Particuology 10 (2012) 352358

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Particuology
journal homepage: www.elsevier.com/locate/partic

Preparation of nanosized hollow silica spheres from Na2 SiO3 using Fe3 O4
nanoparticles as templates
Chun Liu, Aili Wang, Hengbo Yin , Yutang Shen, Tingshun Jiang
Faculty of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, China

a r t i c l e

i n f o

Article history:
Received 16 February 2011
Received in revised form 10 April 2011
Accepted 21 April 2011
Keywords:
Hollow silica spheres
Sodium silicate
Fe3 O4 nanoparticles
Herbicide release

a b s t r a c t
Nanosized hollow silica spheres with average diameters from 43 to 70 nm were prepared by removal
of Fe3 O4 templates with hydrochloric acid from silica-coated Fe3 O4 coreshell composites. The shells of
the hollow silica spheres had nanopores with average diameters of 0.921.25 nm. When the silica-coated
Fe3 O4 coreshell composites were prepared at a high pH value or with a low mole ratio of Na2 SiO3 to
Fe3 O4 , the resulting hollow silica spheres consisted of highly porous shells. When the silica-coated Fe3 O4
coreshell composites were prepared with a high mole ratio of Na2 SiO3 to Fe3 O4 , the resulting hollow
silica spheres had large diameters and thick shells. The release rate of herbicide, ammonium glyphosate,
could be tuned by using hollow silica spheres with different shell thicknesses.
2011 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Sciences. Published by Elsevier B.V. All rights reserved.

1. Introduction
Preparation of hollow-structured materials with high specic
surface area has attracted increasing research interest due to their
potential applications in drug delivery, magnetism, and catalysis.
For example, hollow SiO2 spheres have potential applications in
doxorubicin delivery (Yang, Lee, et al., 2008) and ibuprofen storage (Zhu, Shi, Chen, Shen, & Dong, 2005). Hollow polymer capsules
can be used as potential drug delivery vehicles in tumor therapy
(Wang, Bansal, Zelikin, & Caruso, 2008). Hollow Ni spheres with
diameters in the range of 300450 nm have higher coercivity than
bulk Ni (Bao, Liang, Xu, & Si, 2003). Hollow TiO2 /SiO2 spheres and Pt
nanospheres show good catalytic activities in epoxidation of cyclohexene (Baca et al., 2006) and the oxidation of methanol (Liang
et al., 2004).
Preparation of hollow-structured materials, such as SiO2
(Caruso, Caruso, & Mhwald, 1998; Le, Chen, & Wang, 2004; Tsai
& Li, 2006; Yang, Lee, et al., 2008; Yang, Lind, & Trogler, 2008;
Zhu et al., 2005), Ni (Bao et al., 2003), TiO2 /SiO2 (Baca et al.,
2006), Pt (Liang et al., 2004), Fe3 O4 (Cong et al., 2008; Tada et al.,
2009), TiO2 (Wang, Song, Lin, & Hu, 2006), ZnO (Yang, Chu, Zhang,
Yang, & Liu, 2006), Ta2 O5 (Agrawal et al., 2008), and CdS (Song
et al., 2003), has been investigated by using template, emulsion,
and solgel methods. In particular, the preparation of hollow SiO2

Corresponding author. Tel.: +86 511 88787591; fax: +86 511 88791800.
E-mail address: yin@ujs.edu.cn (H. Yin).

spheres has been much studied since these spheres with permeable
shells can be used for drug delivery, as catalyst support, and heat
and sound insulation materials. Hollow SiO2 spheres are usually
prepared by the template technique. Aggregated Fe3 O4 nanoparticles (Yang, Lee, et al., 2008), poly(vinylpyrrolidone) (Zhu et al.,
2005), polystyrene (Caruso et al., 1998), chitosanpolyacrylic acid
(Tsai & Li, 2006), calcium carbonate nanoparticles (Le et al., 2004),
and amine-functionalized polystyrene (Yang, Lind, et al., 2008)
have been used as templates, while tetraethoxysilane (Le et al.,
2004; Yang, Lee, et al., 2008; Zhu et al., 2005), SiO2 nanoparticles (Caruso et al., 1998), and colloidal silica (Tsai & Li, 2006) have
been used as starting materials, and poly(vinylalcohol) (Yang, Lee,
et al., 2008), cetyltrimethylammonium bromide (Zhu et al., 2005;
Le et al., 2004), and poly-l-lysine (Yang, Lind, et al., 2008) have
been used as shell structure-directing agents. Hollow silica spheres
are prepared after removal of the templates from the silica-coated
template coreshell composites by calcination or dissolution. The
diameters of the resulting hollow silica spheres are usually several
hundred nanometers. It is well known that smaller-sized hollow
silica spheres have larger ratio of surface to volume than largesized ones. But, preparation of small, e.g. <100 nm, hollow silica
spheres has seldom been reported (Le et al., 2004; Yang, Lee, et al.,
2008). On the other hand, using tetraethoxysilane, SiO2 nanoparticles, and colloidal silica as starting materials makes the cost high
and the process complicated. Therefore, preparation of low-cost
nanosized hollow silica spheres is worth investigation.
Our present work reports the preparation of nanosized hollow silica spheres with diameters less than 100 nm using Fe3 O4

1674-2001/$ see front matter 2011 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

doi:10.1016/j.partic.2011.04.009

C. Liu et al. / Particuology 10 (2012) 352358

nanoparticles as templates and low-cost sodium silicate as precursor of the silica shells. The effects of experimental parameters, such
as pH value of reaction solution and silica loading, on the structure
of the resulting hollow silica spheres were investigated. In order
to improve the weeding time of herbicide, the release of herbicide,
ammonium glyphosate, from hollow silica spheres with different
shell thicknesses was also investigated.
2. Experimental
2.1. Materials
Sodium silicate (Na2 SiO3 9H2 O), sodium hydroxide, sulfuric acid (98%), iron trichloride (FeCl3 6H2 O), iron dichloride
(FeCl2 4H2 O), ammonium hydroxide (NH3 H2 O, 25%), hydrochloric
acid (38%), and cetyltrimethylammonium bromide, all of reagent
grade, were purchased from National Shanghai Chemical Co. Ltd.
Ammonium glyphosate was supplied by the SuPo Co. Ltd. as a gift.
The chemicals were used as received without further purication.
Distilled water was used throughout all the experiments.
2.2. Preparation of Fe3 O4 nanoparticles
Fe3 O4 nanoparticles were prepared by the traditional coprecipitation (Massart) method: 200 mL of an aqueous solution
of FeCl3 (2 mol/L) was rst added into a 1000 mL four-necked
ask. Dissolved oxygen was removed by bubbling N2 ; 100 mL of
an aqueous solution of FeCl2 (2 mol/L) was added into the abovementioned solution under stirring at 70 C in 30 min. Then, 150 mL
of ammonium hydroxide (25%) was added dropwise into the mixed
solution in 30 min. The reaction was carried out for 30 min in N2
atmosphere. The as-prepared Fe3 O4 precipitate was ltered and
washed with distilled water until the conductivity of the ltrate
was less than 20 mS/m. The washed Fe3 O4 precipitate was dispersed in deoxygenated water (200 g/L) and used as the template
for preparing hollow silica spheres.

353

to Fe3 O4 were increased from 1.55:1 to 2.32:1, 3.09:1, and 3.87:1,

respectively.
2.4. Preparation of hollow silica spheres
The as-prepared silica-coated Fe3 O4 coreshell composites
were heated to 600 C at a heating rate of 2 C/min and kept at
600 C for 2 h under air to remove CTAB. The calcined samples were
added into hydrochloric acid (38%) at 80 C for 6 h to dissolve the
Fe3 O4 cores. The resulting samples were ltered and washed with
aqueous hydrochloric acid (1 mol/L) and distilled water until the
conductivity of the ltrate was less than 2 mS/m. The as-prepared
hollow SiO2 spheres were heated to 600 C at a heating rate of
2 C/min and kept at 600 C for 2 h under air atmosphere.
2.5. Characterization
XRD data of the Fe3 O4 templates, the silica-coated Fe3 O4
composites, and the hollow silica spheres were recorded on a
diffractometer (D8 super speed Bruke-AEX Company, Germany)
with Ni lter. Scanning elecusing Cu K radiation (1.5418 A)
tron microscopy (SEM, JSM 7001F) and transmission electron
microscopy (TEM, JEM 2100, operating at 120 kV) were used to
investigate the morphologies of the Fe3 O4 templates and the hollow silica samples. The samples for TEM inspection were dispersed
in an anhydrous ethanol solution with ultrasonic treatment for
10 min. Then a few drops of the resulting suspension were placed on
a copper grid coated with a layer of amorphous carbon. The Fourier
transform infrared spectra of the samples were performed by the
KBr pellet technique on a Fourier transform infrared spectrometer (Nicolet Nexus470). The specic surface areas, the pore sizes,
and the pore volumes of the hollow silica spheres were obtained
from a volumetric adsorption analyzer (Quntachrome Corporation,
NOVA2000e). The samples were rst degassed in vacuum at 300 C
for 1 h. Then, measurement was carried out at 196 C over a range
of relative pressures (P/P0 ), where P0 is the saturated vapor pressure, from 0.1 to 1. The specic surface areas and pore sizes were
calculated by BET and BJH methods, respectively.

2.3. Preparation of silica-coated Fe3 O4 composites

2.6. Ammonium glyphosate release
Silica-coated Fe3 O4 composites were prepared by a wet chemical deposition method: 90 mL of the Fe3 O4 aqueous suspension
was diluted by adding 300 mL of deoxygenated water; 0.9 g of
cetyltrimethyl ammonium bromide (CTAB) was added into the
diluted Fe3 O4 aqueous suspension and sonicated for 30 min. CTAB
was used as a shell structure-directing agent. The Fe3 O4 suspension
was transferred into a 2000 mL ask in a water bath and heated to
80 C under stirring at 200 rpm. The Fe3 O4 suspension was adjusted
to a specic pH value by adding a NaOH (10%) aqueous solution.
Then, aqueous solutions of Na2 SiO3 (0.3 mol/L, 400 mL) and H2 SO4
(5%) were titrated into the Fe3 O4 suspension simultaneously with
two constant ow pumps. The mole ratio of Na2 SiO3 to Fe3 O4 was
1.55:1. The ow rate of the Na2 SiO3 aqueous solution was kept
constant and the feeding time was xed at 3 h. The pH value of the
reaction solution was kept constant during the coating process by
adjusting the ow rate of the H2 SO4 aqueous solution. After titration, the suspension was aged for 3 h under stirring. The precipitate
was ltered and washed with distilled water until the conductivity
of the ltrate was less than 20 mS/m. The washed precipitate was
dried in an electric oven at 120 C for 24 h. The dried samples were
kept in a desiccator.
To investigate the effect of pH value on the structure of hollow
silica spheres, the pH values of reaction solutions in the coating
process were xed at 6, 7, 8, 9, and 10, respectively. In order to
increase the thickness of silica shell, the mole ratios of Na2 SiO3

To investigate the herbicide release property of the hollow silica

spheres, ammonium glyphosate was selected as a model herbicide.
An ammonium glyphosate aqueous solution (0.02 g in 3 mL water)
was added to 0.25 g of hollow silica spheres with different shell
thicknesses. The samples were dried at 70 C for 8 h under vacuum
condition. Then, the ammonium glyphosate-loaded hollow silica
spheres were added into 200 mL of water at 20 C under stirring at
150 rpm. The concentration of the released ammonium glyphosate
in the suspension was measured by a UV spectrophotometer at
243 nm at different periods of time after removing hollow silica spheres by centrifugation at 12,000 rpm. The detailed analysis
method was referred to National Standard of the Peoples Republic
of China, GB 20684-2006.
3. Results and discussion
3.1. Crystal structures of iron oxide templates, silica-coated iron
oxide composites, and hollow silica spheres
Fig. 1 shows the XRD spectra of the iron oxide templates, the
silica-coated iron oxide coreshell composites, and the hollow
silica spheres. The XRD patterns of the iron oxide template and
the silica-coated iron oxide coreshell composite only show the
diffraction peaks of Fe3 O4 , appearing at 2 = 30.10 , 35.45 , 43.09 ,

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C. Liu et al. / Particuology 10 (2012) 352358

Fig. 1. XRD patterns for samples of: (a) the iron oxide template; (b) the silica-coated
iron oxide coreshell composite prepared at a pH value of 9 with a mole ratio of
Na2 SiO3 to Fe3 O4 of 1.55:1; and (c) the hollow silica spheres prepared by dissolving
the iron oxide core from the coreshell composite with hydrochloric acid. Symbol
 denotes Fe3 O4 .

53.46 , 56.98 , and 62.57 . After removing the iron oxide cores by
dissolution with hydrochloric acid, the XRD patterns of the hollow
silica spheres show that the remaining silica was in the amorphous
phase. There were no diffraction peaks of iron oxide observed in the
XRD spectra of the hollow silica spheres, indicating that the Fe3 O4
core was completely removed by dissolution with hydrochloric
acid under the experimental conditions.

3.2. TEM image of Fe3 O4 template

Fig. 2 shows the TEM image of the Fe3 O4 template. The asprepared Fe3 O4 template was granular nanoparticles with an
average particle size of 12.8 nm. The Fe3 O4 nanoparticles had an
aggregation tendency.

Fig. 3. SEM image of representative hollow silica spheres prepared by dissolution

of the Fe3 O4 core with hydrochloric acid from the silica-coated Fe3 O4 coreshell
composite, which was prepared at a pH value of 9 with a mole ratio of Na2 SiO3 to
Fe3 O4 of 1.55:1.

3.3. Effect of pH value on hollow silica spheres

Fig. 3 shows a representative SEM image of the hollow silica
spheres prepared by dissolution of Fe3 O4 core from silica-coated
Fe3 O4 coreshell composite with hydrochloric acid. The silicacoated Fe3 O4 coreshell composites were prepared at different pH
values with a mole ratio of Na2 SiO3 to Fe3 O4 of 1.55:1. When the
silica-coated Fe3 O4 coreshell composites were prepared at pH values of 6, 7, 8, 9, and 10, the average diameters of the resulting hollow
silica spheres were 46, 50, 49, 49, and 49 nm, respectively. Open
holes with an average diameter of ca. 5 nm were found in the shell
of the hollow silica spheres (the inset in Fig. 3), suggesting that the
rapid dissolution of the Fe3 O4 core through the thin silica shell with
hydrochloric acid caused the formation of the open holes. The SEM
images also show aggregation of the hollow silica spheres.
Fig. 4 shows the TEM images of the hollow silica spheres, with
average external diameters and the average shell thicknesses of 43,
7.8; 47, 7.4; 50, 7.0; 48, 6.1; 50, 3.5 nm, respectively, when the silicacoated Fe3 O4 coreshell composites were prepared at pH values of
6, 7, 8, 9, and 10. The internal diameters of the hollow silica spheres
were at least twice as much as the average particle size of Fe3 O4
nanoparticles, indicating how the aggregated Fe3 O4 nanoparticles
served as the templates. The average external diameters measured
by TEM analysis were consistent with those observed by SEM analysis. The shell thicknesses decreased with increasing pH values,
because at a high pH value, the hydrolysis speed of Na2 SiO3 was
lower, leading to lower deposition rate of siliceous micelles on the
surfaces of Fe3 O4 templates and subsequently causing the formation of thin shells.
3.4. Effect of mole ratio of Na2 SiO3 to Fe3 O4 on hollow silica
spheres

Fig. 2. TEM image of the Fe3 O4 template.

Fig. 5 shows the SEM images of hollow silica spheres, prepared

by dissolution of the Fe3 O4 cores with hydrochloric acid from the
silica-coated Fe3 O4 coreshell composites, with average diameters
of 49, 56, 61, and 66 nm prepared with mole ratios of Na2 SiO3
to Fe3 O4 of 1.55:1, 2.32:1, 3.09:1, and 3.87:1, respectively. The
diameters of the hollow silica spheres are shown to increase with
increasing mole ratios of Na2 SiO3 to Fe3 O4 .
Fig. 6 shows the TEM images of the hollow silica spheres. The
average external diameters and the average shell thicknesses of the

C. Liu et al. / Particuology 10 (2012) 352358

355

Fig. 4. TEM images of hollow silica spheres prepared by dissolution of the Fe3 O4 cores with hydrochloric acid from the silica-coated Fe3 O4 coreshell composites, which
were prepared at different pH values with a mole ratio of Na2 SiO3 to Fe3 O4 of 1.55:1.

hollow silica spheres were 48, 6.1; 54, 10.6; 64, 17.6; 70, 19.6 nm
when the silica-coated Fe3 O4 composites were prepared with the
mole ratios of Na2 SiO3 to Fe3 O4 of 1.55:1, 2.32:1, 3.09:1, and 3.87:1,
respectively. The average external diameters of the hollow silica spheres observed by TEM analysis were consistent with those
observed by SEM analysis. The shell thickness of the hollow silica
spheres increased with increasing the mole ratios of Na2 SiO3 to
Fe3 O4 .
3.5. N2 adsorption/desorption
In Table 1, for silica-coated Fe3 O4 coreshell composites prepared with a mole ratio of Na2 SiO3 to Fe3 O4 of 1.55:1, the specic
surface area of the resulting hollow silica spheres increased from
211 to 479 m2 /g with increasing the pH values from 6 to 10, while
the average pore size gradually increased from 0.92 to 1.25 nm

and the average pore volume increased from 0.48 to 1.40 cm3 /g.
Removing CTAB by calcination caused the formation of micropores in silica shells. Increasing pH value of the reaction solution
was benecial to the formation of silica hollow spheres with highly
porous-structured shells. On the other hand, when the silica-coated
Fe3 O4 coreshell composites were prepared with different mole
ratios of Na2 SiO3 to Fe3 O4 at a pH value of 9, the specic surface area of the resulting hollow silica spheres decreased from
387 to 199 m2 /g and the average pore volume decreased from
1.08 to 0.45 cm3 /g with increasing the mole ratios of Na2 SiO3 to
Fe3 O4 from 1.55:1 to 3.87:1. When the mole ratios of Na2 SiO3 to
Fe3 O4 were 2.32:1, 3.09:1, and 3.87:1, the average pore sizes of
the resulting hollow silica spheres remained constant at 0.92 nm.
Therefore, it is reasonable to conclude that raising the mole
ratio of Na2 SiO3 to Fe3 O4 caused decrease in the porosity of the
shell.

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C. Liu et al. / Particuology 10 (2012) 352358

Fig. 5. SEM images of hollow silica spheres prepared by dissolution of the Fe3 O4 cores with hydrochloric acid from the silica-coated Fe3 O4 coreshell composites, which
were prepared at a pH value of 9 with different mole ratios of Na2 SiO3 to Fe3 O4 shown under the respective SEM images.

Fig. 6. TEM images of the hollow silica spheres prepared by dissolution of the Fe3 O4 cores with hydrochloric acid from the silica-coated Fe3 O4 coreshell composites, which
were prepared at a pH value of 9 with different mole ratios of Na2 SiO3 to Fe3 O4 shown under the respective SEM images.

C. Liu et al. / Particuology 10 (2012) 352358

357

Table 1
Specic surface area, average pore diameter, and average pore volume of hollow silica spheres.
pH of reaction
solution

Mole ratio of
Na2 SiO3 to Fe3 O4

Specic surface
area (m2 /g)

Average pore
diameter (nm)

Average pore
volume (cm3 /g)

6
7
8
9
10
9
9
9

1.55:1
1.55:1
1.55:1
1.55:1
1.55:1
2.32:1
3.09:1
3.87:1

211
314
348
387
479
335
210
199

0.92
0.93
0.93
1.10
1.25
0.92
0.92
0.92

0.48
0.74
0.82
1.08
1.40
0.79
0.51
0.45

3.6. Evolution of hollow silica spheres

Fig. 7 shows the FT-IR spectra of the Fe3 O4 template, the silicacoated Fe3 O4 coreshell composite, and the hollow silica spheres.
For the Fe3 O4 template, the peaks appearing at 445.6, 590.8, and
644.7 cm1 are ascribed to the stretching vibrations of FeO bonds
(Giri, Thakurta, Bellare, Nigam, & Bahadur, 2005). The spectrum of
the silica-coated Fe3 O4 coreshell composite shows that the peaks
at 458.1, 574.2, and 619.8 cm1 are ascribed to the stretching vibrations of FeO bonds and the peaks at 2847.0 and 2925.8 cm1 , to the
stretching vibrations of CH bonds of CTAB; while stretching vibrations of SiOSi appeared at 458.1, 802.3, and 1088.5 cm1 . After
removing the Fe3 O4 core with hydrochloric acid and calcination
at 600 C for 2 h, the FT-IR spectrum of the resulting hollow silica
spheres only shows the stretching vibrations of the SiOSi bonds
at 466.4, 810.6, and 1092.6 cm1 , implying that the shell structuredirecting agent CTAB and the Fe3 O4 template were completely
removed by the calcination and acid dissolution treatments.
According to the FT-IR results, the evolution of the hollow silica
spheres could be understood to proceed as follows. First, Na2 SiO3
was hydrolyzed to form a large amount of negatively charged
siliceous micelles, which were then deposited on the surface of
the positively charged Fe3 O4 template via electrostatic force. Silica coating layer formed on the surface of the Fe3 O4 template via
polycondensation in the coating process. The cationic surfactant
CTAB molecules combined in the silica shell via electrostatic force,
acted as a framework agent. Calcination of the silica-coated Fe3 O4
coreshell composite caused complete oxidation of the organic
framework agent, resulting in the porous silica coating layer. When
the calcined silica-coated Fe3 O4 coreshell composite was treated
with hydrochloric acid, the Fe3 O4 core was completely removed by
acid dissolution, resulting in the hollow silica spheres with porous
shell.

Fig. 8. Release curves of ammonium glyphosate from dipped hollow silica spheres
with different shell thicknesses of 6.1 (), 10.6 (), 17.6 (), and 19.6 () nm.

3.7. Ammonium glyphosate release

The ammonium glyphosate release curves in Fig. 8, show that
the release rate of ammonium glyphosate decreased with increasing shell thickness: the release time required for 50% ammonium
glyphosate loaded to release from hollow silica spheres with shell
thickness of 6.1, 10.6, 17.6, and 19.6 nm, was respectively ca. 40, 60,
90, and 150 min. When the ammonium glyphosate-loaded hollow
silica spheres with shell thickness of 6.1, 10.6, 17.6, and 19.6 nm
were stirred for 180 min in water, the percentages of ammonium
glyphosate release were 99.8%, 96.9%, 92.1%, and 61.7%, respectively. Furthermore, the initial release rates within the rst 10 min
in terms of unit surface area were 7.7 106 , 6.2 106 , 6.0 106
and 4.3 106 g/(m2 min), respectively, for hollow silica spheres
with shell thickness of 6.1, 10.6, 17.6, and 19.6 nm, showing that the
initial release rates decreased with increasing shell thickness. These
results show that the shell thickness of the hollow silica spheres
signicantly affected the release of ammonium glyphosate.
4. Conclusions

Fig. 7. FT-IR spectra of Fe3 O4 template (a), silica-coated Fe3 O4 coreshell composite
(b), and hollow silica spheres (c).

Nanosized hollow silica spheres with nanoporous-structured

shells were prepared by removal of the Fe3 O4 templates from
silica-coated Fe3 O4 coreshell composites. When the silica-coated
Fe3 O4 coreshell composites were prepared with a mole ratio of
Na2 SiO3 to Fe3 O4 of 1.55:1 at different pH values, the average
external diameters of the resulting hollow silica spheres increased
from 43 to 50 nm with increasing the pH values from 6 to 10,
while the average shell thicknesses of the resulting hollow silica spheres decreased from 7.8 to 3.5 nm. When the silica-coated
Fe3 O4 coreshell composites were prepared at a pH value of 9
with different mole ratios of Na2 SiO3 to Fe3 O4 , the average external diameters and the average shell thicknesses of the resulting
hollow silica spheres increased from 48 to 70 nm and from 6.1 to

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C. Liu et al. / Particuology 10 (2012) 352358

19.6 nm, respectively, with increasing the mole ratios of Na2 SiO3
to Fe3 O4 from 1.55:1 to 3.87:1. Hollow silica spheres with highly
porous shells were obtained when silica-coated Fe3 O4 coreshell
composites were prepared at a high pH value with a low mole ratio
of Na2 SiO3 to Fe3 O4 . The shell thickness of hollow silica spheres
signicantly affected the release rate of ammonium glyphosate.
Acknowledgements
The authors thank Prof. Kangmin Chen (Analysis Center, Jiangsu
University) very much for kindly supporting TEM measurement of
the samples. This work was nancially supported by research funds
from Zhenjiang Science and Technology Bureau (GJ2006006).
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