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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 Introduction


were prepared by means of chemical precipitation
technique. Results from X-ray diffraction, transmis- Because of its unusual chemical and physical proper-
sion electron microscopy (TEM), and Zeta-potential ties in catalytic applications, cerium oxide has been
analyses provide strong microscopic and spectro- extensively employed as catalyst or textural and
scopic evidences to prove that CeO2 particles have structural promoter to support metal or metal oxide
been encapsulated inside amorphous SiO2 shell. As catalysts. In general, the textural-promotion effect is
revealed from TEM investigations, the average grain given by its excellent thermal and mechanical resis-
size of CeO2@SiO2 is significantly smaller than that tance that CeO2 confers to catalysts (Fu et al. 2003;
of uncoated CeO2 nanoparticles prepared under the Zarur and Ying 2000; Tang et al. 2006; Zheng et al.
same conditions, indicating it is an effective method 2005; Bunluesin et al. 1997); and the structural–
to restrict the grain enlargement of nanocrystalline promotion effect is attributed to the capability of
CeO2 by coating a thin layer of SiO2 at elevated cerium in forming crystalline oxides with lattice
temperatures. The CeO2@SiO2 nanoparticles display defects which act as catalytic-active sites (Miki et al.
a similar surface electric character behavior to that of 1990). As the particle size of ceria decreases, the
SiO2, and its dispersibility in water is improved. density of lattice defects increases, which improves the
catalytic activation and promotes the reaction kinetics
Keywords Nanoparticles  CeO2@SiO2  (Reddy et al. 2005). Precipitation method for nano-
Precipitation  Size  Zeta potential  CeO2 growth is one of the most straightforward and
Core-shell nanocomposites 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
J. Mao (&)  Y. Bai  M. J. Tu
College of Materials 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- X-ray diffraction ( XRD) patterns of CeO2 and CeO2
cally pure grade. CeO2 nanoparticles were prepared coated with 15 wt.% SiO2 (called CeO2–15%SiO2 in
using precipitation method by adding ammonia the following text) are shown in Fig. 1. The measured
solution to an aqueous solution of cerium (III) nitrate diffraction angles were consistent with those from the
(Ce(NO3)3). In a typical procedure, 100 mL of standard XRD patterns of CeO2 (JCPDS34-394) with
0.15 M Ce(NO3)3 solution was titrated with 20 mL no extra peaks observed. In the XRD patterns of
of 2 M ammonia solution under vigorous stirring. CeO2–15%SiO2, no additional peak from crystalline
Subsequently, the resulting precipitate was collected SiO2 was detected, indicating that the additives are
by filtration treatment. After being washed with present in an amorphous morphology. The full-width-
deionized water several times, the products were at-half-maximum (FWHM) of the diffraction peaks
dried at 80 °C for 5 h, and then milled for 30 min in from CeO2–15%SiO2 was found to be substantially
an agate mortar. Finally, the respective samples were broader than those of uncoated CeO2, implying a
calcined for 1 h at different temperatures. decreased grain size after coating. The obtained XRD
CeO2@SiO2 nanoparticles were obtained as fol- results provide clear evidences to indicate that the
lows. Take the sample of CeO2 coated with 15 wt.% grain size of CeO2 nanoparticles has been reduced
SiO2 as an example, 6.5 mmol tetraethylorthosilicate after coating with SiO2, which is consistent with
(TEOS) was dissolved into 10 mL ethanol, which TEM observations (Fig. 2).
was added into 100 mL of 0.15 M Ce(NO3)3
solution. Then 20 mL of 2 M ammonia solution TEM analyses
was added dropwise into the preceding solution
under vigorous stirring which was kept for 30 min HRTEM investigations on CeO2 and CeO2–15%SiO2
after the titration process. The subsequent proce- nanoparticles calcined for 1 h at 800 °C are shown in
dures were the same as those for CeO2 nanoparticles Fig. 2.
preparation. The average grain sizes for pure (Fig. 2a) and SiO2-
coated CeO2 (Fig. 2c) nanoparticles were measured to
Sample characterization 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

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


Fig. 2 Electron micrographs of CeO2 (a) and CeO2–15%SiO2 be in favor for potential structural-promotion
(c) nanoparticles with the HRTEM images obtained from the applications.
corresponding marked regions shown in (b) and (d),
respectively
Zeta potential

observed smaller average grain size of CeO2–15%SiO2 For the Zeta-potential measurements, each of the
in HRTEM explains the peak broadening of the XRD samples was dispersed in deionized water by sonica-
patterns in Fig. 1. Since the elastic scattering cross tion. Figure 3 shows the Zeta potential of CeO2, SiO2
section for CeO2 is much higher than that of SiO2 and CeO2–15%SiO2 samples as a function of pH
due to the fact that CeO2 has a significantly larger values in the aqueous solution. The Zeta potential of
average atomic number and crystalline morphology, CeO2 varies from 18 mV to -24 mV with the pH
it is very likely that the dark contrast in Fig. 2c values varying from 2 to 10, and its isoelectric point
corresponds to CeO2 materials while the surrounding (IEP) was found to be 4.43. On the other hand, the
less darker regions correspond to amorphous SiO2 surface electric characterestic of CeO2–15%SiO2 was
coating (see also Zeta-potential measurements), and measured to be the same as that of SiO2, and no IEP
the same principle applies for distinguishing between was detected in these cases.
amorphous SiO2 and the background carbon since the Zeta-potential analyses provide a direct indication
latter gives the least contrast. HRTEM micrographs that the CeO2 nanoparticles have been encapsulated
on CeO2 (Fig. 2b) and CeO2–15%SiO2 (Fig. 2d) inside the amorphous SiO2 shell successfully.
obtained from the regions marked in the corresponding
overview images reveal the nanoparticles consisting of Influence of SiO2 shell on grain size of CeO2
a single phase. For SiO2-coated CeO2, a thin layer of
amorphous material, labeled by the dark arrow on the The average grain size of sample was calculated by the
micrograph, is observed. This is subsequently inden- Scherrer equation using XRD data. The relationship of
tified to be SiO2 from the Zeta-potential measurements the average grain size versus the content of coated
(See Fig. 3), which on the other hand supports the SiO2 is shown in Fig. 4, which clearly shows that
observed contrast. Although the lattice parameters of increasing the SiO2 content leads to a decrease in the
the materials were measured to be comparable with the average grain size. It is interesting to note that there is a
{111}-plane lattice spacing in (b) and (d) of 0.313 and significant reduction of the average grain size for the
0.312 nm, respectively; a slight distortion of CeO2 SiO2 concentration up to 15 wt.% when the roast
lattice in CeO2–15%SiO2 sample was observed, 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 hindering the mass transfer. Increasing the SiO2
deionized water and sonication for 15 min. shell content leads to a decrease of the average
Ultraviolet absorption intensities (wavelength CeO2 grain size. Under the same roast temper-
k = 330 nm, where the ultraviolet absorption spectra ature, the grain size of CeO2 nearly doubles that
of CeO2 suspension has a characteristic absorption of CeO2–15%SiO2; under different roast temper-
peak) of CeO2 and CeO2–15%SiO2 suspensions at ature, there exists a minimum SiO2 content to
different pH values are shown in Fig. 6. It shows that, achieve an effective grain growth suppressing.
within the experimental pH range, a better dispersi- 3. The dispersibility of CeO2 nanoparticles in water
bility of CeO2–15%SiO2 suspension was observed is improved by coating it with SiO2.
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
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