Colloids and Surfaces A: Physicochem. Eng.

Aspects 386 (2011) 135–140

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Fabrication of SiO2 @Ag@SiO2 core–shell microspheres and thermal stability

investigation
Zhiliang Xiu a,b , Yongzhong Wu a,∗ , Xiaopeng Hao a,∗ , Lei Zhang a
a
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
b
Shandong Provincial Key Laboratory of Processing and Testing Technology of Glass & Functional Ceramics, Shandong Polytechnic University, Jinan 250353, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Uniform, dense, and thickness controllable silver shells coated on mono-dispersed SiO2 microspheres
Received 28 March 2011 were prepared by one-pot silver mirror reaction on the surface of Sn2+ -sensitized colloidal SiO2 spheres.
Received in revised form 3 June 2011 Different thickness of SiO2 -encapsulating layer was fabricated by the hydrolysis of tetraethyl orthosilicate
Accepted 10 July 2011
(TEOS) in isopropanol solution. The change of the Ag shell with the heating process could be reflected
Available online 20 July 2011
from the UV–vis absorption spectrum. The outer SiO2 layer provided greatly improved thermal stability
of the Ag shell (20 nm) up to 300 ◦ C.
Keywords:
© 2011 Elsevier B.V. All rights reserved.
Composite materials
Core–shell
Optical properties
Thermal stability

1. Introduction and compact. Zhu et al. further developed a layer-thickness-

Metal nanoparticles (Ag or Au) have drawn much attention own-
ing to their wide applications, such as catalysis, photonic crystals,
plasmonics and surface-enhanced Raman scattering [1–3]. Metal
coated dielectric colloids (e.g., SiO2 , polystyrene) with core–shell
structures have special size-dependent optical, electronic and cat-
alytic properties different from individual nanoparticles [4–6]. For
example, the plasmon resonances of metal nanoshells can be tuned
from the visible to infrared regions of the spectrum by altering the
relative core and shell dimensions, while the optical resonance is
almost a fixed frequency resonance independent of their particle
sizes for metal spheres. In addition, metal nanoshells can induce a
larger local electromagnetic field enhancement compared to indi-
vidual nanoparticles [7,8].
To solve the difficulty of the combination of the metallic and
covalent bonds, many routes have been successfully explored to
fabricate SiO2 @Ag core–shell structures, including pre-treatment
of electro-less deposition, sono-chemical deposition, surface func-
tionalization and layer by layer process [9–13]. Among them, the
pre-treatment of electro-less deposition is a promising method.
Kobayashi et al. first utilized SnCl2 to sensitize the surface of col-
loidal silica spheres and then the Ag+ ions were added and reduced
into Ag nanoparticles deposited on the silica surface [10]. How-
ever, to obtain a denser coating layer, the whole process has to
be repeated several times and the silver layers are not uniform
controllable method including two steps. Sn2+ -sensitized colloidal
SiO2 spheres were first added into a high concentration ammoni-
cal silver nitrate solution to form nanoscaled nuclei on the silica
surfaces, and then they were moved into a low concentration
ammonical silver nitrate solution and formaldehyde to control
the shell growth [14]. Although this method can fabricate dense,
uniform and thickness controllable silver layers, the fabrication
process is complex, time-consuming and also uses poisonous
formaldehyde.
In this work, a simplified and green approach by one-pot sil-
ver mirror reaction on the surface of Sn2+ -sensitized colloidal SiO2
spheres was explored. Glucose was utilized as a mild and green
reductant, and the whole process needed only a few hours. To
further improve its stability, different thickness of SiO2 layer was
coated on the Ag shell by the hydrolysis of TEOS in isopropanol
solution.
2. Materials and methods
2.1. Reagents
Tetraethyl orthosilicate (TEOS), silver nitrate, glucose, Tin (II)
chloride dihydrate, hydrochloric acid (37 wt.%), ammonia (25 wt.%),
ethanol and isopropanol were analytical grade without further
purification.
2.2. Synthesis of SiO2 microspheres

∗ Corresponding authors. Tel.: +86 531 88366218; fax: +86 531 88364864. Uniform and mono-dispersed 400 nm SiO2 microspheres were
E-mail addresses: anew2002@126.com (Y. Wu), xphao@sdu.edu.cn (X. Hao). prepared according to the well-known Stböer process [15]. 21 ml

0927-7757/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2011.07.018
136 Z. Xiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 386 (2011) 135–140

Scheme 1. Fabrication procedure of SiO2 @Ag@SiO2 core–shell microsphere.

TEOS, 9 ml H2 O and 245 ml NH4 OH were added into 225 ml absolute
ethanol and stirred at room temperature for 5 h. The resulting white
colloidal suspension was filtered, washed with distilled water and
absolute ethanol 3 times, and then dried in an oven at 80 ◦ C for 6 h.
2.3. Deposition of Ag nanopartilces on SiO2 microspheres
The Ag nanoparticles were deposited on SiO2 microspheres
using the pretreatment process in electro-less plating. 0.5 g SnCl2
was dissolved in 50 ml 0.1 M HCl to get a 0.053 M SnCl2 aque-
ous solution. 0.1 g SiO2 spheres were dispersed in the SnCl2
aqueous solution by ultrasonic wave for 20 min to obtain Sn2+ -
sensitized SiO2 spheres. After centrifugation and re-dispersion
cycles, 10 ml 5 mg/ml Sn2+ -sensitized SiO2 dispersion was poured
into the 40 ml solution of an equal volume of 0.05 M ammoni-
cal silver nitrate and 0.1 M glucose solution and stirred at room
temperature for 3 h. The concentration of ammonical silver nitrate

Fig. 1. SEM micrographs: SiO2 spheres coated with different thickness of Ag shells (A–D). Representive EDS spectrum (E) and XRD pattern (F) of the SiO2 @Ag core–shell
microspheres. The scale bar represents 300 nm.
 Z. Xiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 386 (2011) 135–140 137

solution varied from 2 to 12 mM. The final products were col-

lected, washed with deionized water 3 times and then dried at 80 ◦ C
for 6 h.

2.4. Fabrication of SiO2 @Ag@SiO2 core–shell microspheres

The above obtained Ag coated SiO2 spheres were dispersed

into solution containing 200 ml isopropanol, 20 ml H2 O, and 9 ml
ammonia. Different amount of TEOS from 160 to 230 ␮l was
added under continuous stirring for 24 h. The products were
then collected and washed by deionized water and anhydrous
ethanol.

2.5. Characterization

X-ray diffraction (XRD) patterns of the powder were examined

using a Bruker/D8-advance with CuK␣ radiation ( = 1.54178 Å).
Scanning electron microscopy (SEM) images were taken with
Fig. 2. UV–visible absorption spectra of the SiO2 @Ag microspheres prepared with
a Hitachi FESEM-4800 field emission microscope equipped different concentration of ammonical silver nitrate solution.
with a Horiba EX-450 energy-dispersive X-ray spectroscopy
(EDS). Transmission electron microscopy (TEM) was taken
using a JEM-100CX transmission electron microscope run-
ning at an accelerating voltage of 100 kV. Ultraviolet–visible
absorption spectra were measured with a Shimadzu UV-2550
spectrophotometer.

Fig. 3. SEM and TEM images of SiO2 @Ag (shell thickness: 20 nm) microspheres encapsulated with 10 (a), 20 (b) and 30 nm (c) SiO2 layer.
138 Z. Xiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 386 (2011) 135–140

Fig. 4. UV–visible absorption spectra of the SiO2 @Ag microspheres encapsulated

with different thickness of SiO2 layer.

3. Results and discussion

3.1. Formation mechanism of SiO2 @Ag@SiO2 microspheres

Scheme 1 describes the formation process of SiO2 @Ag@SiO2

microspheres. First, Sn2+ ions adsorption takes place on the surfaces
of SiO2 microspheres via electrostatic interaction. Second, Sn2+ ions
reduce Ag+ ions to form Ag nuclei deposited on the surfaces of SiO2
spheres as seeds. Third, the remaining Ag+ ions are further reduced
by glucose and Ag nanoparticles grow gradually to form a uniform
silver layer. At last, the outer SiO2 layer forms on the Ag shell by
the hydrolysis of TEOS in isopropanol solution.

3.2. Characterization of SiO2 @Ag microspheres

SEM images of SiO2 @Ag composite microspheres with different

thicknesses of Ag shell are shown in Fig. 1(A–D). When 2 or 4 mM of
ammonical silver nitrate solution were added, the silver nanopar-
ticles deposited on SiO2 spheres were uniform but not compact.
Their average particle sizes were about 8 and 15 nm, respectively.
When the concentration of ammonical silver nitrate solution was
increased to 8 mM, a much denser Ag shell with thickness of about
20 nm formed on the spheres. As the concentration of ammoni-
cal silver nitrate solution further increased, the Ag nanoparticles
on the surfaces of silica spheres grew much bigger. The EDS result
of the coated SiO2 spheres with a 20 nm silver shell (Fig. 1E) con-
firms the existence of Ag, Si, O, Al. Al peaks come from the sample
support, and Si and O peaks results from the silica core. No other
peaks were detected in the EDS measurement, suggesting the high
purity of the silver coating layer. All diffraction peaks in the typical
XRD pattern of the SiO2 @Ag composite microspheres (Fig. 1F) can
be indexed to the face-centered cubic (fcc) structure of metallic Ag
(JCPDS No. 04-0783). The diffraction peaks are sharp, indicating the
high crystallinity of the silver shell.
Fig. 2 shows the UV–visible absorption spectra of the SiO2 @Ag
microspheres with different thickness of the Ag shell. The sizes
of the Ag particles are about 8, 15, 20 and 25 nm as the concen-
tration of ammonical silver nitrate solution is 2, 4, 8 and12 mM,
respectively. For the 8 nm Ag particles deposited SiO2 spheres, an
intense peak around 415 nm appears due to the Mie plasmon res-
onance excitation from Ag nanoparticles [12]. With increasing the
thickness of the Ag shell, the plasmon peak becomes broader and
red-shifted, indicating the formation and growth of the Ag shell. The
plasmon absorption shifts to around 500 nm when the SiO2 spheres
Fig. 5. SEM images of the SiO2 @Ag microspheres heated at 100 (a), 200 (b) and
300 ◦ C (c).
are coated with 15 nm Ag particles. A small shoulder located around
400 nm is ascribed to the formation of larger Ag colloids in the solu-
tion. As the Ag particle sizes increase continuously, the plasmon
resonance absorption in the visible region becomes flat similar to
the results reported by Halas and co-workers [7]. The absorption
at 400 nm becomes stronger indicating the formation of more Ag
colloids in the solution.
3.3. SEM and optical properties of SiO2 @Ag@SiO2 microspheres
Fig. 3 shows the SEM and TEM images of SiO2 @Ag@SiO2 micro-
spheres with different thickness of the outer SiO2 layer. The
thickness of Ag shell is 20 nm. The thickness of the outer SiO2 layer
can be controlled from 10 to 30 nm by adjusting the amount of
TEOS.
After coated with an outer SiO2 layer, the absorption properties
of SiO2 @Ag microspheres change greatly as shown in Fig. 4. The
flat plasmon resonance absorption turns into an intense absorption
band centered at about 500 nm due to changes of dielectric constant
of the environment around the Ag shell [16]. With increasing the
thickness of SiO2 layer, the absorption properties change slightly.
 Z. Xiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 386 (2011) 135–140 139

3.4. Thermal stability of SiO2 @Ag@SiO2 microspheres

As well known, metal nanoparticles could be melted under rel-

ative low temperature owing to small size effect. The melting point
of 5 nm Ag nanoparticles decreases to below 100 ◦ C, despite that
of the bulk Ag material is as high as 960.5 ◦ C [17]. The morphol-
ogy variation of the naked SiO2 @Ag microspheres (the Ag shell is
20 nm) heated at different temperature can be seen in Fig. 5. Heated
at low temperature 100 ◦ C for 3 h, some Ag nanoparticles fell off
the silica core and their sizes varied slightly. When temperature
above 200 ◦ C, the Ag shell began to melt and form large, round Ag
nanoparticles.
The optical properties of SiO2 @Ag@SiO2 microspheres (the Ag
shell is 20 nm) heated at different temperature are shown in Fig. 6.
The spectra of Ag nanoshells have no obvious change when heated
below 300 ◦ C for 3 h. As the temperature increased to 400 ◦ C, the
broad maximum has a ∼50 nm blueshift, suggesting the morphol-
ogy of the Ag shell has experienced some changes. The absorbance
peak further shifts to 415 nm typical for Ag colloid as the heat-
Fig. 6. UV–visible absorption spectra of the SiO2 @Ag@SiO2 microspheres heated at
ing temperature exceeds 500 ◦ C, indicating the Ag shell may be
different temperature.
destructed and transform into discrete Ag nanoparticles.
The morphology changes of the Ag nanoshell can be revealed
from the corresponding SEM and TEM images (Fig. 7). The uncoated
Ag shell The morphology of Ag shell heated below 400 ◦ C changes

Fig. 7. SEM and TEM images of the SiO2 @Ag@SiO2 microspheres heated at 300 (a), 400 (b) and 500 ◦ C (c).
140 Z. Xiu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 386 (2011) 135–140
slightly. As the temperature reaches 500 ◦ C, the Ag shell is melted
completely and recrystallize into large, round and discrete Ag
nanospheres attached to the silica core. This agrees well with the
observed changes in the absorption spectra.
4. Conclusions
One-pot silver mirror reaction was explored to fabricate
SiO2 @Ag core–shell microspheres utlizing glucose as a mild
and green reductant. By changing the concentration of the
precursor-ammonical silver nitrate and glucose solution, differ-
ent particle size and degree of coverage of Ag nanoparticles on
SiO2 microspheres were obtained. Their plasmonic absorption
became red-shifted, flat and involved almost the whole visible light
region with increasing the shell thickness. Encapsulation of a SiO2
layer could greatly enhance the thermal stability of the SiO2 @Ag
core–shell microspheres.
Acknowledgements
This work was supported by NCET (070512), NSFC (Contract No.
50823009, 50721002, 50801042), National Basic Research Program
of China (2009CB930503) and the Key Project of Chinese Ministry of
Education (No. 109096). Thanks to Dr. Edward C. Mignot, Shandong
University, for linguistic advice.
References
[1] A. Wittstock, J. Biener, M. Baumer, Nanoporous gold: a new material for catalytic
and sensor applications , Phys. Chem. Chem. Phys. 12 (2010) 12919–12930.
[2] I. Pastoriza-Santos, L.M. Liz-Marzan, Formation of PVP-protected metal
nanoparticles in DMF , Langmuir 18 (2002) 2888–2894.
[3] S.Z. Zhang, W.H. Ni, X.S. Kou, M.H. Yeung, L.D. Sun, J.F. Wang, C.H. Yan, Formation
of gold and silver nanoparticle arrays and thin shells on mesostructured silica
nanofibers , Adv. Funct. Mater. 17 (2007) 3258–3266.
[4] Z.J. Liang, A. Susha, F. Caruso, Gold nanoparticle-based core–shell and hol-
low spheres and ordered assemblies thereof , Chem. Mater. 15 (2003)
3176–3183.
[5] F. Caruso, Nanoengineering of particle surfaces , Adv. Mater. 13 (2001) 11-+.
[6] T. Pham, J.B. Jackson, N.J. Halas, T.R. Lee, Preparation and characterization of
gold nanoshells coated with self-assembled monolayers , Langmuir 18 (2002)
4915–4920.
[7] J.B. Jackson, N.J. Halas, Silver nanoshells: variations in morphologies and optical
properties , J. Phys. Chem. B 105 (2001) 2743–2746.
[8] K. Tanabe, Field enhancement around metal nanoparticles and nanoshells: a
systematic investigation , J. Phys. Chem. C 112 (2008) 15721–15728.
[9] S.J. Oldenburg, G.D. Hale, J.B. Jackson, N.J. Halas, Light scattering from dipole
and quadrupole nanoshell antennas , Appl. Phys. Lett. 75 (1999) 1063–1065.
[10] Y. Kobayashi, V. Salgueirino-Maceira, L.M. Liz-Marzan, Deposition of sliver
nanoparticles on silica spheres by pretreatment steps in electroless plating ,
Chem. Mater. 13 (2001) 1630–1633.
[11] F. Caruso, R.A. Caruso, H. Mohwald, Nanoengineering of inorganic and hybrid
hollow spheres by colloidal templating , Science 282 (1998) 1111–1114.
[12] Z.J. Jiang, C.Y. Liu, Seed-mediated growth technique for the preparation
of a silver nanoshell on a silica sphere , J. Phys. Chem. B 107 (2003)
12411–12415.
[13] Z.W. Deng, M. Chen, L.M. Wu, Novel method to fabricate SiO2 /Ag composite
spheres and their catalytic, surface-enhanced Raman scattering properties , J.
Phys. Chem. C 111 (2007) 11692–11698.
[14] M.W. Zhu, G.D. Qian, Z.L. Hong, Z.Y. Wang, X.P. Fan, M.Q. Wang, Preparation and
characterization of silica–silver core–shell structural submicrometer spheres ,
J. Phys. Chem. Solids 66 (2005) 748–752.
[15] W. Stböer, A. Fink, E. Bohn, J. Colloid Interface Sci. 26 (1968) 62–69.
[16] P. Mulvaney, L.M. Liz-Marzan, M. Giersig, T. Ung, Silica encapsulation of quan-
tum dots and metal clusters , J. Mater. Chem. 10 (2000) 1259–1270.
[17] Y.X. Qin, M. Hu, H.Y. Li, Z.S. Zhang, Q. Zou, Preparation and field emission prop-
erties of carbon nanotubes cold cathode using melting Ag nano-particles as
binder , Appl. Surf. Sci. 253 (2007) 4021–4024.