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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
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
354
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.
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.
356
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.
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
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.
Fig. 7. FT-IR spectra of Fe3 O4 template (a), silica-coated Fe3 O4 coreshell composite
(b), and hollow silica spheres (c).
358
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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