80% NOx reduction
species, and WO3/CZT with 20% TiO2 showed better deNOx efficiency for NH3-SCR at 350 °C in the presence of H2O and CO2
in feed gas. Xu and Chen et al. [337] reported that W/Fe ratio of redox behavior. The V2O5/CZO catalyst exhibited high activity
FeWm/Ce0.68Zr0.32O2 (m = 0–1.38) monolithic catalysts strongly and selectivity for NH3-SCR of NO and was less prone to unse-
affected the catalytic performance of the catalysts for NH3-SCR lective oxidation of NH3 to N2O. The effect of Nb loading
of NOx. The FeW1.03/Ce0.68Zr0.32O2 catalyst displayed the best amounts on the active sites and surface acidity of NbOm/CZO
catalytic performance, which exhibited 95% NOx conversion for NH3-SCR of NOx was studied by Wu et al. [344]. The catalyst
and nearly 100% N2 selectivity ranging from 250 to 435 °C. with 15% Nb2O5 showed the best NH3-SCR activity and almost
This should be due to the more chemically adsorbed oxygen 100% N2 selectivity in the temperature range of 190–460 °C at
species and Fe3+ active species as well as surface acid sites, a high space velocity of 300000 h−1. Altering the Nb loading
which together contributed to the excellent catalytic activity of amount would lead to the change in the structure and distribu-
the FeW1.03/Ce0.68Zr0.32O2 catalyst. tion of surface supported NbOm species and evolution of elec-
The effect of Mo addition on CZO catalysts for NH3-SCR of tronic interaction between Nb species and CZO support. The
NOx was studied by Liu and He et al. [338]. The addition of Mo electron transfer effect from Nbn+ to Cen+ would result in the
inhibited the growth of CeO2 particles, improved the redox increase of Ce3+, oxygen vacancies, and active oxygen. Moreo-
ability, and increased the amount of surface acidity, especially ver, the total surface acidity of the catalyst was remarkably
the Lewis acidity. All of the characteristics were responsible for enhanced after Nb loading, which could promote NH3 adsorp-
the excellent NH3-SCR performance. Among these, the tion and suppress the NH3 unselective oxidation and be espe-
CeMo0.5Zr2Ox catalyst showed the best SCR activity, SO2/H2O cially beneficial to SCR of NOx at high temperatures (> 300 °C).
durability, and thermal stability. Interestingly, Liu and Li et al. Furthermore, the increased cerium sites with adjacent active
[339] further confirmed the professional effect of Mo additive oxygen contributed to the highly catalytic activity of the
and proposed that the highly dispersed MoO3 not only induced NbOm/CZO catalyst at low temperatures. The effect of Nb in-
the formation of more Brønsted acid and Lewis acid sites on the troduction on the catalytic activity and hydrothermal stability
catalyst surface, but also promoted the redox property of the of CZO catalyst for NH3-SCR of NOx was reported by Liu and He
catalyst. They should be accounted for the enhanced SCR activ- et al. [345]. Nb additive to CZO not only increased the specific
ity. surface area and enhanced redox property, but also boosted the
A series of Mn/CZO catalysts with different Mn loading NH3 adsorption and activation and promoted the reactivity of
amounts were prepared to investigate the NH3-SCR perfor- adsorbed nitrate together with NH3 species. All of the above
mance of NO at low temperature. When Mn loading amounts characteristics were responsible for the excellent NH3-SCR
increased, NO conversion on MnOm/Ce0.5Zr0.5O2 first increased performance. The CeNb3Zr2Ox catalyst exhibited superior SCR
and then decreased. When Mn/(Ce + Zr) = 0.6, the activity activity, high N2 selectivity, and excellent hydrothermal dura-
reached the best. The Ea value of MnOm/Ce0.5Zr0.5O2 catalyst bility, which still possessed high reductivity and abundant acid
was 18.1 kJ/mol, which was lower than that of MnOm/TiO2 (38 sites after being aged at 800 °C.
kJ/mol) [340]. Zhang and Shi et al. [155] combined the experi- Si et al. [346] investigated the effect of zirconium phosphate
ment and theory to investigate MnOm/CZO nanorods for addition to Ce0.75Zr0.25O2 (ZP/CZO) on NH3-SCR of NO. The
low-temperature NH3-SCR of NO. MnOm on the surface of na- ZP/CZO catalyst showed superior catalytic activity and good N2
norods or Mn@CeO2(110) could easily produce a oxygen va- selectivity at 250–450 °C under high space velocity of 300000
cancy distortion. Moreover, the Mn@CeO2(110) model in the h−1 owing to the following two main factors. First, the zirconi-
DFT analysis showed a prominent effect on NO and NH3 ad- um phosphate provided adsorption sites for NH3 on the catalyst
sorption, which resulted in a stronger nitrite intermediate surface, and the cerium sites acted as the redox sites for NO
(NOO*) formation and more attractive interaction with NH3 gas oxidation. The two distinct adsorption sites for NH3 and NOx
compared with those observed in the CeO2(110) model. A con- resulted in a close contact between ads-NH3/NH4+ and
trastive study on the difference between the introduction of ads-NO3−/NO2− species on the ZP/CZO catalyst (as illustrated in
cobalt in the active component and the support of Mn/CZO was Fig. 20), which could rapidly react with NO together with active
made by Shen et al. [341]. Mn/Co-CZO exhibited a higher cata- surface lattice oxygen. Second, the pre-combination of zirco-
lytic activity compared with Mn/CZO and Mn-Co/CZO because nium and phosphate could lower the interactions between
of the highly dispersed manganese oxides, good redox proper- phosphates and cerium ions. Thereby the mobility of surface
ties, more surface acid sites, and surface adsorbed oxygen spe- lattice oxygen on the Ce0.75Zr0.25O2 catalyst was maintained,
cies as well as more Mn4+ ion. Furthermore, Mn/Co-CZO also which was beneficial to obtaining a catalyst with high NH3-SCR
exhibited an outstanding SO2 and H2O-resistance. activity at low temperatures. Subsequently, the modification of
Brückner et al. [342] investigated NH3-SCR of NO at low Ce0.75Zr0.25O2 by phosphate could enhance the hydrothermal
temperature over VOm/CexZr1-xO2 (x = 0–1.0) catalysts. 5% stability and sulfur resistance of the catalyst [347].
VOm/CexZr1-xO2 catalysts with x = 0.7–0.9 seemed to be prom-
ising catalysts, which exhibited almost 100% of both NO con- 4.3.1.3. Effect of preparation condition
version and N2 selectivity at 220 °C, and no deactivation took Effect of calcination temperature on the structure and cata-
place during at least 190 h under a space velocity of 70000 h−1. lytic performance of the WO3/CZO monolithic catalyst for
Reddy et al. [343] studied the effect of acidic and redox proper- NH3-SCR of NOx was studied by Wang and Chen et al. [348]. SCR
ties of a V2O5/CZO catalyst in NH3-SCR of NO. SCR activity of catalytic activity of WO3/CZO was greatly enhanced by mod-
V2O5/ZrO2 was related to the support crystallinity, acidity, and estly rising the calcined temperature. WO3/CZO calcination at
of NO2 reacted with two adjacent NH4+ to generate active com-

plex NO2(NH4+)2. NO2(NH4+)2 finally reacted with one molecule
of NO to produce N2 and H2O and thus finished the catalytic
cycle.
4.3.2. H2-SCR
Until the full transition to the hydrogen economy and zero
emissions of greenhouse gases are realized, H2-SCR might be
considered as a breakthrough NOx control technology in favor
of the current popular NH3-SCR. In 2014, Efstathiou et al. [354]
for the first time reported the catalytic activity of W-promoted
CZO (Ce-rich or Zr-rich) solids towards H2-SCR of NOx. In the
range of 250–350 °C and at GHSV = 51000 h−1, NOx conversions
Fig. 20. Illustration of NH3-SCR reaction route on zirconium phos- were in the 30%–55% range with 85%–92% N2 selectivity (Fig.
phate-CZO. Reprinted from [346] with permission.
21). A good stability of both Zr-rich and Ce-rich W/CZO cata-
lysts was also obtained at 300 or 250 °C even after 66 h on-line
500 °C exhibited the lowest light-off temperature of 173 °C and reaction. The introduction of about 7 vol% H2O in the feed
total conversion temperature of 205 °C, while WO3/CZO calci- stream resulted in a 10%–15% drop in NOx conversions in the
nation at 600 °C showed a broader temperature range range of 250%–300 °C, but an improvement in N2 selectivity by
(220–455 °C) with more than 90% NOx conversion. The calci- about 5%. Moreover, the specific integral reaction rate of
nation temperature at 500 °C for WO3/CZO was favorable for Zr-rich W/CZO towards H2-SCR in the range of 250–350 °C was
stabilizing the structure, increasing the amount of acid sites, as 2–3 times as that on Ce-rich W/CZO solid. Recently, Li et al.
Ce3+, and surface active oxygen species, as well as enhancing [355] prepared a Pd catalyst with highly dispersed Pd
reductivity of the catalyst. All of these together contributed to nanoclusters on an Al-doped CZO mixed oxide for
its better deNOx activity at low temperatures. Zhang et al. [349] low-temperature H2-SCR of NOx with excess O2. The introduc-
investigated the catalytic properties of CeO2-ZrO2-WO3 (CZW) tion of Al into CZO could effectively reduce the crystallite size
catalysts synthesized by various methods for NH3-SCR of NOx. and enhance the specific surface as well as increase the surficial
The CZW catalyst prepared by a hydrothermal method exhib- Ce3+ concentrations and adsorbed oxygen species. As a result, a
ited the optimal performance in the range of 175–450 °C due to remarkable hydrogen spillover ability was achieved. The sup-
the high specific surface area, the good redox behavior, the ported Pd nanoclusters showed 84% NOx conversion in the
large amount of Ce3+, and the chemisorbed oxygen species. temperature range of 100–300 °C.
Moreover, the highly dispersed WO3 species over CZO and the Liotta et al. [356] investigated the effect of the strong met-
abundant Brønsted acid sites were also responsible for the al-support interaction (SMSI) on the catalytic activity of a
excellent SCR activity. Pt/Ce0.6Zr0.4O2 catalyst for H2-SCR of NOx. The catalytic activity
was enhanced for the catalyst pre-treated in H2 at 350 °C com-
4.3.1.4. Mechanisms of NH3-SCR of NOx over nanosize pared with the samples performed at 800 and 1050 °C. Moreo-
ceria-zirconium-based solid solutions ver, transient reactivity tests of NO reduction by H2 were also
According to the studies of Gong et al. [350], Cai et al. [351], conducted. As expected, the sample pre-reduced at 350 °C
Brü ckner et al. [352], and Lee et al. [353], the mechanism of showed higher activity. The pretreatments had no effect on the
NH3-SCR of NOx over CZO followed two distinct reaction path- N2 selectivity at the temperature of the maximum NOx conver-
ways, the L-H mechanism at low temperature (< 200 °C) and sion. Therefore, it demonstrated the presence of SMSI effect
the E-R mechanism at high temperature (> 200 °C): between Pt and ceria and the important role of Pt in promoting
O 2(g )  2  2O   the CZO structural reorganization. Such type of interaction de-
(25) termined a decrease of Pt and ceria reduction temperature and
NO(g)  O   NO2(a )
(26) a stabilization of Pt oxide even in reducing atmosphere at high
2NH 3(g)  2H   2NH 4 (a ) (Br nsted acid site) temperature. Efstathiou et al. [357] reported a series of
(27)
2NH 4  NO 2(a )  NO 2 (NH 4 2 Pt/CexZr1-xO2 (x = 0.4–0.6) solids to be used for the SCR of NO
(28) under lean burn conditions (2.5% O2) using C3H6 and H2 as
NO 2 (NH 4 2  NO    2N 2  3H 2 O  2H  ( 200 o C)
(29) reducing agents. These Pt/CexZr1-xO2 catalysts showed signifi-
NH3(g)  NH3(a ) (Lewis acid site) cant differences for H2-SCR performance in the range of
(30)
NH 3(a )  NH 2(a )  H   e  120–180 °C but practically exhibited the same catalytic behav-
(31)
ior at higher temperatures. It was proved that the active NOx of
NH 2(a )  NO (g)  NH 2  (a )  N 2  H 2 O
(32) H2-SCR path resided within a reactive zone around each Pt na-
In this SCR reaction, gaseous NH3 molecules were first ad- noparticle, which extended to less than one lattice constant on
sorbed on the Brønsted acid sites to generate NH4+ ions. the support surface. In addition, a remarkable activity and N2
Meanwhile, NO molecules were also adsorbed on the catalyst selectivity enhancement was observed at temperature above
surface and were oxidized to NO2 adspecies. Then one molecule 400 °C when both H2 and C3H6 reducing agents were used
Fig. 21. (a) NOx conversion (XNOx, %), H2 conversion (XH2, %), (b) N2 selectivity (SN2) and N2O formation (ppm) in H2-SCR as a function of temperature
over W-CeZr catalysts. Reaction conditions: 520 ppm NOx (NO:NO2 = 9:1), 1.0% H2, 5% O2, 10% CO2 and He as balance gas, GHSV = 51000 h−1. Re-
printed from [354] with permission.
compared to H2-SCR or C3H6-SCR alone. This synergy effect was the chemical stability of CH4 implies high activation tempera-
explained to arise mainly because of the increase of θH in the ture and, usually, a poor selectivity towards the reduction of NO
presence of −CHx species derived from adsorbed C3H6 decom- by CH4 is obtained. Therefore, only a limited number of noble
position on Pt, which blocked sites of oxygen chemisorption. metals can act as the active component, such as Pd
The increase of surface oxygen vacancies promoted the for- [355,362–365]. In 2004, Granger et al. [366] explored CH4 as
mation of a more reactive chelating nitrite (NO2−) species com- alternative in SCR of NO in the presence of oxygen over Pd/CZO
pared to the case of H2-SCR. under lean conditions. The activation procedure under O2 or H2
drastically influenced the catalytic performance of the catalyst.
4.3.3. HC-SCR Pd/Ce0.52Zr0.48O2 showed a higher activity and a better N2 selec-
Although SCR of NOx by NH3 or urea has proven to be an ef- tivity under O2 than that under H2, indicating that oxygen could
fective method for reducing NOx emissions, there are several enhance the activity. Moreover, the stabilization of a metallic or
problems inevitably existing in the present NH3-SCR technolo- oxidic Pd phase led to poor activity in the conversion of NO in
gy, such as NH3 slip, air-heaters fouling storage hazards, ash the absence of oxygen. Azambre et al. [367] reported Pd sup-
odor, equipment corrosion, and high running cost. Thus, a very ported on sulfated CZO catalysts for CH4-SCR of NOx and inves-
significant market potential exists for an improved technology tigated the correlation between catalytic performance and na-
in this area. As a result, SCR of NO by HC derived from on-board ture of active Pd species. The catalytic activity was mainly de-
fuel has attracted a lot of attention in the past years pendent on the Pd loading amount. At low Pd loadings,
[320,358-361], as displayed in Table 7. Brönsted acidity of the sulfated support was beneficial to stabi-
lizing Pd to form highly dispersed Pd species, which existed as
4.3.3.1. CH4-SCR [(PdO)m-H]n+ adducts located in the vicinity of sulfate species.
As the main component of natural gas, CH4 is an attractive The corresponding 0.24%–0.53% Pd/sulfated-CZO catalysts
reductant of NOx for a number of power sources. Nevertheless, exhibited 30%–35% NOx conversion to N2 around 370 °C. By
Table 7
Catalytic activity of nanosize CZO materials in HC-SCR of NOx.
Catalyst Reaction conditions XNO (%) Tr (°C) SN2 (%) Ref.
Ce0.7Zr0.3O2 NO/HC/O2 = 0.0247:0.025:5/30000 h−1 9–27 180–430 — [373]
3%W-CZO NO/NO2/H2/O2/CO2/H2O = 0.0468:0.0052:1/5/10/7/51000 h−1 56 300 77–92 [354]
1% Ni/Al-CexZr1−xO2 NO/NO2/H2/O2 = 0.09:0.01:1:5/60000 h−1 10–12 100–300 — [355]
4% Cu-1% Ag/Ce0.75Zr0.25O2 NO/HC/O2 = 0.2:0.2:10/30000 h−1 56–89 335–550 — [372]
0.1% Pt/Ce0.5Zr0.5O2 NO/H2/O2 = 0.015:0.8:2.5/33000 h−1 60–92 170–300 70–82 [357]
0.1% Pt/Ce0.5Zr0.5O2 NO/HC/O2 = 0.015:0.5:2.5/33000 h−1 50 350 78 [357]
0.1% Pt/Ce0.5Zr0.5O2 NO/H2/HC/O2 = 0.015:0.8:0.5:2.5/33000 h−1 100 450–600 95–98 [357]
1% Pt/Ce0.5Zr0.5O2 NO/HC/O2 = 1:3:3/40000 h−1 80 500 — [375]
1% Pt/Ce0.6Zr0.4O2 NO/HC/O2 = 0.1:0.1:5/60000 h−1 60 250 74 [356]
1% Pd/Al-CexZr1−xO2 NO/NO2/H2/O2 = 0.09:0.01:1:5/60000 h−1 >84 100–300 — [355]
0.89% Pd/Ce0.68Zr0.32O2 NO/HC/O2 = 0.034:0.19:8/112500 h−1 29 243 87 [369]
1% Pd/Ce0.2Zr0.8O2 NO2/CH4 = 1:1/4200 h−1 100 495–700 100 [368]
Sulfated 1% Pd/Ce0.52Zr0.48O2 NO/CH4/O2 = 0.015:0.15:7/40000 h−1 5–15 250–500 — [367]
0.52% Rh/Ce0.62Zr0.38O2 NO/HC/O2 = 0.0247:0.025:5/30000 h−1 52 360 — [374]
0.4% Rh/Ce0.5Zr0.5O2 NO/HC/O2/H2O = 0.05:0.1167:0.5/500000 h−1 100 400–600 — [370]
0.44% Rh-0.54%Pd/Ce0.68Zr0.32O2 NO/HC/O2 = 0.034:0.19:8/112500 h−1 28 288 81 [371]
0.44% Rh-0.91%Pt/Ce0.68Zr0.32O2 NO/HC/O2 = 0.034:0.19:8/112500 h−1 16 289 85 [371]
XNOx, SN2 and Tr denote NOx conversion, N2 selectivity, and reaction temperature range of NO complete conversion, respectively.
contrast, higher Pd loading amounts were detrimental for the 1827.2 ppm of NO, and 1908.1 ppm of C3H6 concentration cor-
SCR reaction due to the promoted formation of PdOm clusters, responding to NO conversion of 82.9%.
which showed more active in the selective oxidation of CH4. In
addition, the introduction of H2O to the feed was unfavorable 4.3.3.3. Other CxHy-SCR
due to the prevention of NOx and CH4 sorption at low-medium Compared with CH4-SCR and C3H6-SCR, more research has
temperatures. The reaction intermediates involved in CH4-SCR been performed on SCR of NOx with a mixture of HC repre-
and the factors controlling the reactivity of Pd/CZO catalyst sentative of the exhaust gas from fossil fuel combustion (C3H8,
were studied by Azambre et al. [368]. By DRIFTS of adsorbed C3H6, and C7H8) over CZO catalysts. Costa et al. [373] studied
CO, it was found that Pd species on Ce0.2Zr0.8O2 were mainly the relationship between the surface properties and deNOx
present in Pdx+ ionic form surrounded by surface oxygens or activity of CZO. CexZr1-xO2 (x = 0.17–0.8) were active in deNOx
small PdOm clusters cationic form. The investigation of temper- reaction, and their catalytic activities varied with the different
ature-programmed surface reaction in CH4 + NO2 atmosphere cerium amounts and reached the maximum for x = 0.62 with
indicated that CH4-SCR reaction on Pd/Ce0.2Zr0.8O2 was initiated 27% NOx transformation to N2 at 322 °C. Subsequently, Costa et
at 280 °C and yielded almost 100% N2 above 500 °C. al. [374] investigated CZO-supported rhodium catalyst for NOx
DRIFTS-MS and TGA experiments showed that deNOx activity reduction, and the catalytic activities were evaluated by iso-
was due to a surface reaction between adsorbed COx species, thermal steady-state experiments using a mixture of exhaust
which were generated by CH4 activation on reduced Pd sites gases of HC. The addition of Rh on Ce0.62Zr0.38O2 considerably
with ad-NxOy species presumably located on the support. The improved the catalytic activity during the deNOx process as-
detrimental effect of O2 on deNOx was due to the promotion of sisted by HC, and decreased by about 34 °C for the temperature
the complete combustion of CH4 assisted by the ceria-zirconia of NOx conversion to N2, which went up to 57%. The effect of
component at the expense of SCR reaction above 320 °C. support on the three-way catalytic HC-NO-O2 reaction over
Pt/CZO catalysts under reducing conditions was investigated
4.3.3.2. C3H6-SCR by means of operando X-ray absorption near edge structure
Compared to H2, CH4, much more efforts have been made to [375]. The formation of active metallic Pt sites and the
improve NO removal using C3H6 as reductant. Thomas et al. self-poisoning effect of adsorbed carbonaceous species on me-
[369] investigated C3H6-SCR of NOx on Pd/Ce0.68Zr0.32O2 cata- tallic Pt should determine the start-up behavior of catalytic
lysts (Pd/CZO). The addition of Pd to CZO significantly pro- reaction over supported Pt catalysts. The oxygen reactivity in
moted the reduction of NO by C3H6, and the catalyst still exhib- the support oxide was also important for reducing the catalytic
ited relative high deNOx activity even in the presence of 1.7% start-up temperature in addition to the suitable Pt reduction
H2O. Pd/CZO displayed much higher N2 selectivity than temperature.
Pd0/SiO2, indicating that the lean deNOx mechanism occurring
on these catalysts should be different from that of Pd0/SiO2. 4.3.3.4. Mechanisms of HC-SCR of NOx over nanosize
Haneda et al. [370] studied the catalytic performance of Rh ceria-zirconium-based solid solutions
supported on CZO for C3H6-SCR of NO. The catalytic activity of The reduction mechanism of NOx by HC over CZO is very
Rh/CZO strongly depended on the Ce/Zr ratio. Rh/Ce0.50Zr0.50O2 complex [376–381]. According to the mechanism proposed by
showed the best activity. Moreover, the activity of Rh/CZO for Djéga-Mariadassou et al. [379] (as shown in Fig. 22), the first
C3H6-SCR of NO also depended on the reaction gas conditions. step of this catalyst is to oxidize NO to NO2. The second step is
The presence of O2 could inhibit NO reduction by C3H6, espe- the mild oxidation of HC by NO2 to form oxygenate species,
cially for Rh/Ce0.74Z0.26O2. The effect of the nature of platinum which plays an important role in the catalyst regeneration
group metals (PGMs: Pd, Rh, Pt) on the lean C3H6-assisted re- process. The release of N2 occurs in step 3. It involved NOx dis-
moval of NO on Ce0.68Zr0.32O2-supported catalysts was investi- sociation and followed by the formation of N2 and scavenging of
gated by Thomas et al. [371]. The order of reactivity of the adsorbed oxygen species left from NO dissociation. The
CZO-supported PGMs was Pd ≥ Pt ≥ Rh, and CZO-supported removal of the adsorbed oxygen was due to the total oxidation
catalysts exhibited higher N2 selectivity than those supported of an activated reductant (CxHyOz). In addition, both steps 2 and
on SiO2 or Al2O3. The higher catalytic activity of Pd-based cata- 3 have to turn over simultaneously. However, at the molecular
lysts for C3H6-SCR of NOx might be associated with the greater level, the both steps were not in the same catalytic cycle.
ability of the PdOx phase to adsorb NO2.
Amin et al. [372] studied the catalytic activity of
CZO-supported Cu and Ag for C3H6-SCR of NO. Compared to
Cu(4)/Ag(1)/CeO2, Cu(4)/Ag(1)/Ce0.75Zr0.25O2 displayed higher
deNOx activity in the range of 250–350 °C. The SMSI and high
redox property of the support exhibited by the
Cu(4)/Ag(1)/Ce0.75Zr0.25O2 catalyst were considered to be the
main reasons of the improvement of C3H6-SCR performance. In
addition, reaction temperature was found to affect NO reduc-
tion activity more significantly than NO and C3H6 concentra- Fig. 22. Catalys-assisted de NOx reaction: each cycle corresponds to one
tions. The optimum conditions were estimated to be 415.4 °C, function (F1, F2, and F3).
4.3.4. CxH2x+1OH-SCR does not need any reductants and is simple and economical. NO
For deNOx reaction, it has been reported that when a hy- is thermodynamically unstable. However, it does not decom-
drocarbon is able to catalytically reduce NOx, its corresponding pose easily due to its high Ea value (364 kJ/mol). Therefore, a
alcohol must also be useful for such a process [382]. The role of proper catalyst is needed to lower Ea value in order to facilitate
CH3OH in the reduction of NOx to N2 was investigated over the decomposition. Research in this domain has been exten-
H3PW12O40-Pt/CZO [383]. The reduction of NOx went through sively performed on noble metal-supported catalysts
two stages. First, during the lean mode for 2 min, NOx (NO/NO2 [387,388], metal oxides [389–394], carbon [395–397], and
= 1) were stored in the catalyst; second, they were reduced into zeolite-based catalysts [398–404]. Whereas, little research was
N2 during the rich period (CH3OH injection 1 min). With CH3OH, reported on the direct decomposition of NOx over CZO-based
NOx storage efficiency of H3PW12O40-Pt/CZO was stable and catalysts. Cheng et al. [405] prepared nanosize CZO-supported
high (ca. 100%), and about 55% of stored NOx were reduced H3PW12O40 (HPW) for NO capture and decomposition. CZO
into N2 by alternative lean/rich cycles. CxHyOz intermediate exhibited remarkable promotion effect on the capture of NOx.
species derived from methanol were thought to be the inter- For HPW/CZO prepared by a mechanical grinding method, NOx
mediate reductants for NOx. adsorption efficiency was considerably enhanced with increas-
Azambre et al. [384] studied the catalytic performance of ing HPW loading amounts in the range of 20%–70%. However,
sulfated CZO catalysts for SCR of NOx by ethanol. The sulfated the deNOx efficiency decreased with increasing loading of HPW
CZO catalysts were prepared by direct sulfation of the crystal- (> 70%). Subsequent to the adsorption process, the adsorbed
lized CZO nanopowders with 0.5 mol/L H2SO4. The sulfation NOx decomposed to N2 upon heating from 150 to 450 °C, with a
treatment enhanced the SCR activity via the promotion of al- N2 yield of 27.3%. Yang et al. [406] reported a Ce-Cu-Zr/ZSM-5
ternative pathways for the formation of N2 and the prevention catalyst prepared by an ion-exchange method showing high
of combustion reactions at medium temperatures. Moreover, catalytic activity for NO decomposition in the presence of O2,
NOx conversion was shown to exceed 30% on most of SCR cat- and the highest NO conversion was up to 75%. This indicated
alysts in the range of 250–400 °C. Above 350–400 °C, the N2 that the introduction of CZO could promote the formation of a
selectivity was close to 100% and an optimum deNOx yield of new highly active site, which facilitated oxygen mobilization
48% was achieved for a sulfated catalyst with a Ce molar frac- and desorption, thereby enhanced the activity of catalysts.
tion of 0.5. Azambre and his coworkers [385] further studied
the effect of Ag, Pd and Co additive on the SCR of NOx by ethanol 4.4.2. N2O direct decomposition
over sulfated CZO catalysts. The metal promoters have a dis- Besides NO, nitrous oxide (N2O) has drawn ever increasing
crete effect on C2H5OH-SCR activity, often negative and some- attention in the past decades because of its detrimental green
times positive. Positive effects essentially arised from the for- house effect and ozone-depleting action [322,407–410]. Thus,
mation of acetaldehyde, which was the most effective reductant the development of highly active catalysts to purify N2O is be-
of the system. It occurred mostly in the presence of Ag species coming an important issue. Imamura et al. [411] investigated
in the +1 oxidation state. By contrast, the Pd catalyst was not the effects of structural composition and calcination tempera-
effective for C2H5OH-SCR because it induced a depletion of the ture of the catalysts on the catalytic performance of Rh/CZO for
organics needed for NOx reduction by promoting total oxida- N2O decomposition. The incorporation of Zr into ceria signifi-
tion reactions. Another negative effect was the inhibition of the cantly enhanced its thermal stability to retain high specific sur-
most active cerium sites of the support, which led to a decrease face area even at the calcination temperature of 900 °C.
of the SCR activity at low temperatures and the shift of deNOx Rh/Ce0.7Zr0.3O2 exhibited the optimal catalytic activity due to
window towards the high temperatures. the highly dispersed Rh species exposed to the support surface.
Djéga-Mariadassou et al. [386] investigated the catalytic Nevertheless, too high calcination temperature (1200 °C) led to
performance of 1-propanol-assisted reduction of NOx over a the remarkable decrease of catalyst surface area and the ag-
Ir/Ce0.6Zr0.4O2 catalyst. This catalytic material showed a pro- gregation of Rh.
motional effect of iridium on the conversion of NOx. So far, NOx direct decomposition over metal surfaces, oxides,
Ir/Ce0.6Zr0.4O2 exhibited a higher NOx reduction (25% at 225 or zeolites is faced to some serious practical difficulties. NOx
°C) than Ce0.6Zr0.4O2 (19% at 260 °C). 1-Propanol was activated decomposition process is a high-temperature reaction, which is
at lower temperatures over the Ir catalyst. Moreover, R-NOx undesirable. NOx dissociation over single crystal metal easily
species were found to be the intermediates of the deNOx pro- reoxidizes the metal surface, which in turn hinders the NOx
cess, which provided the partially oxidized species required by dissociation process. So, a reducing agent is needed to scavenge
the deNOx model. the dissociated oxygen. From an exhaust catalysis view, it is not
sufficient to dissociate NOx, and other pollutants like CO and HC
4.4. Nanosize ceria-zirconium-based solid solutions for NOx should also be oxidized. Therefore, NOx reduction by H2, HC,
direct decomposition and NH3 is more attractive for NOx abatement.
4.4.1. NO direct decomposition 4.4.3. Mechanisms of NOx direct decomposition over nanosize
Although several methods exist to eliminate NO, direct de- ceria-zirconium-based solid solutions
composition of NO to N2 and O2 (NO → 1/2N2 + 1/2O2) is It is widely accepted that N2O decomposition is a sensitive
recognized to be one of the most attractive methods because it reaction to oxygen mobility.
N 2 O    N 2 O toward NO + CO reaction. However, based on the results dis-

(33)

N2O  N2  O  played in Fig. 23, there was no obvious correlation between
(34)
acidity and catalytic activity for NO + CO reaction over
2O  O 2  2
(35) Pt/WO3/CeO2/ZrO2 catalysts in the absence of oxygen. With
In this mechanism, the asterisk (*) is a coordinatively un- excess oxygen, Pt/WO3/CZO and Pt/WO3/ZrO2 catalysts
saturated site of oxidic transition for N2O adsorption. The first showed higher NO conversion to N2 and N2O particularly at low
step for N2O decomposition was the adsorption of N2O followed temperature. This was attributed to the enhanced acidity from
by its decomposition, leading to N2 formation in association ZrO2 and WO3 in the Pt/WO3/CeO2/ZrO2 catalysts in the pres-
with surface oxygen. In this classical model, oxygen formation ence of excess oxygen.
occurred through recombination of two adsorbed atomic oxy-
gen species (O*) or through reaction of N2O with adsorbed 4.5.2. Pd-based ceria-zirconium catalysts
atomic oxygen species. Wang et al. [420] prepared a series of mesoporous
Ce0.6Zr0.4O2 solid solutions with cationic defects by a surfac-
4.5. Nanosize cerium-zirconium-based solid solutions for tant-controlled synthesis method, and the pore size of
simultaneous removal of CO and NOx Ce0.6Zr0.4O2 could be governed by the incorporation of the sur-
factant into solid network and the calcination temperature. In
The simultaneous removal of CO and NOx in the presence or the cold start of reaction, NO reduction by CO with excess oxy-
absence of O2, CO2, and H2O is a proper model reaction, which is gen over the 3% Pd/Ce0.6Zr0.4O2 catalyst presented 100% se-
different from real automobile exhaust emission. However, the lectivity to N2. At reaction temperatures below 200 °C, NO re-
fundamental studies using the supported noble and non-noble strained the oxidation of CO. However, above 200 °C, CO oxida-
metal catalysts were performed to get more insight into the tion showed an inhibition effect on NO conversion, and there
nature of this reaction [412–416], as shown in Table 8. was a reaction competition between NO reduction by CO and
CO oxidation by O2. The key factor of the reaction competition
4.5.1. Pt-based ceria-zirconium catalysts was the concentration of CO and O2. The different oxygen con-
Rao et al. [417] reported CZO-supported Rh catalysts for NO centration also influenced Pd state. High coverage of Pd surface
+ CO reaction. The activation of the reductant was difficult on by oxygen was favorable for NO oxidation to NO2 but sup-
the bare support, and the presence of Rh was necessary to ac- pressed NO decomposition to N* and O*. Fernández-García et al.
tivate and spill it over to the support. Moreover, the bulk oxy- [421] investigated the light-off behavior for CO + NO reaction
gen vacancy played an important role in promoting NO conver- over Pd/CZO/Al2O3 catalysts prepared by the ME method. The
sion over Rh/CZO catalysts, and oxygen vacancy gradient was promoting effect of CZO was present in both CO oxidation and
indicated as the main driving force for NO dissociation. Ihm et NO reduction reactions, and it was dependent on the charac-
al. [418] investigated the catalytic activities of Pt/WO3/CZO teristics of the promoter and the nature of the reaction. CO
catalysts for NO + CO reaction with or without oxygen. Pt/CeO2 oxidation activity was greatly enhanced by contact between Pd
and Pt/CZO could be readily reduced by CO, while the reduc- and the 3-D aggregated promoter, and the catalytic activity
tion was significantly inhibited with the introduction of WO3 increased with increasing CZO content. Fernández-Garcıa and
for Pt/WO3/CZO. It was due to that WO3 addition suppressed co-workers [422] further studied the catalytic activity of a se-
the formation of the active sites for NO reduction. Pt/WO3/ZrO2 ries of Pd-Cr bimetallic catalysts supported on a CZO/Al2O3
showed a slightly higher activity than Pt/ZrO2. As reported by mixed support for CO + NO + O2 reaction. The catalytic activi-
Regalbuto and Wolf [419], Pt-WO3 adlineation sites exhibited ties of these bimetallic catalysts were strongly influenced by
very high NO dissociation activity and increased the activity the nature of the support. For the Al2O3 support, an interaction
Table 8
Catalytic Activity of nanosize CZO materials in simultaneous removal of CO and NOx.
Catalyst Reaction conditions T (°C) XNO (%) XCO (%) Ref.
1.23CuO/Ce0.67Zr0.33O2 0.05 g/NO:CO/He = 1:2:17/12000 h−1 400 100 — [416]
4% Cu/CexZr1−xO2 0.1 g/NO:CO/He = 0.3:0.3:99.4/50000 h−1 400 100 92~96 [425]
0.4CuO/CexZr1−xO2/γ-Al2O3 0.05 g/NO:CO/He = 1:2:17/12000 h−1 400 100 — [426]
yCuO/CexZr1−xO2 (y = 0.3, 0.6, 0.9, 1.2, 1.5) 0.05 g/NO:CO/He = 1:2:17/12000 h−1 400 100 — [429]
yCo-0.5Cu/Ce0.67Zr0.33O2 (y = 0.08, 0.16, 0.32) 0.05 g/NO:CO/He = 1:2:17/24000 h−1 400 100 (y = 0.08) 90 [428]
0.08Mn-0.5Cu/Ce0.67Zr0.33O2 0.05 g/NO:CO/He = 1:2:17/24000 h−1 400 100 90 [429]
0.5% M/Ce0.6Zr0.4O2 (M = Rh, Pt) 0.04-0.008 g/NO:CO/He = 1:3:96/12000–50000 h−1 400 100 (M = Pt) — [417]
1% Pt/15%WO3-Ce0.65Zr0.35O2 0.5 g/NO:CO/He = 0.5:0.5:99/40000 h−1 400 90 73 [418]
y% Rh/Ce0.65Zr0.35O2 (y = 0.05~1) 0.5 g/NO:CO/O2/He = 0.1:1:0.45:98.45/40000 h−1 400 100 100 [424]
1% Pd/Ce0.5Zr0.5O2 3.4 g/NO:CO/O2/He = 1:1:0.45:97.55/30000 h−1 400 18 100 [421]
3% Pd/Ce0.6Zr0.4O2 0.05 g/NO:CO/O2/He = 0.023:0.0685:1:98.908/70000 h−1 400 70 100 [420]
1% PdNi/Ce0.5Zr0.5O2 NO:CO/O2/He = 0.1:1:0.45:98.45/30000 h−1 400 30 100 [423]
1% PdCr/Ce0.5Zr0.5O2/Al2O3 3.4 g/NO:CO/O2/He = 0.1:1:0.45:98.45/30000 h−1 400 6 68 [422]
XNOx, XCO and T are denoted as NOx conversion, CO conversion and reaction temperature, respectively.
Fig. 23. Catalytic activities for the removal of NO + CO over various catalysts (CO: 0.5%, NO: 0.5%). Reprinted from [419] with permission.
between Pd and Cr existed in the calcination state, and the with 40% N2 yield at 150 °C due to its abundant surface reac-
mixed oxide phase containing Pd+ and Cr3+ appeared to be the tive oxygen sites and high reducibility, and N2 yield > 85% was
main factor leading to the enhancement in CO oxidation and the obtained for all Zr-containing catalysts at 250 °C and above.
decrease in NO reduction compared with the monometallic Gao et al. [426] studied the effects of Ce/Zr molar ratios on the
system. In the case of the CZO/Al2O3 mixed support, the intro- physicochemical properties of CuO/CexZr1-xO2/γ-Al2O3 catalysts
duction of Cr was less influential for catalytic activity. The effect for NO + CO reaction. The ceria-rich catalyst showed higher
of Ni on the catalytic activity of Pd-Ni/CZO/Al2O3 catalysts for activity and TOF value towards NO reduction compared with
stoichiometric CO and NO elimination was investigated by Mar- the pure ceria and zirconia-rich ones due to the difference in
tínez-Arias et al. [423]. A significant dependence on the support the interaction among Cu, CexZr1-xO2, and γ-Al2O3 support. Dong
nature in terms of catalytic changes was produced by Ni. The et al. [427] prepared a series of CuO/CexZr1-xO2 catalysts with
introduction of Ni considerably promoted the CO oxidation different Cu loading amounts and Ce/Zr molar ratios and stud-
activity over the CZO/Al2O3-supported catalyst. This was due to ied the correlation of structural characteristics with catalytic
the changes of Pd distribution over the support, which favored performance for NO reduction by CO. The ceria-rich (pseudo-
the formation of active Pd-CZO interfaces. The significant ex- cubic t'') phase could disperse and stabilize the copper species
tent of such a promoting effect revealed an important role of more effectively and resulted in stronger interaction with cop-
the particle size of CZO component on such catalytic processes. per than the zirconia-rich (t) phase. Furthermore, compared
with the zirconia-rich phase, the synergistic interaction of Cu
4.5.3. Rh-based ceria-zirconium catalysts with ceria-rich phase easily promoted the reduction of copper
Compared with Pt- and Pd-based CZO catalysts, Rh-based species and surface oxygen as well as the activation of ad-
CZO catalysts get relatively less attention. In 2009, Ihm et al. sorbed NO species. Therefore, the CuO/Ce0.8Zr0.2O2 catalyst
[424] prepared CZO by supercritical synthesis and CP methods exhibited the higher activity for NO reduction than
as support for a Rh catalyst. The catalytic activities of the cata- CuO/Ce0.5Zr0.5O2 and the CuO/Ce0.2Zr0.8O2 catalysts.
lysts were investigated for NO + CO reaction. Rh/CZO prepared Compared with CZO-supported mono-metal catalysts, bina-
by a supercritical synthesis method exhibited better reducibil- ry metal oxides possess more active species, which may be
ity and higher thermal stability as well as better performance more favorable for the catalytic reaction of NO + CO. Dong and
for the catalytic reduction of NO by CO than that prepared by a co-workers [428] investigated the activity of binary metal ox-
CP method. CZO prepared by the supercritical synthesis meth- ides Ce0.67Zr0.33O2 supported CuO-CoOm catalysts for the re-
od showed more potential applications as catalyst support due moval of NO and CO. The addition of cobalt species significantly
to its sparsely-agglomerated morphology and higher thermal improved the activity of NO + CO by promoting the reduction of
stability. dispersed copper oxide. FT-IR results further revealed that the
addition of cobalt oxide changed the adsorption type of NO and
4.5.4. Cu-based ceria-zirconium catalysts CO on the catalysts, and oxidized NO dimers into ionic NO3−,
In addition to CZO-supported noble metals (Pt, Pd, Rh) cat- and then these partial surface active species might be reduced
alysts, considerable efforts have been devoted to developing into low-valence state above 300 °C. Subsequently, they inves-
promising Cu-based catalysts for NO + CO reaction. Zhang et al. tigated the effect of MnOm modification on the activity of the
[425] investigated the catalytic activity of 4% Cu/CexZr1-xO2 (x CuO/Ce0.67Zr0.33O2 catalyst for NO reduction by CO [429]. The
= 0–1.0) catalysts for the reduction of NO by CO. The incorpora- introduction of Cu and Mn species induced the expansion of
tion of Zr4+ into CeO2 could stabilize Cu+ species, which was lattice and the decrease of microstrain of CZO, thereby pro-
favorable for the initial reductive chemisorption of NO to N2O. moting the formation of oxygen vacancies. The addition of Mn
Cu/Ce0.75Zr0.25O2 showed an excellent low temperature activity species could promote the reduction of the catalysts and assist
copper oxide in changing the valence and supplying oxygen. and then N2O and CO2 were produced. When the temperature
These reduction behavior was dependent on the loading was over 300 °C, the catalyst could be reduced by CO to Cu+ and
amounts of MnOm and the impregnation procedure. In addition, Co2+ ions. The catalytic reduction of NO to N2 was generated by
the introduction of MnOm could not change the adsorption type CO. The main Cu+ species contributed to N2O reduction by CO,
of NO, but readily facilitated the activation of the adsorbed NO while the dispersed cobalt oxides played an important role in
species. As a result, these factors were responsible for the en- N2O decomposition and reduction by CO, as shown in Eqs. (51)
hancement of activity and selectivity through MnOm modifica- and (52).
tion.
4.6. Nanosize cerium-zirconium-based solid solutions for
4.5.5. Mechanisms of simultaneous removal CO and NO reaction simultaneous removal of NOx and soot
over nanosize ceria-zirconium-based solid solutions
There are two mechanisms related to simultaneous removal The simultaneous removal of NOx and soot using one cata-
CO and NO, the redox mechanism and the organonitrogen lytic material was proposed for the first time by Yoshida et al.
mechanism. The redox mechanism involves an initial dissocia- [435], which seems to be one of the most effective and eco-
tion-chemisorption of NO, which forms a N2O intermediate and nomic after-treatment techniques. The key challenge is to find a
an oxidized surface, and then CO further reduces N2O into N2 catalyst that can achieve a high rate of soot oxidation in com-
and restores the original catalytic surface [237,430]. By con- bination with substantial NOx reduction at sufficiently low
trast, the organonitrogen mechanism includes the generation of temperature. Several kinds of catalysts such as precious metals
isocyanate compounds as an intermediate [431,432]. In the [436–439], transition metal oxides [440], alkaline metal oxides
catalytic reduction of NOx, the two reaction mechanisms may [441], perovskite-like type oxides [442–446], and ceria-based
occur simultaneously, and the contribution of each mechanism oxides [285,447,448] have shown good catalytic activities for
may depend on the reductant type, catalyst nature, and reac- simultaneous removal of NOx and soot. Especially, CZO is one of
tion conditions (temperature, space velocity, concentration, the key components owing to its excellent OSC property and
etc.) [433,434]. Zhang and Kaliaguine et al. [430] proposed that robust stability [156,214].
CO + NO reaction mechanism on Cu/CZO involved the dissocia-
tion and reduction of chemisorbed NOx. 4.6.1. Effect of preparation conditions
At the 50–250 °C low-temperature region: The key features of CZO that exhibited the catalytic perfor-
Cu   NO  Cu 2 NO  (39) mance of the simultaneous removal of NOx and soot were in-
Cu NO   Ce 4  O  Cu 2  NO 2  (nitrite)  Ce3
2
vestigated by Bueno-Lopez et al. [449]. The catalytic activity of
(40)
Cu 2 NO 2   Ce 4  O  Cu 2   NO3 (nitrate)  Ce3
the catalyst for soot combustion was dependent on both spe-
(41) cific surface area and Ce/Zr molar ratio, which closely depend-
2Cu 2 NO   Ce3  Cu 2  NO   Cu 2  Ce3  ed on the preparation procedures, but NOx conversion was very
Cu 2 N 2 O 2 Cu 2  Ce 4  O  2Cu   N 2O  Ce 4  O 
(42) low. The surface distribution of cations was associated with the
Cu 2 N 2 O 2 Cu 2  Ce3  O  2Cu   N 2  Ce 4  O  homogeneity of CZO according to the different synthesis pro-
(43)
At the high-temperature range above 250 °C: cedure. The specific surface area of CZO was usually lower than
Cu  NO  CO  Ce3  Cu  NCO  Ce 4 O  (44) 90 m2/g. Nevertheless, constant T50 could be obtained for the
Cu  NCO  Cu   NO  2Cu   N 2  CO 2 catalysts with specific surface areas above this value, i.e., there
(45) was a minimum temperature that could be lowered by in-
Cu  NCO  Ce 4 O   Cu   Ce3  1 / 2N 2  CO 2
(46) creasing the surface area of the catalyst (Fig. 24).
Oxidation of intermediate carbonaceous species: The effect of the cerium precursor salt on the catalytic activ-
Ce 4  O   CO  Ce 4   COO   CO 2  Ce3 ity of CZO for the removal of NOx and soot was reported by
(47)
Ce 4  O   CO 2  Ce3  carbonate García-García et al. [450]. CZO prepared with (NH4)2Ce(NO3)6
(48)
showed higher catalytic activity than the counterpart catalysts
Sun and Dong et al. [428] reported a possible reaction
prepared with a Ce(NO3)3·6H2O precursor, and ceria-rich cata-
mechanism over CuCo/CZO catalysts for NO + CO reaction:
lysts with ceria-rich exhibited better catalytic performance
than the corresponding zirconia-rich ones.
(49)
4.6.2. Effect of rare earth doping
The property of CZO can be adjusted by dopants, and thus
(50) their catalytic activity for the elimination of NOx and soot is
Cu   N 2 O  Cu 2  N 2 O   N 2  Cu 2 O  

Cu  CO
 Cu   CO 2 enhanced. Dulgheru et al. [451] studied the effects of rare earth
(51) (La, Nd, Pr)-modified CZO for catalytic removal of NOx and soot.
Co2  N2O  Co3  N2O  N2  Co3O  Co2  O2 
CO
 CO2
(52) The rare earth dopants increased the activity of CZO. Especially,
NO was assumed to preferentially adsorb over dispersed the doping of La and Pr significantly enhanced the
copper oxide or oxygen vacancy sites of CZO to form chelating low-temperature activity due to the increased formation of
nitrite and cis-N2O22− below 300 °C (Eqs. (49) and (50)). These NO2. Whereas, the effect was less pronounced for a Nd-doped
adsorbed NOx species reacted with CO activated by Cu+ species, sample. Bueno-López et al. [452] investigated the effect of Nd
NO can be oxidized to NO2 by the catalyst owing to the thermal

equilibrium compositions. Therefore, most of NO is not reduced
and directly emitted to atmosphere, which can result in great
harmful to human health. Thus, an additional reductant needs
to be added into this reaction process. Based on this considera-
tion, Cheng et al. [181,182,184] prepared a Fe-doped 3DOM
CZO material that could simultaneously remove soot and NOx
from diesel engine exhausts. Ammonia was used as a reductant
for NOx removal. 3DOM Ce-Zr-based mixed oxides were syn-
thesized by a carbon-template method and varied Fe content in
the mixed oxide. Those materials showed high efficiency in
simultaneous removal of NOx and soot in intermediate temper-
atures (285–420 °C with 100% NOx conversion), which essen-
tially meets the demand of diesel engine exhaust emissions.
Fig. 24. T50 versus BET surface area of the catalysts for the removal of Moreover, the addition of Fe to Ce-Zr lowered the temperature
NOx and soot. Reprinted from [449] with permission. of soot combustion to a level that was typically achieved by
more expensive Pt catalysts (Fig. 25). The importance of the
doping on the physicochemical properties and catalytic activity open 3DOM texture in soot capture and combustion was
for the elimination of NOx and soot over CZO. Four oxides in- demonstrated by comparison to a mesopore or particle mixed
cluding CeO2, Ce0.9Nd0.1O2, Ce0.73Zr0.27O2, and Ce0.64Zr0.27Nd0.09O2 oxide of the same composition. Furthermore, DFT calculation
were prepared by a CP method. Ce0.64Zr0.27Nd0.09O2 showed the was used to understand the surface reducibility of the mixed
best catalytic activity due to the improved thermal stability and oxides and gain insight into the role of Fe and surface oxygen
redox properties. Moreover, it was confirmed that the higher vacancies in the reaction mechanism of NOx reduction and soot
activity of Ce0.64Zr0.27Nd0.09O2 was closely related to the for- oxidation. It showed that substitution of Fe in CZO increased
mation of less stable surface nitrates and nitrites species. Thus, the number of oxygen vacancies (Fig. 26), thereby enhancing
it provided alternative and faster NO2 production pathways. the catalytic performance of simultaneous removal of NOx and
soot. Ce/Zr ratios affected the catalytic activity [181]. A 3DOM
4.6.3. Effect of transitional metal doping Ce0.85Fe0.1Zr0.05O2 sample exhibited the optimal catalytic activi-
It is generally accepted that reaction pathways for the com- ty with a maximum concentration of CO2 at 415 °C and nearly a
bustion of soot over CZO-supported active metal catalysts can 100% NO conversion in the range of 365–503 °C. In addition,
be divided into two sections according to different tempera- 3DOM Ce0.8M0.1Zr0.1O2 (M = Mn, Co, Ni) catalysts were also pre-
tures. At low temperatures, soot is directly oxidized by active pared, and the 3DOM Ce0.8Mn0.1Zr0.1O2 catalyst displayed the
oxygen species that are migrated from the surface of maximum concentration of CO2 at 402 °C for soot combustion
CZO-supported catalysts. At high temperatures, both NO2 and and excellent NH3-SCR performance at 374–512 °C [183]. The
active oxygen species promote soot oxidation, and especially specific 3DOM architecture, high Ce3+/Ce4+ ratio and amount of
NO2 as an intermediate reactant plays a dominant role. In this chemisorbed oxygen species, good low-temperature reductive
process, NO2 serving as the oxidizer is reduced, and soot acting property, and the abundant of acid sites should be responsible
as the reducer is oxidized. Thus, the simultaneous removal of for the excellent catalytic efficiency of Ce0.8M0.1Zr0.1O2 (M = Fe,
soot and NOx is realized. However, it is noted that only a part of Mn, Co, Ni) for the simultaneous elimination of NOx and soot.
Fig. 25. CO2 concentration (left) and NO conversion (right) as a function of temperature upon exposure of 3DOM Ce0.9-xFexZr0.1O2 catalysts loosely
mixed with model soot. Reaction conditions: 1000 ppm of NH3, 1000 ppm of NO, 3% O2 and balance N2, GHSV = 25000 h−1. Reprinted from [182] with
permission.
Fig. 26. (a) Structure of Fe-doped CeO2(111) as the stoichiometric surface and with one and two oxygen vacancies; (b) Adsorption of NH3 and NO on
Fe-doped CeO2(111) with one oxygen vacancy (Fe1Ce1−xO2−y(111)); Fe-doped CeO2(111) with the oxygen vacancy preadsorbed by O2
(O2*Fe1Ce1−xO2−y(111)). Color scheme: white, Ce4+; green, Ce3+; red, O; orange, O to be removed; purple, Fe; blue, N; bright white, H. Reprinted from
[182] with permission.
actions between CZO and Al2O3, thereby leading to various at-

4.7. Three-way catalytic removal for the exhausts from gasoline om rearrangements during the aging process. The catalyst
engines prepared by the modified CP method maintained superior tex-
tural and structural properties as well as reductive behavior
Nowadays, three-way catalysts consisted of noble metals after being aged, which exhibited high catalytic performance
(Pt, Rh, Pd), sub-catalysts (CeO2, CeO2-ZrO2, etc.), and mono- with 10% conversion temperatures of C3H8, CO, and NO of 327,
lithic ceramic supports (alumina, 2MgO·2Al2O3·5SiO2, etc.) 164, and 208 °C, respectively. These were obviously lower than
comprise the state-of-the-art gas after-treatment technology, that of the catalysts synthesized by the conventional CP method
which are installed in gasoline-powered vehicle emission con- and mechanical mixing route. Hu et al. [7] synthesized nanosize
trol systems for simultaneous conversion of CO, NOx and un- CZY using a hydrothermal method. TWCs-containing CZY dis-
burnt HC [453]. Improving performance of catalysts for vehicle played a higher catalytic activity. Zhang et al. [469] prepared
exhaust is the key issue to meet the increasing standard of Ce1-xZrxO2 (x = 0–0.8) nanoparticle powders by a mild urea hy-
emission regulations. Many research groups have pioneeringly drolysis hydrothermal method. Ce1-xZrxO2 (x = 0.4–0.6) pow-
and deeply studied the properties of CZO and its important role ders preferred a metastable t'' phase to t' phase due to small
in three-way catalysis [454–459]. It has been found that the crystallite size effect. The stabilization of pseudocubic t'' struc-
preparation process [460–462] and material composition ture led to the high strain level in Ce1-xZrxO2 (x = 0.4–0.6) crys-
[463–466] can significantly influence the concentration of ac- tal lattice. Moreover, a linear relationship between the lattice
tive Ce4+ species and structural properties in the solid solution, strain and OSC value of the CeO2-ZrO2 catalyst was observed,
as shown in Table 9. and this correlation could be used as a tool to evaluate its OSC
and help to fabricate new CeO2-ZrO2 catalysts with higher OSC
4.7.1. Effect of preparation conditions and better redox performance. Zhou and co-workers [470]
Zhou et al. [467] investigated the effect of synthesis condi- reported the effect of mechanical mixing and CP methods on
tions (pH values of the solution of metal precursors and aging the redox behavior and catalytic performance of the three-way
temperature) on properties of Ce0.67Zr0.33O2 prepared by a CP CZA catalysts. CZA prepared by the CP method exhibited better
method and its application in Pd-based TWCs. The crystallite thermal stability than that prepared by mechanical mixing due
size of CZO increased significantly with increasing aging tem- to the presence of stronger interaction between CZO and Al2O3,
perature during precipitation, while OSC dropped and no nota- which was helpful for maintaining large surface area and small
ble effect on porosity of CZO was observed. Moreover, the particle size and inhibiting the formation of α-alumina phase
structural properties of CZO were affected by the pH value under the high-temperature condition. Moreover, it could also
during precipitation. Pd-based TWCs supported on this CZO improve the thermal stability of Pd/CZA catalysts. They further
support showed the best catalytic activity. Chen et al. [468] studied the preparation methods (CP, homogeneous precipita-
investigated the effect of synthesis methods (CP, mechanical tion, ME and hydrothermal method) on the catalytic perfor-
mixing, and modified CP method) on the structural properties mance of Ce0.67Zr0.33O2-supported Pd TWCs [471]. The prepara-
and catalytic performance of Pd/Ce0.5Zr0.5O2-Al2O3 TWCs. The tion methods significantly influenced the physicochemical
different preparation methods gave rise to the different inter- properties of Ce0.67Zr0.33O2 mixed oxides. The catalyst prepared
Table 9
Catalytic activities of nanosize CZO materials in three-way catalytic removal.
T50 (°C)
Three-way catalyst Reaction conditions Ref.
HC CO NO NO2
Ce0.68Zr0.27Nd0.05O2 NO/C3H6/C6H6/CO/O2/CO2/H2O/GHSV = 0.1:0.012:0.018:0.03:5:3/2/42000 h−1 520 — — — [492]
Pd/Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 230 160 232 180 [489]
Pd/5%La-Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 215 181 213 187 [485]
Pt/La0.1Ce0.4Zr0.5O1.9-Al2O3 NO/C3H6/CO/O2/GHSV = 1:1.067:7:7.8/50,500 h−1 350 333 370 — [487]
Pt-Rh/Y0.075La0.075Ce0.35Zr0.50O2-Al2O3 NO/C3H8/CO/O2/CO2/H2O/GHSV = 0.1:0.05:0.72:6.21:10:8.33/34000 h−1 222 170 189 — [488]
Pd/10%Pr-Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 200 148 173 156 [489]
Pd/8%Pr-Ce0.33Zr0.67O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.25:0.55:0.275:5:6.21/43000 h−1 250 209 261 212 [490]
Pd/5%Pr-Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 212 155 178 158 [489]
Pd/5%Nd-Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 218 184 206 170 [491]
Pt-Rh/NdxCe0.35Zr0.55O1.95-Al2O3 NO/C3H8/CO/O2/CO2/H2O/GHSV = 0.1:0.081:0.646:6.21:12:10/34000 h−1 259 160 211 — [493]
Pd/5%Sm-Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 220 178 183 180 [495]
Pd/5%Y-Ce0.2Zr0.8O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 233 181 207 181 [495]
Pd/5%Cr-Ce0.67Zr0.33O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 280 203 305 235 [502]
Pd/5%Mn-Ce0.67Zr0.33O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 279 130 258 182 [502]
Pd/1%Fe-Ce0.67Zr0.33O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 252 115 240 126 [496]
Pd/5%Co-Ce0.67Zr0.33O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 245 161 210 167 [497]
Pd/5%Ni-Ce0.67Zr0.33O2 NO/NO2/C3H6/C3H8/CO/O2/GHSV = 1:0.3:0.67:0.33:7.5:7.45/43000 h−1 264 161 184 184 [498]
T50 is denoted as 50% conversion temperatures of HC, CO, NO and NO2.
by the CP method amplified the stoichiometric window for the

fresh and aged catalyst due to suitable pore distribution, better 4.7.3. Effect of alkali or alkali-earth metals doping
OSC value, good redox property, and textural stability. Ba and Sr are reported to be two excellent promoters for
Al2O3, which can effectively suppress the decrease of specific
4.7.2. Effect of pretreatment conditions specific surface area and inhibit the transformation of the Al2O3
Liotta et al. [472] investigated the effect of redox pretreat- phase at high temperature in the three-way catalytic reaction
ment on the structural composition of CZO for three-way catal- [476–479]. Zhou’s group [480] reported the effect of BaO dop-
ysis. The changes of structure resulted from different calcina- ing on the structure and catalytic performance of Pd/CexZr1-xO2
tion treatments were brought back by the redox cycles. The (x = 0.2–0.8) catalysts for automobile emission control. BaO
reductive behavior of CZO was not changed by repeated cycles, addition significantly promoted the catalytic activity of HC and
and the loss of surface area did not affect the total OSC. In addi- NOx conversions due to promoting the formation of oxygen
tion, the alternative reductive and oxidative treatments led to vacancy and improving active oxygen mobility resulting from
reversible change of the solid solution composition around the electronic and structural modifications. After thermal aging
nominal value of Ce0.6Zr0.4O2. Zhou et al. [473] found that the treatment, Zr-rich catalysts (CeO2/ZrO2 < 1) underwent less
catalytic activities of Pd/CZO-Al2O3 catalysts were affected by severe deterioration of the catalytic activity compared with
thermal treatment. The surface oxygen desorption capacity and Ce-rich catalysts (CeO2/ZrO2 ≥ 1) due to better thermal stabil-
lattice oxygen mobility decreased due to the sintering of sup- ity, and Pd/Ce0.5Zr0.5O2BaO presented the optimally catalytic
ports after being calcined at high temperature, which was un- performance. Subsequently, they probed the role of Ba in TWCs
favorable for the dispersion of active species, leading to the loss Pd/Ce0.5Zr0.5O2 using in-situ DRIFTS [481]. The introduction of
of three-way catalytic activities. Anderson et al. [474] in- Ba weakened the strong adsorption of HC reactants on the cat-
vesigated the effect of oxychlorination treatments on the redox alyst surface and accelerated NO dissociation. It facilitated the
and oxygen storage and release properties of Pd-Rh/CZO/Al2O3 formation of intermediates (CN and NCO) due to the excellent
model TWCs. Thermal aging could not only lead to the decrease electron-donating ability of Ba. Thereby Ba-modified catalysts
of metal dispersion, but also result in a loss of OSC as oxygen exhibited much higher catalytic activity for HC and NOx conver-
storage component. A series of complex feed-streams were sions than the unmodified one. However, the introduction of Ba
performed on Ce0.68Zr0.32O2 mixed oxide to investigate its per- led to the loss of active sites, thus it inhibited CO oxidation at
formance as TWCs by González-Velasco et al. [475]. The low temperatures. Wang et al. [482] investigated the effect of
pre-reducing treatment could greatly enhance both different amounts of Sr doping on the catalytic performance of
low-temperature NO reduction activity and N2 selectivity. Alt- Pd/Ce0.67Zr0.33O2 catalysts for automobile emission control. Sr
hough a remarkable decrease in the specific surface area of the doping enhanced the low-temperature activity and the thermal
mixed oxide took place after being aged at 900 °C, the catalytic stability of the Pd phase owing to the improved oxygen mobili-
activity of the aged sample remained similar or even better ty and OSC. Pd-based TWCs supported on Ce0.67Zr0.33Sr0.03O2.03
than the fresh one due to the increased OSC value. Therefore, support exhibited the optimal activity for C3H8 and NO conver-
CO and HC emissions during cold-start state could be reduced sion as well as broadened activation temperature window. Shi
by placing the catalytic converter nearer the outlet to the en- et al. [483] conducted a comparative study of the catalytic per-
gine exhaust, where the CZO-based catalyst would be heated formance over SrO and BaO doping CeO2-ZrO2 for TWCs.
faster. Ce0.35Zr0.55Sr0.10O1.9 (CZS) and Ce0.35Zr0.55Ba0.10O1.9 (CZB) were
prepared by an oxidation-CP method with H2O2 as oxidizing exhausts from gasoline engines over nanosize
agent, and then they were used for preparing TWCs with a low ceria-zirconium-based solid solutions
loading amount of Pt and Rh. The incorporation of Sr2+ ions into Shi et al. [483] proposed that the mechanisms of three-way
CZO could retain a higher OSC value than the introduction of catalytic removal for the exhausts from gasoline engines on
Ba2+ ions. Moreover, the introduction of Sr2+ ions favored the Pt-Rh/Ce0.35Zr0.55Sr0.10O1.9/La-stabilized Al2O3 (LA) and
formation of homogeneously face-centered cubic phases and Pt-Rh/Ce0.35Zr0.55Ba0.10O1.9/LA were as follows:
maintained the stability of lattice cell units. Therefore, the cat- CO  O2  CO 2
(53)
alyst modified by Sr2+ exhibited a better catalytic activity and C3H8  O 2  CO2  H 2 O
(54)
wider activation temperature window. CO  NO  CO2  N 2
(55)
O2  Ce2O3  CeO2
4.7.4. Effect of rare earth doping (56)
With ever increasingly rigorous emission regulations are NO  Ce2O3  CeO 2  N 2
(57)
being implemented, taking into account that a significant por- The first three steps (Eqs. (53)–(55)) were involved in the
tion of toxic emissions is produced during cold start, it is nec- elimination of pollutants over TWCs. The fourth step (Eq. (56))
essary to place TWCs closer to the engine in order to attain played a role in adjusting the ratio of oxidant/reductant. The
their light-off activity immediately after the start up of the en- last step referred to the reduction of NOx in TWCs at λ < 1.
gine. Consequently, the catalysts should be capable of tolerating Steam-reforming and water-gas shift reactions would take
high temperature. Therefore, better thermal stability and high- place when H2O was present in exhaust gas. H2 would be pro-
er OSC are urgent for the development of new-generation duced to react with NO. CZO could supply active oxygen species
TWCs. A great amount of research has demonstrated that the resulting from the cerium charge transformation CeO2 ↔ Ce2O3
doping rare earth metal can improve the three-way catalytic when alkaline-earth metal oxides were incorporated to CZO
activity and temperature operation window, as shown in Table lattice. They would react with the adsorbed NO on the catalyst:
9 [484–498]. NO  O2  NO2
(58)
Subsequently, NO2 reacted with alkaline-earth metal oxides,
4.7.5. Effect of transition metal doping
for example SrO and BaO:
Effect of different amounts of Fe-modified CeO2-ZrO2 on the NO 2  BaO  BaO - NO 2
physicochemical properties and catalytic behavior of TWCs for (59)
Then BaO-NO2 reacted with NO and produced nitrite:
automotive emission control was investigated by Zhou et al.
BaO - NO 2  NO  BaO(NO 2 ) 2
[496,497]. The Pd/CZFe(1%) catalyst exhibited optimal cata- (60)
lytic performance for CO, HC, NO, and NO2 eliminations. The Furthermore, nitrite further reacted with NO2 and produced
doping of 1% iron oxide promoted the formation of homoge- nitrate:
neous Ce-Zr-Fe-O ternary solid solution, which not only facili- BaO(NO2 ) 2  NO2  BaO(NO3 )2
(61)
tated the reduction of Ce4+ → Ce3+ and the generation of oxygen Excess oxygen was stored in CZO materials (Eq. (56)) at λ >
vacancy and then improved the interaction between Fe and 1 based on the former step. Meanwhile, NOx was also stored in
Ce-Zr, but also enhanced Ce redox behavior. The introduction CZO materials, and then released at λ < 1 and reduced on the
of cobalt oxide by the CP method considerably enhanced the noble metal sites, leading to the enhancement of NOx conver-
catalytic activity of Pd-based TWCs with T50 for HC at 245 °C, sion under wider air/fuel ratios.
for CO at 161 °C, for NO at 210 °C, and for NO2 at 167 °C. It
should be due to the formation of more homogeneous ternary 4.7.7. Summary of cerium-zirconium-based material for
solid solution, which improved OSC and the interaction be- three-way catalytic removal of exhausts from gasoline engines
tween CZO and cobalt metal. In addition, Zhou et al. [498–500] x
2CCe  Oo  2Ce'Ce  VO  1 / 2O 2
(62)
also reported the introduction of Ni promoted the redox be- MO 
CeO2
 M 'Ce  VO  1 / 2O 2
havior of Pd/CZO catalysts, leading to the increase of OSC of (63)
M 2O3 
CeO 2
 2M 'Ce  2O Ox  VO  1 / 2O 2
samples, and Pd/CZNi(3%) exhibited the optimal catalytic per- (64)
formance compared with other catalysts. Zhou et al. [501,502] There are two kinds of oxygen vacancies in cerium-base
investigated the behavior of Pd supported on transition metals materials. One is produced by the revivification of Ce4+ through
(M = Cr, Mn, Fe, Co, Ni) modified Ce0.67Zr0.33O2 oxides under Eq. (62), and the other is produced by doping ions through Eqs.
stoichiometric CO + HC + NOx + O2 reaction conditions. The (63) and (64) [503–505]. The OSC and redox properties of a
incorporation of transition metals especially Fe and Co strongly cerium-based oxygen storage material are closely related to the
improved the oxygen mobility and greatly enhanced the OSC of oxygen vacancy concentration, migration rate of oxygen va-
CZO and the corresponding catalysts. The introduction of Fe cancy, surface area, and the formation of anion defects
and Co into CZO was more beneficial to forming homogeneous [506,507]. The lattice defects formed in the bulk of CZO can
Ce-Zr-M-O ternary solid solution and therefore promoting the make the bulk lattice oxygen and oxygen vacancies to be used
reduction of Pd/CZO. As a result, the catalytic activities of the in catalytic reaction, but the OSC and thermal stability still can
catalysts were significantly enhanced (Fig. 27). not meet the ever increasingly stringent emission standards.
Thus, it urgently needs to further improve oxygen vacancy,
4.7.6. Mechanisms of three-way catalytic removal for the lattice defect, OSC, and thermal stability of CZO. The introduc-
Fig. 27. Conversion of (a) HC, (b) NO, (c) CO, and (d) NO2 over various catalysts as a function of reaction temperature under stoichiometric CO + HC +
NOx + O2. Reaction condition: NO(0.1%)-NO2(0.03%)-C3H6(0.067%)-C3H8(0.033%)-CO(0.75%)-O2(0.745%) in Ar. Reprinted from [502] with permis-
sion.
tion of a third metal to the CZO material may be a feasible way. atmospheric CO2 reduction. This process is a catalytic hydro-
The influence of extra metal doping mainly includes the fol- genation reaction (Sabatier reaction):
lowing two aspects. One way is to change the radius of dopant CO2  4H 2  CH 4  2H 2O H 298 K = -252.9 kJ/mol
(65)
ions to make the lattice atoms rearrangement and crystal Much research has been devoted to this particular reaction
structure producing different degrees of distortion, which can over Ni-based CZO catalysts. Roger and co-workers [509,510]
effectively reduce the diffusion resistance of oxygen in crystal reported that the Ce/Zr ratio and Ni loading distinctly affected
lattice. The other way is to introduce a valence state lower than the catalytic performance of Ni/CZO catalysts for CO2 methana-
Ce4+ and Zr4+ cation and by the charge balance of crystal lattice tion. The catalyst with Ce/Zr mole ratio of 72/28 and 10% Ni
to form oxygen vacancy and then improve the diffusion rate of exhibited the best activity. Kawi et al. [511] proposed that the
bulk oxygen. preparation methods can influence the catalytic activity of CO2
methanation over Ni/CZO catalysts. The catalyst prepared by
4.8. Nanosize cerium-zirconium-based solid solutions for CO2 ammonia evaporation showed a higher activity than the coun-
transformation terpart catalysts synthesized by impregnation and deposition
precipitation methods due to stronger metal-support interac-
The emission of CO2 originated from human activity is a sig- tions between Ce and Ni species. Roger et al. [509] also found
nificant factor resulting in the rapid global warming. The cata- that noble metals (Rh, Ru) dopping significantly enhanced the
lytic transformation of CO2 into useful stuffs is recognized to be catalytic performance of Ni/CZO catalysts for CO2 methanation
one of the economic and effective ways to mitigate CO2 buildup due to the higher dispersion of Ni species. Wang et al. [512]
[508]. The key challenge is to develop an effective catalyst that investigated the effect of Ru dopping amount on Ni/CZO cata-
can achieve a high CO2 conversion at low temperature. Among lysts for CO2 methanation. Ru promoted the catalytic activity of
the catalysts, CZO is one of the key components owing to its catalyst for CO2 conversion and the catalyst with 3 wt% Ru
excellent OSC property and robust stability. And this part showed the optimal activity with CO2 conversion and methane
mainly focuses on three CO2 transformation reactions over selectivity of 98.2% and 100%, respectively. Zhang et al. [513]
CZO: methanation, reforming and chemical transformations. proposed that the addition of 5 wt% Co can increase the oxygen
vacancy and defect of Ni/CZO catalysts, and thereby promote
4.8.1. CO2 methanation the catalytic activity for CO2 methanation.
CO2 methanation is a green and promising method for the Although the reaction of CO2 methanation is a simple pro-
cess, it appears to be difficult to reach a consensus on the reac- Ni-M/CZO catalyst activity for CO2 reforming of CH4. The addi-
tion mechanism. The main controversy concentrates on the tion of Rh distinctly enhanced the activity and stability of the
nature of intermediate compound and the formation scheme of catalyst. In addition to Ni as active species, other metals such as
methane. Kawi et al. [511] proposed that the mechanism of CO2 Pt and Co were also supported on CZO and investigated for CO2
methanation on Ni/CZO catalyst was as follows. At temperature reforming of CH4 reaction. Resasco et al. [521] prepared a se-
below 150 °C, CO2 first adsorbs on the surface of Ni/CZO as ries of Pt-based CZO catalysts with different Ce/Zr ratios for
mono- and/or bi-dentate carbonate, and then these carbonate CO2 reforming of CH4. It was found that Pt/Ce0.5Zr0.5O2 exhibit-
species react with dissociated hydrogen to form hydrogenated ed an optimal activity and a good correlation between catalytic
carbonates. When the temperature is above 250 °C, these hy- activity and reducibility. Su et al. [52] reported Co-based CZO
drogenated carbonate species further react with dissociated catalysts with two Ce/Zr ratios (0.33/0.67, 0.6/0.4) for CO2
hydrogen to generate monodentate carbonate. These interme- reforming of CH4. The catalyst with the Ce/Zr ratio of 0.6/0.4
diate species convert into formaldehyde-like and methoxy spe- showed a better activity due to its better reducibility, higher Co
cies followed by dissociating to CH4. The methanation of CO2 dispersion, and alkalescence of Co/Ce0.6Zr0.4O2 surface. Mean-
proceeds by CO2 direct hydrogenation to form methane with- while, it should be noted that Pt- and Co-based CZO catalysts
out the formation of CO as intermediate. possess a lower activity than Ni/CZO for CO2 reforming of CH4.
However, the Ni-based catalyst readily induced deactivation
4.8.2. Reforming with CO2 and methane due to coke deposition. Thus, the introduction of a second ac-
CO2 reforming of CH4 to synthesis gas is considered to be an tive metal should be necessary.
efficient and attractive approach to eliminate green house gas- Idem et al. [514,522] proposed that the mechanism of CO2
es. This process is called dry reforming of methane reaction: reforming of CH4 on Ni/CZO was as follows:
CO2  CH 4  2CO  2H 2 H 298 K = 247 kJ/mol CH 4  2S  CH x  (4  x)H (s)
(66) (67)
Idem et al. [514] investigated the catalytic activity of where, (s) represents the active sites on Ni/CZO surface. CH4
Ni-based CZO catalysts for CO2 reforming of CH4. Compared first adsorbs on S and then dissociates to CHx fragments. The
with Ni/ZrO2 and Ni/Ce-doped ZrO2 catalysts, Ni/CZO showed adsorbed H atoms reacts to produce H2:
higher resistance to carbon deposition due to its enhanced (4  x)H (s)  (4  x / 2)H 2  S
(68)
low-temperature reducibility. It is well known that the deacti- CHx fragments were oxidated on Ni/CZO surface to form CO
vation of catalyst induced by active metal sintering is a thorny and H2:
and challenging subject in this reaction. Wang and co-workers CH x  2(Ce  Zr)O2  CO  (x / 2)H 2  (Ce  Zr)2 O3  S
(69)
[515] prepared a series of mesoporous CZO-supported Ni cata-
Eq. (70) represents the oxidation of reduced sites on Ni/CZO
lysts by a CTAB-assisted method. The catalyst exhibited out-
surface by CO2 to generate CO and initial Ni/CZO. Therefore, the
standing stability and initial activity for CO2 reforming of CH4
reaction can readily proceed forward by the highly mobile ox-
reaction. It should be attributed to its large specific surface area
ygen species supplied by the high OSC and reducibility of
and high dispersion of NiO. Liu et al. [516] synthesized a
Ni/CZO.
Ni/CZO/MSU-H catalyst by a hydrothermal method for CO2
CO2  (Ce  Zr)2 O3  CO  2(Ce  Zr)O 2
reforming of CH4. Owing to the enhanced OSC for the synergis- (70)
tic effect between MSU-H and CZO, Ni/CZO/MSU-H presented
high resistance to coke. In addition, the property of CZO could 4.8.3. CO2 for the synthesis of dimethyl carbonate
be adjusted by dopants, thus their catalytic activity for CO2 re- It is generally accepted that dimethyl carbonate (DMC) is an
forming of CH4 was improved. Noronha et al. [517] reported important chemical intermediate in chemical industry and di-
that the introduction of Al to CZO could significantly promote rect synthesis of DMC from CO2 and methanol is an environ-
the oxygen mobility of the Ni/CZO/Al2O3 catalyst, and thereaf- mentally friendly chemical process [523]. Tomishige et al. [524]
ter it inhibited the formation of carbon from blocking metallic employed CZO as a catalyst for the synthesis of DMC from CO2
particle. Idem and co-workers [518] studied the effect of metals and methanol reaction. They found that the catalytic activity of
dopping (M = Al, Ba, Ca, Hf, La, Pr, Sm, Sr, Tb, and Y) on catalyst is closely related to the calcination temperature, and
Ni/CZMO catalysts for CO2 reforming of CH4. The results the higher calcination temperature can induce more active
showed that the dopants increased the activity of Ni/CZMO. surface and thereby enhance the activity. Kim et al. [525–527]
Especially, the doping of Ca, La, and Y considerably boosted the reported that the catalytic activity of the catalyst for this reac-
low-temperature activity because of the increased Ni disper- tion was dependent on the preparation method and the catalyst
sion, OSC, and reducibility. Meanwhile, the introduction of a prepared by a decomposition method using adipic acid exhib-
second active metal is another important method to improve ited the highest specific surface area (170 m2/g) and best cata-
the catalytic activity of the Ni/CZO catalyst for CO2 reforming of lytic performance. Saha et al. [528] synthesized a highly active
CH4. Lee et al. [519] investigated the effect of Mg doping on the and stable CZO/graphene catalyst for direct synthesis of DMC
physicochemical properties and catalytic activity for CO2 re- from CO2 and methanol. They proposed that the introduction of
forming of CH4 over Ni/CZO. Ni-Mg/CZO showed better cata- grapheme significantly promoted the formation of highly crys-
lytic activity than Ni/CZO due to the improved thermal stability. talline nanostructures and thereby improved its activity. Jung
Moreover, Kiennemann et al. [520] studied the influence of the et al. [529] prepared a series of Ga2O3-modified CZO catalysts
introduction of the second metal (M = Co, Fe, and Rh) on and investigated their catalytic activity for direct synthesis of
DMC from CO2 and methanol. 5 wt% Ga2O3/CZO showed the moval of harmful substances vary dramatically. For example,
best activity. Jung and co-workers [530] further studied the the space velocity of automobile exhausts could be as high as
effect of acidity of catalyst on the catalytic performance for hundreds of thousands, and the changes of the exhaust tem-
synthesis of DMC from CO2 and methanol. They prepared perature vary from dozens of Celsius degrees when cold start-
PW12O40-modified CZO catalysts for this reaction. The results ing to seven or eight hundred Celsius degrees when speeding
revealed that the modification of CZO by PW12O40 greatly im- up.
proved the activity of catalyst for synthesis of DMC from CO2 In addition, the environmental catalysts should also possess
and methanol because of the enhancement of Brønsted acid high mechanical strength, because the amount of gases to be
sites provided by PW12O40 and that the acidity played a key role treated is often large. The catalysts ought to withstand the
in influencing the catalyst activity. Liu et al. [531] for the first pressure of fluid flushing. Moreover, the catalysts should be
time prepared ionic liquid 1-ethyl-3-methylimidazolium bro- easy to be prepared, cheap and wear-resisting, and low pres-
mide ([EMIM]Br)-modified CZO catalyst for synthesis of DMC sure drop.
from CO2 and methanol. The catalytic performance of CZO materials possess good redox and OSC. They are excel-
[EMIM]Br/CZO increased for DMC production, and it provided lent environmental catalysts or acted as the assistant of pre-
a promising alternative for the selective production of DMC cious metal catalysts. Although the lattice defects forming in
from methanol and CO2. CZO can be helpful to the catalytic reaction, the OSC and ther-
Kumar et al. [532,533] proposed that the mechanism of mal stability should be further improved to meet the require-
synthesis of DMC from CO2 and methanol on CZO was as fol- ments of environmental catalysts for high activity, high selec-
lows. tivity, high stability and high adaptability. From the typical cat-
CH3OH first adsorbs on acidic and basic sites of CZO surface alytic reactions described above, it can be deduced that the
and then dissociates to CH3+, OH−, CH3O−, and H+, respectively: methods to improve the properties of CZO catalysts are as fol-
CH 3OH  CH 3  OH  Acidic sites of the catalyst lows: (1) adopting a suitable preparation method to design and
(71)
CH 3OH  CH 3O   H  Basic sites of the catalyst improve the microstructure texture and physicochemical
(72)
properties of CZO; (2) supporting active metals to enhance
Then, CH3O− reacts with CO2 to form CH3OCO2− on the basic
catalytic performance of CZO; (3) introduction of additional
sites of CZO:
components into CZO to further increase the degree of lattice
CH 3O   CO 2  CH 3OCO 2  Basic sites of the catalyst
(73) oxygen deficiency, improve OSC, and then enhance the catalytic
Finally, CH3OCO2− reacts with CH3+ to form DMC, and H+ reactivity, selectivity, and adaptability of environmental catalysts.
acts with OH− to generate H2O: The addition of additional components including rare earth,
CH 3OCO 2   CH 3  DMC transition and alkaline earth or other metals can also inhibit the
(74)
H   OH   H 2O transformation of crystal phase of CZO and then improve the
(75)
thermal stability of environmental catalysts.
Doping rare earth oxides with variable state into CZO can
4.9. Summary of nanosize cerium-zirconium-based materials
not only enhance their lattice defects and improve the redox
for environmental catalysis
property of catalyst, but also significantly enhance lattice de-
fects such as the number of oxygen vacancies. Additionally,
Environmental catalysis, which can transform pollutants
doping rare earth elements into CZO can also form a ternary
into harmless substances or valuable stuff, is now recognized as
solid solution, which may improve the thermal stability of CZO
one of the most useful methods to reduce environmental pollu-
[536].
tion in the world [534,535]. CZO is used as the active compo-
Transition metals have unfilled valence orbit, and their
nent, support, or oxygen storage material, and it is indispensa-
properties are quite different from other elements. There are
ble to purify pollutants in environmental catalysis. The main
many single electrons in the electron configuration of the ele-
characteristics of environmental catalysts are as follows.
ment in this part, which are readily to lose, so these metals
(a) High activity. The catalysts should be extremely efficient
have a variable valence state. The unique electron configura-
to remove the hazardous substances. Because the concentra-
tion of transition metals determines their good
tion of the harmful substances in exhausts is usually low, it is
low-temperature redox properties. The previous reviews show
only the catalysts with high activity that can efficiently remove
that the introduction of transition metals into CZO can form a
them.
solid solution structure and the modified CZO exhibits good
(b) High selectivity. The exhaust gas compositions to be
low-temperature redox properties. The transition metals sup-
disposed are often complex, and the catalysts should possess
ported catalysts possess a low ignition temperature, which
high selectivity.
realize the purification treatment of automobile exhaust under
(c) High stability. The gases to be treated often contain some
cold start condition. The common transition metals used for
toxic ingredients. Therefore, the catalysts should have strong
doping CZO are Mn, Cu, Fe, Co, Ni, and Cr, etc.
toxicity resistance, high chemical stability, and long lifetime.
Alkaline earth metals can form ternary solid solution with
Moreover, the catalysts should have high thermal stability and
CZO to some extent, but the solid solubility varies greatly with
wide operation temperature window.
the change of ion radius of alkaline earth metals. The ion radii
(d) High adaptability. The reaction conditions for the re-
of Mg2+, Ca2+, Sr2+ and Ba2+ are 0.66, 1.12, 1.25, and 1.42 Å, re-
spectively [537,538]. Among them, Ca2+ and Sr2+ exhibit higher cient catalysts. CZO materials should be further improved to
solid solubility with CZO because of their appropriate ion radii, meet the requirements of environmental catalysts for the high
but Mg2+ and Ba2+ show lower solid solubility with CZO. The activity, the high selectivity, the high stability, and the high
effect of doping different alkali earth metals on the catalytic adaptability. It is anticipated that further investigations will
properties of CZO is different. Ca and Sr are easily distributed in expand the understanding for their structure and physico-
the lattice of CZO to form ternary solid solution structure, chemical properties and contribute to the development in the
which can improve the thermal stability and OSC performance practical processes for more widely fields such as catalysis and
of CZO based catalysts. separation, energy storage and utilization, and optical or aero-
The oxides of Al2O3 and SiO2 can remarkably affect the cata- space materials.
lytic performance of CZO. Although they can not be soluble with
cerium and zirconium, they can interact with each other to Conflicts of interest
generate new dispersive phase, which can inhibit catalyst from
sintering at high temperature and improve its stability, redox There are no conflicts to declare.
and OSC performance.
Acknowledgments
5. General conclusions and perspectives
This work was financially supported by the National Natural
Different from the other rare earth oxides, ceri- Science Foundation of China (21673290, U1662103).
um-zirconium-based solid solutions and related oxides are
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Graphical Abstract
Chin. J. Catal., 2019, 40: 1438–1487 doi: S1872-2067(19)63400-5
Structure, synthesis, and catalytic properties of nanosize ceri-
um-zirconium-based solid solutions in environmental catalysis CO, VOC and NH3
oxidation
Jixing Liu, Zhen Zhao, Chunming Xu, Jian Liu *
Environmental
China University of Petroleum; Shenyang Normal University
Soot, HC and PM
catalysis
combustion
NOx removal
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mental catalysis, such as the purification for nitrogen oxides (NOx), CO, hy-
drocarbon (HC), CO2 and solid particulate matters (PM). CO2 transformation
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铈锆固溶体的结构、合成及在环境催化领域中的应用
刘计省a, 赵震a,b, 徐春明a, 刘坚a,*
a
中国石油大学(北京)化学工程与环境学院重质油国家重点实验室, 北京102249
b
沈阳师范大学化学化工学院能源与环境催化研究所, 辽宁沈阳110034
摘要: 二氧化铈作为一种特殊的立方萤石结构, 是应用最为广泛的稀土氧化物. 同时, 它也是一种合适的催化剂载体, 可以

促进活性组分的均匀分布, 提高催化活性. 但纯二氧化铈在高温下容易发生团聚, 导致比表面积严重降低, 而锆(Zr)掺杂所
形成的铈锆固溶体(CZO)会显著提高铈基催化剂的稳定性. 在Zr含量较低时, CZO主要呈现立方萤石结构, 随着Zr含量增
加, CZO结构逐渐由立方相转变为正方相, 并最终形成单斜相. 此外, 与其它稀土氧化物不同, CZO由于其独特的结构性
质、可控的组成、良好的氧化还原性能以及氧储存性能(OSC)而备受关注.
截至目前, 由于其特殊的物理化学性质和有序的空间形貌, 纳米尺寸CZO格外引人关注. 其形貌主要包括纳米粉末、
一维纳米棒、纳米管、纳米带、纳米线、二维纳米薄膜、三维纳米笼、三维介孔、大孔和多级孔. 基于其不同的形貌及
有序的空间结构, CZO材料呈现不同的性质, 并且已被广泛应用于多相催化领域. 然而, 不同形貌CZO材料的性能仍然有
进一步提升的空间, 例如: 提高材料的稳定性及机械强度; 探索环境友好型合成路径; 考察反应时间、温度、溶液pH值、
Ce和Zr源的浓度和构型、金属掺杂等对形貌的影响; 研究不同形貌CZO纳米材料的物理化学性质; 阐明CZO结构、形貌与
其催化性能之间的关系.
环境催化可将污染物转化为无害或有价值的物质, 因而被认为是当今减少环境污染最有用的方法之一. 而CZO作为
活性组分、载体和氧存储材料具有优异的催化活性、较高选择性、高稳定性和极强的适应能力, 是环境催化领域消除污染
物过程中必不可少的组分, 因而被广泛应用于催化CO、VOC、Soot、PM和HC燃烧、NOx选择性催化还原和直接降解、CO2
转化等反应. 研究发现: 采用合适的制备方法能够改善CZO的结构和物理化学性质; 调节Ce/Zr摩尔比能促进CZO基材料
的氧化还原性能; 负载活性金属如贵金属Pt、Rh、Pd或过渡金属Mn、Co、Cu等可提高CZO的催化性能; 引入第三组分不
仅可以增加CZO晶格氧缺陷, 改善其OSC, 进而提高其催化活性、选择性和稳定性, 还可以抑制晶体转变, 提高CZO催化剂
的热稳定性. 然而, 自1970年代至今, 进一步提高CZO基催化剂的OSC和热稳定性以满足日益严峻的环保要求迫在眉睫.
关键词: 铈锆固溶体; 结构; 合成; 方法; 环境催化
收稿日期: 2019-05-28. 接受日期: 2019-07-03. 出版日期: 2019-10-05.

*通讯联系人. 电话: (010)89732278; 传真: (010)69724721; 电子信箱: [email protected]
基金来源: 国家自然科学基金(21673290和U1662103).
本文的电子版全文由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).

Structure, Synthesis, and Catalytic Properties of Nanosize Cerium-Zirconium-Based Solid Solutions in Environmental Catalysis

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Structure, Synthesis, and Catalytic Properties of Nanosize Cerium-Zirconium-Based Solid Solutions in Environmental Catalysis

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Chinese Journal of Catalysis 40 (2019) 1438–1487

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

1. Introduction heterogeneous catalytic reactions [11–18], including methane

* Corresponding author. Tel: +86-10-89732278; Fax: +86-10-69724721; E-mail: [email protected]

Fig. 2. Metastable-stable phase diagram in CexZr1-xO2

3.1.1. Co-precipitation method

3.1.6. Micro-emulsion method

critical drying (CPS), CP with common drying (CPC), and im-

3.1.7. Self-assembly method

m2/g in specific surface area. Moreover, the nanotubes pos-

3.2.3. 2-D cerium-zirconium-based solid solutions

3.2.4.4. Hierarchically porous cerium-zirconium-based solid

was based on the use of a CTAB-assisted gas bubbling reduc-

4.1.3. Volatile organic compounds (voc) elimination 4.1.3.1.1. CH4 oxidation

MnOm/Al2O3/Ce0.45Zr0.45Y0.10O1.95 exhibited the best catalytic  y-z y-z

4.1.4. Soot combustion 4.1.4.1. Effect of support composition

the ceria surface, which might lower the activation energy of

NOx produced from the combustion of fossil fuels such as

of NO2 reacted with two adjacent NH4+ to generate active com-

N 2 O    N 2 O toward NO + CO reaction. However, based on the results dis-

NO can be oxidized to NO2 by the catalyst owing to the thermal

actions between CZO and Al2O3, thereby leading to various at-

by the CP method amplified the stoichiometric window for the

2014, 4, 6602–6607. gew. Chem. Int. Ed., 2011, 50, 2326–2329.

摘要: 二氧化铈作为一种特殊的立方萤石结构, 是应用最为广泛的稀土氧化物. 同时, 它也是一种合适的催化剂载体, 可以

收稿日期: 2019-05-28. 接受日期: 2019-07-03. 出版日期: 2019-10-05.

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