RESEARCH PAPER
Preparation and characterization of size-controlled CeO2
nanoparticles coated with SiO2
Jian Mao • Yu Bai • Lin Gu •
Peter A. van Aken • Ming Jing Tu
Received: 14 January 2009 / Accepted: 15 September 2009
Ó Springer Science+Business Media B.V. 2009
Abstract CeO2@SiO2 (core@shell) nanoparticles
were prepared by means of chemical precipitation
technique. Results from X-ray diffraction, transmis-
sion electron microscopy (TEM), and Zeta-potential
analyses provide strong microscopic and spectro-
scopic evidences to prove that CeO2 particles have
been encapsulated inside amorphous SiO2 shell. As
revealed from TEM investigations, the average grain
size of CeO2@SiO2 is significantly smaller than that
of uncoated CeO2 nanoparticles prepared under the
same conditions, indicating it is an effective method
to restrict the grain enlargement of nanocrystalline
CeO2 by coating a thin layer of SiO2 at elevated
temperatures. The CeO2@SiO2 nanoparticles display
a similar surface electric character behavior to that of
SiO2, and its dispersibility in water is improved.
Keywords Nanoparticles
CeO2@SiO2

Precipitation
Size
Zeta potential

Core-shell nanocomposites
J. Mao (&)
Y. Bai
M. J. Tu
College of Materials
Introduction
Because of its unusual chemical and physical proper-
ties in catalytic applications, cerium oxide has been
extensively employed as catalyst or textural and
structural promoter to support metal or metal oxide
catalysts. In general, the textural-promotion effect is
given by its excellent thermal and mechanical resis-
tance that CeO2 confers to catalysts (Fu et al. 2003;
Zarur and Ying 2000; Tang et al. 2006; Zheng et al.
2005; Bunluesin et al. 1997); and the structural–
promotion effect is attributed to the capability of
cerium in forming crystalline oxides with lattice
defects which act as catalytic-active sites (Miki et al.
1990). As the particle size of ceria decreases, the
density of lattice defects increases, which improves the
catalytic activation and promotes the reaction kinetics
(Reddy et al. 2005). Precipitation method for nano-
CeO2 growth is one of the most straightforward and
convenient ways to realize the mass industrial pro-
duction; however, the necessary high-temperature
roast process increases the particle sizes, leading to a
significant loss of the catalysts’ activity (Bunluesin
et al. 1998; Craciun et al. 1998). Therefore, controlling
the size of CeO2 nanocrystallines in growth process is
the key to enhance its catalytic performance.
This study focuses mainly on the synthesis of
CeO2@ SiO2 nanoparticles with controlled size and
material characteristics including crystal structure,
surface properties, and Zeta potential are also
investigated.
 J Nanopart Res

Experimental procedure Results and discussion

Sample preparation XRD results

All reagents used in our experiments were analyti-
cally pure grade. CeO2 nanoparticles were prepared
using precipitation method by adding ammonia
solution to an aqueous solution of cerium (III) nitrate
(Ce(NO3)3). In a typical procedure, 100 mL of
0.15 M Ce(NO3)3 solution was titrated with 20 mL
of 2 M ammonia solution under vigorous stirring.
Subsequently, the resulting precipitate was collected
by filtration treatment. After being washed with
deionized water several times, the products were
dried at 80 °C for 5 h, and then milled for 30 min in
an agate mortar. Finally, the respective samples were
calcined for 1 h at different temperatures.
CeO2@SiO2 nanoparticles were obtained as fol-
lows. Take the sample of CeO2 coated with 15 wt.%
SiO2 as an example, 6.5 mmol tetraethylorthosilicate
(TEOS) was dissolved into 10 mL ethanol, which
was added into 100 mL of 0.15 M Ce(NO3)3
solution. Then 20 mL of 2 M ammonia solution
was added dropwise into the preceding solution
under vigorous stirring which was kept for 30 min
after the titration process. The subsequent proce-
dures were the same as those for CeO2 nanoparticles
preparation.
Sample characterization
X-ray diffraction ( XRD) patterns of CeO2 and CeO2
coated with 15 wt.% SiO2 (called CeO2–15%SiO2 in
the following text) are shown in Fig. 1. The measured
diffraction angles were consistent with those from the
standard XRD patterns of CeO2 (JCPDS34-394) with
no extra peaks observed. In the XRD patterns of
CeO2–15%SiO2, no additional peak from crystalline
SiO2 was detected, indicating that the additives are
present in an amorphous morphology. The full-width-
at-half-maximum (FWHM) of the diffraction peaks
from CeO2–15%SiO2 was found to be substantially
broader than those of uncoated CeO2, implying a
decreased grain size after coating. The obtained XRD
results provide clear evidences to indicate that the
grain size of CeO2 nanoparticles has been reduced
after coating with SiO2, which is consistent with
TEM observations (Fig. 2).
TEM analyses
HRTEM investigations on CeO2 and CeO2–15%SiO2
nanoparticles calcined for 1 h at 800 °C are shown in
Fig. 2.
The average grain sizes for pure (Fig. 2a) and SiO2-
coated CeO2 (Fig. 2c) nanoparticles were measured to
be about 40 ± 15 and 5 ± 3 nm, respectively. The

The structure of samples was examined using X-ray

diffraction (XRD, Philips X’Pert Pro) with Cu ∇
∇ CeO2
K-Alpha radiation (1.5418 Å). The Zeta-potential
measurements were performed with MARVEN
NANO ZS-90 apparatus at 25 °C, the isoelectric ∇
point (IEP) was determined by measuring the
∇
Intensity

variation of the Zeta potential with pH values.

Specimens for transmission electron microscopy
∇
(TEM) investigations were collected on carbon films
supported by copper grids. High-resolution trans- ∇
∇ ∇ ∇
mission electron microscopy (HRTEM) was per- ∇ CeO2
formed by using JEOL 4000EX (JEOL, Tokyo,
Japan) transmission electron microscope operated CeO2-15%SiO2
at an acceleration voltage of 400 kV. The interpret-
20 30 40 50 60 70 80
able resolution defined by the contrast transfer
2 Theta (°)
function of the objective lens is 0.16 nm. Ultraviolet
absorption spectra were measured by SHIMADZU Fig. 1 X-ray diffraction patterns of CeO2 and CeO2 coated
UV–1700 spectrophotometer. with 15% wt SiO2 calcined for 1 h at 800 °C

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J Nanopart Res
Fig. 2 Electron micrographs of CeO2 (a) and CeO2–15%SiO2
(c) nanoparticles with the HRTEM images obtained from the
corresponding marked regions shown in (b) and (d),
respectively
observed smaller average grain size of CeO2–15%SiO2
in HRTEM explains the peak broadening of the XRD
patterns in Fig. 1. Since the elastic scattering cross
section for CeO2 is much higher than that of SiO2
due to the fact that CeO2 has a significantly larger
average atomic number and crystalline morphology,
it is very likely that the dark contrast in Fig. 2c
corresponds to CeO2 materials while the surrounding
less darker regions correspond to amorphous SiO2
coating (see also Zeta-potential measurements), and
the same principle applies for distinguishing between
amorphous SiO2 and the background carbon since the
latter gives the least contrast. HRTEM micrographs
on CeO2 (Fig. 2b) and CeO2–15%SiO2 (Fig. 2d)
obtained from the regions marked in the corresponding
overview images reveal the nanoparticles consisting of
a single phase. For SiO2-coated CeO2, a thin layer of
amorphous material, labeled by the dark arrow on the
micrograph, is observed. This is subsequently inden-
tified to be SiO2 from the Zeta-potential measurements
(See Fig. 3), which on the other hand supports the
observed contrast. Although the lattice parameters of
the materials were measured to be comparable with the
{111}-plane lattice spacing in (b) and (d) of 0.313 and
0.312 nm, respectively; a slight distortion of CeO2
lattice in CeO2–15%SiO2 sample was observed,
20
CeO2
SiO2
10 CeO2-15% SiO2
Zeta potential / mV
0
1 2 3 4 5 6 7 8 9
pH
-10
-20
-30
Fig. 3 Zeta potential of the CeO2, SiO2 and CeO2–15%SiO2
samples as a function of pH value of the solution at 25 °C. The
isoelectric point of CeO2 nanoparticles is 4.43
indicating the presence of crystal defects which can
be in favor for potential structural-promotion
applications.
Zeta potential
For the Zeta-potential measurements, each of the
samples was dispersed in deionized water by sonica-
tion. Figure 3 shows the Zeta potential of CeO2, SiO2
and CeO2–15%SiO2 samples as a function of pH
values in the aqueous solution. The Zeta potential of
CeO2 varies from 18 mV to -24 mV with the pH
values varying from 2 to 10, and its isoelectric point
(IEP) was found to be 4.43. On the other hand, the
surface electric characterestic of CeO2–15%SiO2 was
measured to be the same as that of SiO2, and no IEP
was detected in these cases.
Zeta-potential analyses provide a direct indication
that the CeO2 nanoparticles have been encapsulated
inside the amorphous SiO2 shell successfully.
Influence of SiO2 shell on grain size of CeO2
The average grain size of sample was calculated by the
Scherrer equation using XRD data. The relationship of
the average grain size versus the content of coated
SiO2 is shown in Fig. 4, which clearly shows that
increasing the SiO2 content leads to a decrease in the
average grain size. It is interesting to note that there is a
significant reduction of the average grain size for the
SiO2 concentration up to 15 wt.% when the roast
temperature is 1,200 °C (the SiO2 concentration is up
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 J Nanopart Res

65 versus temperature in the curve of CeO2–15%SiO2 is

60 slower than that in the curve of CeO2. The grain size
800 °C
55 1200 °C of CeO2 nearly doubles that of CeO2–15%SiO2 at the
50 same temperature.
45 It is obvious that the SiO2 shell plays an important
Grain size / nm

40 role in controlling the grain size of CeO2. The reason

35 is that the SiO2 shell can suppress the grain enlarge-
30 ment of CeO2 nanoparticles through hindering the
25
mass transfer. Moreover, an effective suppression
20
under different roast temperatures needs a minimum
15
SiO2 content, as seen from Fig. 4, only when the SiO2
10
content is up to 5 wt.% and 15 wt.%, respectively, for
5
the roast temperatures of 800 °C and 1,200 °C, the
0 5 10 15 20 25 30
grain growth can be effectively inhibited.
The Content of coated SiO2 / wt%

Influence of SiO2 layer on the dispersibility

Fig. 4 The average grain size of CeO2 coated with different
content SiO2 (samples were calcined for 1 h at 800 °C and of CeO2 nanoparticles
1,200 °C, respectively)
Dispersibility of CeO2 and SiO2-coated CeO2 sus-
pension at different pH values was investigated by
70
ultraviolet absorption methods. The absorption is
60 directly proportional to the concentration of solid
CeO2
particles in suspension according to Reylengh equa-
50 CeO2-15% SiO2
tion (Song et al. 2008):
Grain size / nm

40 A ¼ kn
30 where A is the absorbance of suspension, n is the solid
particles number of suspension per unit volume, and k
20
is the absorbance constant. Higher absorbance usually
10 means better dispersibility of the suspension. The
0.01 wt.% CeO2 and SiO2-coated CeO2 suspension
0

200 400 600 800 1000 1200 2.3

Temperature / °C 2.2 CeO2
2.1 CeO2@SiO2
Fig. 5 The grain size of CeO2 and CeO2–15%SiO2 calcined at
2.0
different temperatures for 1 h
Absorhance

1.9
1.8
to 5 wt.% when the roast temperature is 800 °C); a 1.7
further increase of the SiO2 content, however, leads to 1.6
only a slight reduction of the average grain size. 1.5
The average grain sizes of CeO2 and CeO2– 1.4
15%SiO2 calcined at different temperatures are 1.3
shown in Fig. 5. Without SiO2 coating, the average 1.2
grain size of CeO2 augments with the increase of 2 4 6 8 10
roast temperature. However, the average grain sizes pH
of CeO2–15%SiO2 almost remain the same (less than
Fig. 6 Ultraviolet absorption (k = 330 nm) of CeO2 and
10 nm) when the temperature is below 800 °C. CeO2@SiO2 (15 wt.% SiO2) suspension, concentration is
Furthermore, the increasing tendency of grain size 0.01 wt.%

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J Nanopart Res
were prepared respectively by dispersing samples in
deionized water and sonication for 15 min.
Ultraviolet absorption intensities (wavelength
k = 330 nm, where the ultraviolet absorption spectra
of CeO2 suspension has a characteristic absorption
peak) of CeO2 and CeO2–15%SiO2 suspensions at
different pH values are shown in Fig. 6. It shows that,
within the experimental pH range, a better dispersi-
bility of CeO2–15%SiO2 suspension was observed
than that of CeO2 suspension. Experimental observa-
tions from Fig. 3 indicate that the Zeta potential of the
CeO2 suspension reaches higher values when pH
values are less than three, or more than eight. Under
these conditions, better dispersibility can be achieved
(Fig. 6). However, the Zeta potential is zero when the
pH value equals to 4.43, the dispersibility appears to be
the worst under this circumstance (Fig. 6). After SiO2
coating, no IEP appears in the Zeta curve of CeO2–
15%SiO2, and the absolute value of Zeta potential
increases when the pH values vary from 2 to 10
(Fig. 3). This implies that SiO2-coated treatment
improves the dispersibility of CeO2 nanoparticles.
Although a slight aggregation of CeO2@SiO2
particles occurs as observed from the HRTEM image
in Fig. 2c, the dispersibility of CeO2@SiO2 particles
seen from Fig. 2c is, in fact, still far better than that
of CeO2 particles in Fig. 2a. Moreover, when
CeO2@SiO2 particles are used in a specific applica-
tion, the SiO2 shell itself can be in favor of further
hydrophilic or oleophilic surface modification attrib-
uted to its surface radicals.
In addition, ceria is an amphoteric metal oxide and
reacts with acid or alkali, to some extent, SiO2-coated
CeO2 structure facilitates to solve this problem, thus
expanding its application fields.
Conclusions
1. The CeO2@SiO2 nanoparticles were prepared by
employing coprecipitation method. XRD, TEM,
and Zeta-potential characterizations revealed that
the CeO2 was encapsulated with an amorphous
SiO2 shell.
2. SiO2 shell plays an important role in controlling
the grain size of CeO2 nanoparticles. The reason
is attributed to the fact that the SiO2 shell
suppresses the CeO2 grain enlargement through
hindering the mass transfer. Increasing the SiO2
shell content leads to a decrease of the average
CeO2 grain size. Under the same roast temper-
ature, the grain size of CeO2 nearly doubles that
of CeO2–15%SiO2; under different roast temper-
ature, there exists a minimum SiO2 content to
achieve an effective grain growth suppressing.
3. The dispersibility of CeO2 nanoparticles in water
is improved by coating it with SiO2.
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