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Ultrasonic-assisted ultra-rapid synthesis of monodisperse

meso-SiO
2
@Fe
3
O
4
microspheres with enhanced mesoporous structure
Hongfei Liu, Shengfu Ji

, Hao Yang, Huan Zhang, Mi Tang


State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, PR China
a r t i c l e i n f o
Article history:
Received 15 June 2013
Received in revised form 19 August 2013
Accepted 19 August 2013
Available online 28 August 2013
Keywords:
Ultrasonic
Ultra-rapid
Coreshell structure
meso-SiO
2
@Fe
3
O
4
microspheres
Magnetic
Mesoporous silica
a b s t r a c t
A coreshell-type of meso-SiO
2
@Fe
3
O
4
microsphere was synthesized via an ultrasonic-assisted surfac-
tant-templating process using solvothermal synthesized Fe
3
O
4
as core, tetraethoxysilane (TEOS) as silica
source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by
FT-IR, XRD, TEM, N
2
adsorptiondesorption technology, and vibrating sample magnetometer (VSM). The
results show that as-prepared meso-SiO
2
@Fe
3
O
4
(E) and meso-SiO
2
@Fe
3
O
4
(C) microspheres, treated by
acetone extraction and high temperature calcination, respectively, still maintain uniform coreshell
structure with desirable mesoporous silica shell. Therein, the meso-SiO
2
@Fe
3
O
4
(E) microspheres possess
a distinct pore size distribution in 1.83.0 nm with large specic surface area (468.6 m
2
/g) and pore
volume (0.35 cm
3
/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is
much shorter than that of the conventional method (1224 h). The morphology of microspheres and
the mesoporous structure of silica shell are signicantly inuenced by initial concentration of CTAB
(C
CTAB
), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of
ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including
hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and
deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving
the homogeneity of silica shell and the monodispersity of meso-SiO
2
@Fe
3
O
4
microspheres.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Recently, various types of magnetic mesoporous silica nano-
composites (MMSNs) with magnetic responsibility and mesopor-
ous structure have attracted much attention due to their
potential applications in catalysis, drug/DNA/gene delivery, water
treatment, multimodal imagine, and so on [1,2]. Among them,
coreshell-type MMSN microspheres with large Fe
3
O
4
spherical
cores (100300 nm) and MCM-41 family ordered mesoporous
silica shells have been the subject of extensive researches because
to their unique features, including high thermal and chemical
stabilities, favorable biocompatibility and superparamagnetism,
simple functionality, high available surface area, and large pore
volume [35]. The most representative coreshell-type MMSN
microspheres (Fe
3
O
4
@nSiO
2
@mSiO
2
) with perpendicularly aligned
mesoporous shells were rstly synthesized by Zhao and coworkers
through a two-step coating process [4]. Subsequently, some
modied coreshell-type MMSN microspheres with different
specic function were obtained upon the similar two-step coating
process [57]. During this two-step coating process, uniform Fe
3
O
4
microspheres are rstly precoated with a thin silica layer through a
modied stber process, and this layer is indispensable for the
deposition of uniform mesoporous silica shell through a surfac-
tant-templating approach with cetyltrimethyl ammonium
bromide (CTAB) as the templates. Therein, the thin silica layer
and uniform mesoporous silica shell are derived from slow hydro-
lysis of tetraethyl orthosilicate (TEOS) (at least 1224 h of mechan-
ical stirring at room temperature). As a result, relatively complex
preparation routes and long-time coating processes limit their
applications in some way. Additionally, these above mentioned
coreshell-type MMSN microspheres exhibit poor monodispersity
which is bad for their applications in bio-elds and liquidsolid
heterogeneous catalysis. Therefore, exploration of new strategies
to rapidly and facilely synthesize coreshell-type MMSN micro-
spheres with desirable monodispersity is in high demand.
Over the past decades, ultrasonic method has been widely used
in the preparation of powdery nanomaterials owing to its special
cavitation process composed of formation, growth, and collapse
of microbubbles in liquid solution [810]. During this process,
extremely high peak temperature (>5000 K), pressure (>20 MPa),
and cooling rates (over 10
11
K/s) are attained inside the cavities
due to the transient collapsing of the bubbles [11], meanwhile,
microjet stream and shock wave are generated inside the liquids
solution [12]. Considered these unique properties in the ultrasonic
1350-4177/$ - see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ultsonch.2013.08.010

Corresponding author. Tel./fax: +86 10 64419619.


E-mail address: jisf@mail.buct.edu.cn (S. Ji).
Ultrasonics Sonochemistry 21 (2014) 505512
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j our nal homepage: www. el sevi er . com/ l ocat e/ ul t son
irradiated solution, the ultrasonic technique was used in the syn-
thesis of zeolites and mesoporous silicas, such as MCM-22 [13],
SBA-15 [14], and MCM-41 [15], and it was proven that the ultra-
sonic treatment was effective to shorten synthesis period and im-
prove pore structure. Very recently, ultrasonic approach has been
successfully applied for the fabrication of various composites with
distinct coreshell structure [1618]. Among them, a rapid sono-
chemical synthesis of monodisperse nonaggregated Fe
3
O
4
@SiO
2
magnetic nanoparticles with nonporous silica shell was reported
[12], and it was shown that the coating process was accelerated
many-fold in the presence of a 20 kHz ultrasonic eld. Therefore,
it is believed that the ultrasonic holds many prospects for resolving
aforementioned problems, long-time preparation time and poor
monodispersity, in the synthesis of coreshell-type MMSN
microspheres.
In this work, we report, for the rst time, an ultrasonic-assisted
ultra-rapid synthesis of coreshell meso-SiO
2
@Fe
3
O
4
microspheres
with Fe
3
O
4
core and homogeneous mesoporous silica shell by a
CTAB-templating approach. The structure and physical properties
of as-prepared meso-SiO
2
@Fe
3
O
4
(E) and meso-SiO
2
@Fe
3
O
4
(C)
microspheres, which are treated by acetone extraction and high
temperature calcination, respectively, were studied by XRD, TEM,
N
2
adsorptiondesorption technique and VSM. The inuences of
initial concentration of CTAB, ultrasonic irradiation power and
ultrasonic irradiation time to the structural properties of meso-
SiO
2
@Fe
3
O
4
(E) microspheres were investigated systematically. Fi-
nally, the formation mechanism of meso-SiO
2
@Fe
3
O
4
microspheres
prepared by ultrasonic-assisted method was discussed.
2. Experimental
2.1. Synthesis of Fe
3
O
4
Briey, 4.32 g of FeCl
3
6H
2
O and 12.0 g of sodium acetate were
dissolved in 160 mL of glycol under stirring. The obtained homoge-
neous yellow solution was transferred to a 200 mL Teon-lined
stainless-steel autoclave. The autoclave was sealed and heated at
200 C. After heated for 12 h, the autoclave was naturally cooled
to room temperature. The obtained black magnetite particles were
separated with a permanent magnet, washed with ethanol for six
times, and dried in vacuum at 60 C for 24 h.
2.2. Synthesis of meso-SiO
2
@Fe
3
O
4
0.1 g of as-prepared Fe
3
O
4
microspheres was dispersed into the
mixture solution of 80 mL of ethanol, 10 mL of deioned water, 4 mL
of concentrated ammonia aqueous solution (28 wt%), and a certain
amount of CTAB. After this, the mixture solution was homogenized
by ultrasonication (frequency = 40 kHz, power = 150 W) for 10 min
to form a homogeneous dispersion. Subsequently, TEOS (0.25 mL)
in ethanol (24 mL) was injected into the synthesis system under
ultrasonic irradiation. After the reaction was performed for a cer-
tain time, the product was separated with a permanent magnet,
washed with deionized water for three times, and dried in vacuum
at 50 C for 12 h to obtain the meso-SiO
2
@ Fe
3
O
4
microspheres. The
template removal was studied by two different methods:
(i) Solvent extraction: as-prepared meso-SiO
2
@Fe
3
O
4
micro-
spheres were dispersed in acetone and kept at 80 C under
N
2
protection for 24 h. This procedure was repeated twice.
The product was dened as meso-SiO
2
@Fe
3
O
4
(E).
(ii) High temperature Calcination: as-prepared meso-SiO
2
@Fe
3
O
4
microspheres were calcined for 3 h at 450 C under N
2
pro-
tection. The heating rate was set to 1 C/min. The product
was dened as meso-SiO
2
@Fe
3
O
4
(C).
To study the inuence of different preparation conditions on the
structure and properties of meso-SiO
2
@Fe
3
O
4
(E) particles, various
conditions including initial concentration of CTAB (C
CTAB
= 0
10.29 mmol/L), ultrasonic irradiation power (P = 60150 W) and
ultrasonic irradiation time (t = 540 min) were chosen and their ef-
fects were investigated during the preparation process.
2.3. Characterization
Power X-ray diffraction (XRD) patterns were collected on a
D/Max 2500 VB2+/PC diffractometer with Ka irradiation of Cu
(k = 1.5418 , 200 kV, 50 mA). The N
2
adsorptiondesorption
analysis was tested on an ASAP 2020 M automatic specic surface
area and aperture analyzer, and the specic surface area determi-
nation and pore volume analysis were performed by Brunauer
EmmettTeller (BET) and BarrettJoynerHalenda (BJH) methods,
respectively. Transmission electron microscopy (TEM) and high-
resolution (HR) TEM images were taken with a JEOL (JEM-2100)
transmission electron microscope operated at 200 kV accelerating
voltage. Magnetic properties of the samples were measured on a
vibration sample magnetometer (VSM; Lake Shore Model 7400)
under magnetic elds up to 20 kOe.
3. Results and discussion
3.1. Characteristics of as-prepared meso-SiO
2
@Fe
3
O
4
microspheres
3.1.1. XRD of samples
Fig. 1 shows the typical XRD patterns of Fe
3
O
4
, meso-SiO
2
@Fe
3-
O
4
(E) and meso-SiO
2
@Fe
3
O
4
(C), where meso-SiO
2
@Fe
3
O
4
particles
were synthesized under following condition: C
CTAB
= 6.86 mmol/L,
P = 150 W and t = 30 min. From Fig. 1a, the wide-angle XRD pat-
terns of all samples show obvious diffraction peaks, which can be
readily indexed to face center cubic magnetite phase (Fe
3
O
4
, JCPDS
No. 19-0629). For meso-SiO
2
@Fe
3
O
4
(E) and meso-SiO
2
@Fe
3
O
4
(C),
the broad peak at 2h = 2030 can be assigned to the amorphous
silica (SiO
2
, JCPDS No. 29-0085) [6]. From Fig. 1b, the low-angle
XRD patterns of meso-SiO
2
@Fe
3
O
4
(E) and meso-SiO
2
@Fe
3
O
4
(C)
present obvious (100) peak at around 2.5 and invisible (110)
and (200) peaks, which suggest the ordered mesopore symmetry,
revealing the existence of short-range ordered mesoporous
structure [5,6]. The decrease of intensity of (100) peak for
meso-SiO
2
@Fe
3
O
4
(C) sample may be due to the high temperature
treatment, which results in the decrease of ordering of the meso-
porous structure.
3.1.2. TEM of samples
The TEM images of meso-SiO
2
@Fe
3
O
4
samples are shown in
Fig. 2. For meso-SiO
2
@Fe
3
O
4
(E), monodisperse microspheres with
uniform coreshell structure are clearly exhibited in Fig. 3a, from
which it is obvious that the Fe
3
O
4
core is well coated by a silica
shell with thickness of about 50 nm. From HRTEM image
(Fig. 3c), we can observe abundant of wormlike mesopores in the
silica shell, which is different with perpendicularly aligned mesop-
ores presented in Fe
3
O
4
@nSiO
2
@mSiO
2
microspheres prepared by
traditional two-step coating process [46]. Noteworthily, meso-
SiO
2
@Fe
3
O
4
(C) microspheres still exhibit uniform coreshell struc-
ture with about 50 nm silica shell (Fig. 3b), and the silica shell keep
the similarly wormlike mesopores (Fig. 3d), reecting the favorable
thermostability of as-prepared meso-SiO
2
@Fe
3
O
4
microspheres.
3.1.3. N
2.
adsorptiondesorption analysis of samples
In order to directly characterize the textural properties of as-
prepared meso-SiO
2
@Fe
3
O
4
microspheres, meso-SiO
2
@Fe
3
O
4
(E)
and meso-SiO
2
@Fe
3
O
4
(C) microspheres were analyzed by N
2
506 H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512
adsorptiondesorption technology. Fig. 3 shows the N
2
adsorp-
tiondesorption isotherms and the pore size distribution curves
of Fe
3
O
4
and meso-SiO
2
@Fe
3
O
4
microspheres. It can be seen that
the Fe
3
O
4
particles exhibit III-type isotherm and corresponding
pore size distribution curve presents non-porous structure. For
meso-SiO
2
@Fe
3
O
4
(E), we can observed a typical IV-type curve with
a steep increase in the P/P
0
range of 0.040.25 (Fig. 3a), and corre-
sponding pore size distribution curve presents a sharp peak cen-
tered at the mean value of 2.3 nm (Fig. 3b). The products
obtained via traditional two-step coating process have the same
N
2
adsorptiondesorption characteristic [46]. Unusually, there is
an obvious H1 hysteresis loop consisting one broad capillary con-
densation step at P/P
0
of 0.450.95 indicated by black arrow in
Fig. 3a, which indicates the presence of textual mesopores [5].
The same phenomenon was observed in the ultrasonic-assisted
synthesis of ordered mesoporous silica SBA-15 [14]. The BET sur-
face area and BJH pore volume of meso-SiO
2
@Fe
3
O
4
(E) micro-
spheres are calculated to be 468.6 m
2
/g and 0.35 cm
3
/g,
respectively, which are higher than that of samples obtained by
traditional two-step coating process [46]. For meso-SiO
2
@Fe
3
O
4
(C), the N
2
adsorptiondesorption isotherm exhibits a similar IV-
type isotherm with an unobvious H1 hysteresis loop, but the pore
size distribution curve presents a relatively broad peak at value of
1.83.0 nm, conrming the decrease of ordering of the mesopore
structure after high temperature calcination. The BET surface area
and BJH pore volume of meso-SiO
2
@Fe
3
O
4
(E) microspheres de-
crease to 356.3 m
2
/g and 0.29 cm
3
/g, respectively.
3.1.4. VSM of samples
Fig. 4 shows the magnetization curves of Fe
3
O
4
and meso-
SiO
2
@Fe
3
O
4
microspheres. All curves appear nonlinear and
reversible characteristic with no hysteresis (zero coercivity and
no remanence), exhibiting superparamagnetic behavior. The
Fig. 1. (a) Wide-angle XRD patterns and (b) low-angle XRD patterns of samples.
Fig. 2. TEM images of the samples: (a) and (c) meso-SiO
2
@Fe
3
O
4
(E); (b) and (d)
meso-SiO
2
@Fe
3
O
4
(C).
Fig. 3. (a) N
2
adsorptiondesorption isotherms and (b) pore size distribution curves
of samples.
H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512 507
saturation magnetization (Ms) values of meso-SiO
2
@Fe
3
O
4
(C) and
meso-SiO
2
@Fe
3
O
4
(E) are 44.72 and 40.38 emu/g, respectively,
which can completely meet the requirement of the magnetic sep-
aration. The slight increase of Ms. values for meso-SiO
2
@Fe
3
O
4
(C)
microspheres may be due to the Ostwald ripening during high
temperature calcination [19].
From above results, it can be found that, in the ultrasonic-as-
sisted synthesis of meso-SiO
2
@Fe
3
O
4
microspheres, the use of
ultrasonic can effectively shorten the coating period of mesoporous
silica from 1224 h to 40 min, and obtained meso-SiO
2
@Fe
3
O
4
microspheres still exhibit uniform coreshell structure with desir-
able mesoporous silica shell after acetone extraction or high tem-
perature calcination.
3.2. Effect of synthesis conditions on structure and properties of as-
prepared meso-SiO
2
@Fe
3
O
4
(E) microspheres
In consideration of the extraordinary mesoporous shell of meso-
SiO
2
@Fe
3
O
4
(E) microspheres. It is necessary to study several repre-
sentative processing parameters, such as initial concentration of
CTAB, ultrasonic irradiation power and ultrasonic irradiation time,
which may inuence the structure and/or properties of product in
the ultrasonic-assisted synthesis process. Therefore, three series of
meso-SiO
2
@Fe
3
O
4
(E) samples were prepared when any of the
above variables was changed independently of the others.
3.2.1. Initial concentration of CTAB
Fig. 5 shows the low-angle XRD patterns of meso-SiO
2
@Fe
3
O
4
(E)
microspheres which were synthesized with different C
CTAB
,
whereas the other variables were held constant (P = 150 W and
t = 30 min). As shown in Fig. 5, no diffraction peak is observed in
the low-angle XRD pattern (a) of sample prepared without CTAB.
The patterns (bf) of samples obtained with CTAB present obvious
(100) peak at around 2.5 and invisible (110) and (200) peaks,
revealing the existence of short-range ordered mesoporous struc-
ture [5,6]. And the ordering of this mesoporous structure is im-
proved with the C
CTAB
increased from 1.76 to 6.86 mmol/L
according to the gradually enhanced intensity of (100) peak. More-
over, nearly unchanged intensity of (100) peak at 10.29 mmol/L of
C
CTAB
suggests that excess CTAB is unnecessary for ultrasonic-as-
sisted synthesis of meso-SiO
2
@Fe
3
O
4
microspheres.
Fig. 6 shows the N
2
adsorptiondesorption isotherms and pore
size distribution curves of meso-SiO
2
@Fe
3
O
4
(E) microspheres
obtained with different C
CTAB
. The sample obtained without CTAB
presents non-porous characteristics. In the presence of CTAB, the
N
2
adsorptiondesorption isotherms of all samples exhibit distinct
IV-type isotherm with H1 hysteresis loop, and corresponding pore
size distribution curves present a distinct peak at value of 1.8
3.0 nm, indicating the presence of short-range ordered mesopores
[4]. Furthermore, the intensity of the pore size distribution gradu-
ally enhances with the increase of C
CTAB
from 1.76 to 6.86 mmol/L,
conrming the improvement of the mesoporous structure, but it
remains nearly unchanged at C
CTAB
of 10.29 mmol/L. Meanwhile,
it can be seen from Table 1 that the BET surface area and BJH pore
volume of samples increase rst and then decrease with the in-
crease of C
CTAB
.
Fig. 7 shows the TEM images of meso-SiO
2
@Fe
3
O
4
(E) micro-
spheres obtained using different C
CTAB
. It can be observed from
Fig. 7ac and eg that as-prepared meso-SiO
2
@Fe
3
O
4
(E) micro-
spheres keep monodisperse coreshell structure and their meso-
porous structure of silica shell becomes increasingly clear in the
C
CTAB
range of 06.86 mmol/L. However, the microspheres ob-
tained at 10.29 mmol/L of C
CTAB
show serious aggregation which
may account for their slight decrease of BET surface area and BJH
volume.
From above results it can be inferred that the monodispersion
and mesoporous structure of as-prepared meso-SiO
2
@Fe
3
O
4
(E)
microspheres are signicantly inuenced by C
CTAB
. Low C
CTAB
has
adverse effects on mesoporous structure of silica shell and high
C
CTAB
goes against the monodispersion of microspheres. The opti-
mum C
CTAB
for ultrasonic-assisted synthesis of meso-SiO
2
@Fe
3
O
4
(E)
microspheres is about 6.86 mmol/L.
3.2.2. Ultrasonic irradiation power
Fig. 8 shows the TEM images of meso-SiO
2
@Fe
3
O
4
(E) micro-
spheres which were synthesized under different P of 60, 90, 120,
and 150 W, respectively, whereas the other variables were held
constant (C
CTAB
= 6.86 mmol/L and t = 30 min). From Fig. 8a, it can
be seen that Fe
3
O
4
microspheres exhibit serious aggragation be-
cause of the non-uniform mesoporous SiO
2
coating under 60 W
of P. With the P increased from 90 to 150 W, the uniformity of
the mesoporous silica shell and the monodispersity of meso-SiO
2
@-
Fe
3
O
4
(E) microspheres are improved obviously (Fig. 8bd). There-
fore, it can be concluded that the P have important effects on the
architectural feature of obtained microspheres [12,17].
Fig. 4. Magnetization curves of samples: (a) pure Fe
3
O
4
; (b) meso-SiO
2
@Fe
3
O
4
(E);
(c) meso-SiO
2
@Fe
3
O
4
(C).
Fig. 5. Low-angle patterns of meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained using
different C
CTAB
: (a) 0; (b) 1.76; (c) 3.43; (d) 5.19; (e) 6.86; and (f) 10.29 mmol/L.
(P = 150 W and t = 30 min).
508 H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512
Fig. 9 shows the N
2
adsorptiondesorption isotherms and pore
size distribution curves of meso-SiO
2
@Fe
3
O
4
(E) microspheres ob-
tained using different P. As a whole, all samples exhibit distinct
IV-type isotherms with an obvious H1 hysteresis loop (Fig. 9a),
and corresponding pore size distribution curves emerge a distinct
peak at 1.83.0 (Fig. 9b). With the increase of P, the intensity of
the pore size distribution enhances apparently, and the BET surface
area and BJH pore volume keep continuous increase (Table 1), indi-
cating the enhancement of mesoporous structure of the silica shell.
Same results were shown in ultrasonic synthesis of mesoporous
molecular sieve (MCM-41) [15]. Therefore, it can be believed that
using relatively high P is benecial to synthesize monodisperse
meso-SiO
2
@Fe
3
O
4
(E) microspheres with favorable mesoporous sil-
ica shell.
3.2.3. Ultrasonic irradiation time
To gain insight into the formation process of mesoporous silica
shell of the meso-SiO
2
@Fe
3
O
4
(E) microspheres under ultrasonic
irradiation, time-dependent experiments were carried out. Fig. 10
shows the TEM images of meso-SiO
2
@Fe
3
O
4
(E) microspheres under
different t of 5, 10, 20, 30, and 40 min, respectively, whereas the
other variables were held constant (C
CTAB
= 6.86 mmol/L and
P = 150 W). In general, it can be observed from Fig. 10 that all sam-
ples present monodisperse coreshell microspheres (Fig. 10ae),
and the thickness of silica shell increases from 5 to 50 nm
(Fig. 10fj) with the extension of t, revealing the gradual formation
of that silica shell. When t is only 5 min, only a thin SiO
2
(average
thickness of 5 nm) layer without obvious mesoporous structure
can be observed (Fig. 10a and f). Subsequently, as t prolonged to
10 min, it can be noticed from the image contrast that there exist
obvious wormlike mesopores in the silica shell (Fig. 10b and g),
and that wormlike mesoporous structure is increasingly clear
when t is 20 min (Fig. 10c and h). With further extended t to
30 min and more, the morphology structure and thickness (about
50 nm) of mesoporous silica shell keep unchanged (Fig. 10d,e,i
and j), revealing the fully formed of the mesoporous silica shell
during the 30 min of synthesis time.
Fig. 11 shows the N
2
adsorptiondesorption isotherms and pore
size distribution curves of meso-SiO
2
@Fe
3
O
4
(E) microspheres syn-
thesized under different t. As shown in Fig. 11, when t is only
5 min, the N
2
adsorptiondesorption isotherm and pore size distri-
bution curve conrm that there is no mesoporous structure in the
thin silica shell. As t prolonged to 10 min, the sample exhibits dis-
tinct IV-type isotherm and corresponding pore size distribution
curve emerge a broad peak in 1.83.0 nm. With t further extended
to 20 min and more, the intensity of the pore size distribution
gradually enhances. In addition, Table 1 shows that the BET surface
area and BJH pore volume of samples increase gradually and then
remain nearly unchanged with the extension of t.
Therefore, we can conclude that there is close relationship be-
tween mesoporous structure of silica shell and t. The mesoporous
silica shell of as-prepared meso-SiO
2
@Fe
3
O
4
(E) microspheres is
composed by two parts: inner nonporous layer, and outer meso-
porous layer with a pore size distribution in 1.83.0 nm.
Fig. 6. (a) N
2
adsorptiondesorption isotherms and (b) pore size distribution curves
of the meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained using different C
CTAB
. (P = 150 W
and t = 30 min).
Table 1
Textural and structural characteristics of samples prepared in different preparation conditions.
Sample C
CTAB
a
(mmol/L) P
b
(W) t
c
(min) S
BET
(m
2
g
1
)
d
V
BJH
e
(cm
3
g
1
) Dv
f
(nm)
1 0 150 30 32.3 0.07 8.0
2 1.76 150 30 142.6 0.11 3.3
3 3.43 150 30 209.0 0.16 3.1
4 5.19 150 30 306.4 0.24 2.8
5 6.86 150 30 468.6 0.35 2.3
6 10.29 150 30 398.1 0.32 2.6
7 6.86 60 30 153.9 0.13 3.3
8 6.86 90 30 315.5 0.26 2.9
9 6.86 120 30 414.3 0.31 2.4
10 6.86 150 5 23.7 0.04 7.2
11 6.86 150 10 103.4 0.17 5.9
12 6.86 150 20 245.2 0.22 3.2
13 6.86 150 40 441.4 0.34 2.3
a
Initial concentration of CTAB.
b
Ultrasonic irradiation power.
c
Ultrasonic irradiation time.
d
Multipoint BET surface area.
e
BJH method cumulative desorption pore volume.
f
Average pore diameter.
H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512 509
3.3. Formation mechanism of ultrasonic-assisted synthesized meso-
SiO
2
@Fe
3
O
4
microspheres
Based on the above results and discussion, the ultrasonic-as-
sisted synthesis process of meso-SiO
2
@Fe
3
O
4
microspheres can be
summarized in schematic illustration as shown in Scheme 1. Com-
pared with the classical two-step coating process [46], the ultra-
sonic-assisted synthesis route has only one CTAB-templating
approach, but as-prepared meso-SiO
2
@Fe
3
O
4
microspheres present
similar coreshell structure with an inner nonporous silica layer.
Actually, the presence of this inner nonporous silica layer can not
only serve as nucleation seeds for growth of mesoporous silica
layer [2] but also protect magnetic cores to improve the thermal
and chemical stability of meso-SiO
2
@Fe
3
O
4
microspheres [20].
In addition to simplify the coating procedure, the applied
ultrasonic environment plays some signicant roles in formation
of meso-SiO
2
@Fe
3
O
4
microspheres. In conventional synthesis of
coreshell-type MMSN microspheres, the formation process of
Fig. 7. TEM images of the meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained using different C
CTAB
: (a) and (e) 0; (b) and (f) 3.43; (c) and (g) 6.86; (d) and (h) 10.29 mmol/L
(P = 150 W and t = 30 min).
Fig. 8. TEM images of the meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained under
different P: (a) 60; (b) 90; (c) 120; (d) 150 W. (C
CTAB
= 6.86 mmol/L and t = 30 min).
Fig. 9. (a) N
2
adsorptiondesorption isotherms and (b) pore size distribution curves
of the meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained under different P. (C
CTAB
= 6.86 -
mmol/L and t = 30 min).
510 H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512
mesoporous silica shell based on CTAB-templating stber method
has been summarized as follow [2]: rstly, TEOS molecules were
alkaline hydrolyzed, and then hydrolyzed precursors and
templates (CTAB) co-assembled into composite micelles through
electrostatic interaction. Subsequently, the composite micelles
aggregated, precipitated from the solution because of the conden-
sation of hydrolyzed precursors, and formed the nanosized
oligomers. Finally, these precipitated nanosized oligomers depos-
ited on the magnetic particles, shaping an ordered mesostructured
silica layer. In our ultrasonic-assisted synthesis of monodisperse
meso-SiO
2
@Fe
3
O
4
microspheres, the ultrasound gave full play to
the role of process intensication. Therein, the most obvious per-
formance was ultra-rapid synthesis time. The acceleration role of
the ultrasound was mainly manifested in following aspects. On
the one hand, because the hydrolysis-condensation process of
TEOS was known to be temperature sensitive [21], transient high
temperature produced by cavitation process would lead to strong
local acceleration of this hydrolysis-condensation process. On the
other hand, microjet stream and shock wave generated inside the
liquids solution by cavitation process could effectively enhance
the mass transfer [2224], thereby improving the co-assembly of
hydrolyzed precursors and templates (CTAB). Furthermore, the
ultrasonic could effectively intensify the secondary nucleation on
the solid surface [12,23,24], thereby accelerate the deposition of
silica oligomers on the magnetic particles. Therefore, the synthetic
process of meso-SiO
2
@Fe
3
O
4
microspheres was comprehensively
accelerated by ultrasound. Besides the acceleration role, ultrasoni-
cally forced oscillations of the cavitation bubble could also improve
the homogeneity of silica shell and the monodispersity of meso-
SiO
2
@Fe
3
O
4
microspheres [12,17], hence the meso-SiO
2
@Fe
3
O
4
microspheres synthesized in ultra-rapid coating period could still
maintain favorable monodispersity with uniform mesoporous sil-
ica shell.
Fig. 10. TEM images of the meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained in different t: (a) and (f) 5 min; (b) and (g) 10 min; (c) and (h) 20 min; (d) and (i) 30 min; (e) and (j)
40 min. (C
CTAB
= 6.86 mmol/L and P = 150 W).
Fig. 11. (a) N
2
adsorptiondesorption isotherms and (b) pore size distribution
curves of the meso-SiO
2
@Fe
3
O
4
(E) microspheres obtained in different t.
(C
CTAB
= 6.86 mmol/L and P = 150 W).
Scheme 1. Formation of ultrasonic-assisted synthesized meso-SiO
2
@Fe
3
O
4
microspheres.
H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512 511
4. Conclusions
In summary, ultrasonic technique has been successfully applied
for the CTAB-templating synthesis of monodisperse coreshell-
type meso-SiO
2
@Fe
3
O
4
microspheres with favorable mesoporous
silica shell. Compared with the conventional synthetic method,
the use of ultrasonic irradiation can effectively simplify the coating
procedure from two steps to only one step and greatly shorten
coating period of mesoporous silica shell from 1224 h to
40 min. Even so, as-prepared meso-SiO
2
@Fe
3
O
4
microspheres
maintain uniform coreshell structure with desirable mesoporous
silica shell after acetone extraction or high temperature calcina-
tion. Therein, the mesoporous silica shell of meso-SiO
2
@Fe
3
O
4
(E)
microspheres presents unique two-layer structure: inner nonpo-
rous layer, and outer mesoporous layer with a pore size distribu-
tions in 1.83.0 nm. In addition, the monodispersion and
architectural features of as-prepared meso-SiO
2
@Fe
3
O
4
(E) micro-
spheres are signicantly inuenced by initial concentration of
CTAB, ultrasonic irradiation power and time. Especially, strong
ultrasonic irradiation power is benecial to obtain monodisperse
meso-SiO
2
@Fe
3
O
4
(E) microspheres with favorable mesoporous sil-
ica shell. Finally, we also conclude that the ultrasound play the
acceleration role during the whole coating process of mesoporous
silica shell, including hydrolysis-condensation of TEOS, co-assem-
bly of hydrolyzed precursors and CTAB, and deposition of silica
oligomers. And ultrasonically forced oscillations of the cavitation
bubble is favorable for improving the homogeneity of silica shell
and the monodispersity of meso-SiO
2
@Fe
3
O
4
microspheres.
Acknowledgements
Financial funds from the National Natural Science Foundation of
China (Grant No. 21173018 and 21136001) are gratefully
acknowledged.
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