Preparation of novel magnetic hollow mesoporous silica microspheres

and their efcient adsorption

Fangyingkai Wang
a,b
, Yulin Tang
c
, Bingbo Zhang
a
, Bingdi Chen
a
, Yilong Wang
a,
a
The Institute for Advanced Materials & Nano Biomedicine, Tongji University, School of Medicine, Shanghai 200092, PR China
b
School of Materials Science and Engineering, Tongji University, Shanghai 200092, PR China
c
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science & Engineering, Tongji University, Shanghai 200092, PR China
a r t i c l e i n f o
Article history:
Received 8 May 2012
Accepted 26 June 2012
Available online 1 August 2012
Keywords:
Hollow microspheres
Mesoporous silica materials
Magnetic property
Yolk-shell template
Adsorbent
a b s t r a c t
Magnetic hollow mesoporous silica microspheres (MHMSs) were successfully prepared by employing
yolk-shell magnetic silica spheres as the template together with the coating of tetraethoxysilane
(TEOS)/hexadecyl trimethoxysilane (C
16
TMS) hybrid. The microstructure and properties of MHMSs were
studied by TEM, SEM, XRD, BET, and VSM characterizations. The average diameter of MHMSs was about
300 nm and the mesoporous shell thickness was totally around 70 nm. The 11 nm magnetite nanoparti-
cles were homogeneously embedded in the mesoporous silica shell. Meanwhile, the adsorption and sep-
aration process of Rhodamine B were carried out to demonstrate that the material could be used for the
adsorbent.
2012 Elsevier Inc. All rights reserved.
1. Introduction
Hollow mesoporous silica spheres (HMSs) have received great
attention in the scientic area of drug delivery system as well as
the adsorbent due to their unique properties such as low toxicity,
biocompatibility, high specic surface area and huge interior space,
which could provide greater drug loading volume and better
adsorption ability compared to conventional mesoporous silica
materials [13]. Amount of studies have focused on the fabrication
of the HMS with the specic size and structure together with the
surface functionalities [4,5]. Typically, HMS have been prepared
via the template-assisted methodology including both soft-tem-
plate and hard-template types [620].
Recently, HMS containing superparamagnetic nanoparticles has
attracted signicant interests owing to their magnetic resonance in
the condition of an external magnetic eld existed. Up to now, a
number of synthesizing strategies have been concluded to prepare
the magnetic hollow mesoporous silica spheres (MHMSs). Zhu
et al. has prepared the rattle-like Fe
3
O
4
@SiO
2
hollow mesoporous
spheres using the colloidal carbon spheres absorbed with iron pre-
cursor as the templates, Fe
3
O
4
core was synthesized by reduction
after mesoporous silica shell formed [21]. MHMSs was also ob-
tained via the solgel process on the basis of carboxylic PS latex
and Fe
3
O
4
heteroaggregates using as the template. Under this cir-
cumstance, part of MHMSs surface has been blocked by the ad-
hered secondary particles or self-aggregation [20]. Zhou et al. has
synthesized porous magnetic hollow silica nanospheres via sol
gel reaction with the template of Fe
3
O
4
/CaCO
3
composites [22].
However, poor colloidal stability of the template led to the aggre-
gation of obtained hollow nanoparticles. Meanwhile, saturation
magnetization of the aforementioned MHMSs in above cases was
comparatively low because of the complex preparation procedure
and template characteristics. Aiming to achieve a superior applica-
tion of the MHMSs, two issues must be taken into account to en-
sure their higher loading capacity and better magnetic resonance
in addition to the necessity of the simple synthesizing process
[23,24]. That is, the magnetic nanoparticles should not block the
mesoporous pores, and the composites have higher magnetite con-
tents. Therefore, a facile and reproducible method is necessary to
synthesize MHMSs with distinct mesoporous structure and favor-
able magnetic resonance.
In this study, we presented a facile synthesis methodology for
the preparation of MHMSs composed of the oleic acid coated
Fe
3
O
4
nanoparticles (OAIOs) and the mesoporous silica compo-
nents via employing a yolk-shell PS@Fe
3
O
4
/silica nanocomposite
as the template. Based on the yolk-shell structured template with
silica surface, the mesoporous silica shell could be easily obtained
through co-condensation of TEOS/C
16
TMS in the solgel process
due to strong afnity. After calcination, the organic porogen and
PS latex were removed simultaneously. The obtained MHMSs
possessed a large cavity and free mesopore. The magnetic
0021-9797/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.06.088

Corresponding author. Fax: +86 21 65983706.

E-mail address: yilongwang@tongji.edu.cn (Y. Wang).
Journal of Colloid and Interface Science 386 (2012) 129134
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nanoparticles would be stable attributing to the existence of origi-
nal amorphous silica shell. In addition, the adsorption and separa-
tion properties of MHMSs were demonstrated as well.
2. Materials and methods
2.1. Materials
All reagents used were analytical grade and available commer-
cially. Ferric chloride (FeCl
3
6H
2
O), ferrous chloride (FeCl
2
7H
2
O),
and oleic acid (OA, 90%) were purchased from Shanghai Chemical
Reagents Company. Styrene (St), 2,2-azobis(isobutyronitrile)
(AIBN), toluene, Rhodamine B, and ammonium hydroxide (NH
4
OH,
28 wt.%) were purchased from Sinopharm Chemical Regent Com-
pany (Shanghai, China). Tetraethoxysilane (TEOS) and sodium
dodecyl sulfate (SDS) were purchased from SigmaAldrich (USA).
Hexadecane (HD) and Hexadecyltrimethoxysilane (C
16
TMS) were
purchased from Acros Organics (USA). The aforementioned chemi-
cals were used as received. Styrene was washed rst with 5 wt.%
sodium hydroxide solution and stored with the temperature of
20 C before use. High-purity nitrogen gas, provided by a local
supplier, was applied in sparging solutions without further puri-
cation. Deionized (DI) water was adopted throughout the entire
experiment.
2.2. Methods
2.2.1. Preparation of the Yolk-shell superparamagnetic composite
template
To start with, Fe
3
O
4
nanoparticles were prepared by solvother-
mal reaction [25]. The typical preparation process was described as
follows: 7.82 g of FeCl
2
7H
2
O and 19.0 g of FeCl
3
6H
2
O were dis-
solved in 80 mL of DI water with nitrogen protection. The disper-
sion was heated up to the temperature of 80 C and kept for
0.5 h. 50 g of NH
4
OH (28 wt.% aqueous solution) was added quickly
afterward, which is followed by adding 3.76 g of oleic acid. The dis-
persion was further heated at 80 C for 3 h. In the end, the disper-
sion was cooled down to the ambient temperature. The obtained
oleic acid modied Fe
3
O
4
nanoparticles (OAIOs) were collected
using a magnet and washed to neutralize with DI water. OAIOs
were further puried with ethanol and DI water three times each.
With the synthesized OAIOs, the yolk-shell magnetic silica tem-
plates nanoparticles were prepared through a one-pot synthesis
process combined with a miniemulsion polymerization and sol
gel reaction according to our previous work [26]. Typically, the
water phase, consisting of 40 g of DI water and 0.092 g of SDS,
and the oil phase, containing 9 g of St, 0.4 g of Hexadecane,
55 mg of OAIOs and 1 g of TEOS, were prepared under 200 W son-
ication (KQ-400KDV, Kun Shan Ultrasonic Instruments Co. Ltd.).
Being mixed up, they were mechanically stirred in a three-necked
ask at the rate of 250 rpm for 1 h. After that, the dispersion was
miniemulsied for 10 min at 500 W with a duty cycle of 50% with
a Scientz-IID sonier (Ningbo, China) in an ice bath. Before poly-
merization, the miniemulsion system was transferred to a three-
necked ask and degassed with N
2
for 30 min under 250 rpm
mechanical stirring after adding 0.09 g of AIBN. The polymerization
was initiated by heating at the temperature of 80 C. After 1 h poly-
merization, 0.035 mL of NH
4
OH was added into the reaction sys-
tem to catalyze the solgel process. The yolk-shell magnetic
composites spheres were obtained another 5 h later. The extra
reactive was removed from the products by washing with DI water
for two times with a magnet.
2.2.2. Preparation of the magnetic hollow mesoporous silica spheres
The templates obtained from the previous step were dispersed
in a solution composed of 10 g of DI water, 58.5 g of ethanol, and
3.22 g of NH
4
OH. Mixture of 5 mL ethanol, 0.138 mL of TEOS, and
0.051 mL of C
16
TMS was added dropwise under vigorous stirring.
The solgel reaction has proceeded for 2 h at room temperature.
The excess TEOS and C
16
TMS were separated from the product par-
ticles by three cycles of centrifugation and redispersion in the eth-
anol plus with three cycles of magnetic separation and
redispersion in the DI water. Finally, the organic parts of the poro-
gen were removed by calcination at 823 K for 5 h to obtain the
magnetic hollow mesoporous silica spheres.
2.2.3. Adsorption and separation
In a typical procedure, the obtained MHMSs (5 mg) was added
into 5 ml of Rhodamine B aqueous solution in a certain concentra-
tion to be sonicated for 30 s. Subsequently, they were separated
Scheme 1. Schematic illustration of preparation of the magnetic hollow mesoporous silica microspheres using the PS@Fe
3
O
4
/silica yolk-shell structures as the template and
the adsorption of Rhodamine B.
130 F. Wang et al. / Journal of Colloid and Interface Science 386 (2012) 129134
through a magnetic eld immediately. After the adsorption and
separation processes, the residual solution was diluted to a certain
concentration and measured on a UVVis spectrophotometer. The
adsorption efciency of Rhodamine B by the MHMSs was calcu-
lated by the following equation:
p
A
0
A
e
A
0
100% 1
where p is the percentage of Rhodamine B adsorbed, A
0
is the UV
Vis absorption of the initial dye solution, and A
e
is the UVVis
absorption of the residual dye solution.
2.3. Characterizations
TEM images and Energy dispersive X-ray (EDX) analysis were
taken with a Philips Tecnai 20 transmission electron microscope
(the Netherlands), operating in the condition of 200 kV. The ob-
tained products were washed twice in DI water using an external
magnetic eld and dispersed in DI water and collected using car-
bon-coated copper grids afterward. SEM images were obtained
via JEOL SM4800 scanning electron microscope (Japan) operating
at 10.0 kV. A thin gold lm was sprayed onto the sample before
the measurements. XRD patterns were recorded on Rigaku D/
max-RA powder diffraction meter (Rigaku, Japan). The Brunauer
EmmettTeller (BET) methodology was utilized to calculate the
specic surface area. The pore volume and pore size distribution
were derived from the desorption or adsorption branches of iso-
therms using the BarrettJoynerHalenda (BJH) model. The Vibrat-
ing Sample Magnetometer (VSM, LakeShore 7407, USA) was
applied to investigate the magnetic samples at room temperature.
3. Results and discussion
3.1. Preparation of magnetic hollow mesoporous silica microspheres
The schematic illustration of the preparation of the magnetic
hollowmesoporous silica microspheres is shown in Scheme 1. OAI-
Os (Scheme 1a) were pre-prepared by the classical coprecipitation
methodology. The following steps mainly include two parts: the
rst part was synthesis of the template spheres with yolk-shell
structures consisting of polymer cores and Fe
3
O
4
/silica hybrid
shells. The second part was the preparation of the hollowmesopor-
ous silica magnetic composite spheres by conducting a typical sol
gel methodology to obtain the silica coating via polycondensation
of TEOS and the organic alkylsilane followed with calcination. There
are three main advantages of our methodology in comparison with
the previously published studies, considering the syntheses of the
magnetic hollow mesoporous silica spheres: (1) using the yolk-
shell magnetic silica/polymer composites spheres with the Fe
3
O
4
/
silica hybrid shell as the template. The thin silica coating on Fe
3
O
4
surface was not only increasing the thermal stability of Fe
3
O
4
nano-
crystals during the calcination but also enhancing the afnity of the
mesoporous silica and the template. Meanwhile, the magnetic
nanoparticles were embedded in the silica shell, so that they would
not block the mesoporous pores. (2) The instinct space between the
polymer core and inorganic shell of the templates contributed to
the formation of the mesoporous silica shell both inside and outside
Fig. 1. TEM images of magnetic hollow mesoporous silica microspheres at (a) low magnication and (b) high magnication, (c) SEM image and (d) TEM-EDX patterns of
magnetic hollow mesoporous silica microspheres.
F. Wang et al. / Journal of Colloid and Interface Science 386 (2012) 129134 131
of the hollow magnetic spheres. (3) Polymer core of the templates
could be simultaneously removed during the calcination to fabri-
cate the mesoporous structure. The yolk-shell composites tem-
plates were prepared according to our previous work [26]. A
mixture including Styrene monomer, HD, TEOS precursor, OAIOs,
and the water phase was miniemulsied to form the miniemulsion
droplet systems, in which the monomer polymerization was carried
out and phase separations were started. Finally, yolk-shell struc-
tured templates were prepared as shown in Fig. 2b.
In the second part, the magnetic hollow mesoporous silica
spheres were synthesized using C
16
TMS as the porogen in a con-
vention solgel reaction. The mesoporous silica coating tends to
form on both the inner and outer layer on the Fe
3
O
4
/silica hybrid
shell of the template (Scheme 1c). The organic groups and the PS
cores of the obtained particles were removed by calcination at
823 K for 5 h to lead to the hollow mesoporous nal product
(Scheme 1d).
The structure and morphology of resultant MHMSs are pre-
sented in Fig. 1. Fig. 1a and b depicts the TEM image of MHMSs
at both low and high resolution, from which the hollow and mes-
oporous structure are displayed distinctly. It was found that the
magnetic nanoparticles were embedded in thin solid shells that
were covered by mesoporous structures at both inner and outer
sides. The average diameter was about 300 nm and the total thick-
ness of the mesoporous layer was around 70 nm. SEM image
(Fig. 1c) indicates that the obtained MHMS nanoparticles maintain
quasi-spherical prole on the whole. Besides C and Cu peaks from
the TEM grid, Energy-dispersive X-ray spectrum (Fig. 1d) illus-
trated the signals of Fe, Si, and O elements involved in the
composites.
Fig. 2 presents the TEM and SEM images of the samples ob-
tained at each stage that has been described in Scheme 1. Fig. 2a
gives the TEM image of the oleic acid modied Fe
3
O
4
nanoparticles,
which can be stably dispersed in the organic solvent such as 1-oc-
Fig. 2. TEM image (a) of the iron oxide nanoparticles, TEM (b), and SEM image (c) of the yolk-shell magnetic composites template; TEM image of the magnetic composites
before calcination (d), and TEM (e), and SEM (f) images of the obtained magnetic hollow mesoporous silica spheres. Scale bars are 50 nm for (a, b, d, and e) and 200 nm for (c
and f).
132 F. Wang et al. / Journal of Colloid and Interface Science 386 (2012) 129134
tane and cyclohexane. The average size of the Fe
3
O
4
nanoparticles
was about 11 nm. After one-pot synthesis process on the basis of
the Fe
3
O
4
nanoparticles reported in our previous work [26], a ter-
nary magnetic composite spheres with yolk-shell structure com-
posed of iron oxide/silica hybrid shell and polystyrene core were
prepared (as shown in Fig. 2b). This kind of yolk-shell magnetic
composites was used as the template for preparation of the
MHMSs due to their unique structure. There was an instinct space
between the hybrid shell and polymer core as well as the openings
on their surface (as shown in Fig. 2c), which endowed the coating
of the mesoporous silica on both sides of the hybrid shell in the
solgel reaction. In Fig. 2d, it was obviously seen the coating of
the silica/organosilane hybrid on the yolk-shell composites tem-
plate with the thickness of 24 nm and the PS cores still remain.
Fig. 2e and f gave the nal products after calcination, in which
the mesopores formed and inner PS cores were removed simulta-
neously. It was worth noting that the amount of magnetic nano-
particles embedded in the MHMSs kept unchanged as that in the
template due to protection by the thin silica coating. The Fe
3
O
4
nanoparticles hardly blocked the newly-formed mesopore, which
could benet for the efcient adsorption property.
3.2. XRD spectra
XRD patterns of Fe
3
O
4
nanoparticles and Fe
3
O
4
@mesoporous
silica hollow microspheres are shown in Fig. 3. Characteristic dif-
fraction peak at 2h of 30.2, 35.7, 43.3, 53.6, 57.2, and 62.6
were assigned to the [220], [311], [400], [422], [511], and
[440] lattice planes of Fe
3
O
4
. Consistence of two curves indicated
that there was no crystal transition of the magnetic nanoparticles
within the calcination process.
3.3. Magnetization property
As for the magnetic properties, the magnetic hysteresis loops of
yolk-shell magnetic templates and MHMS spheres are presented in
Fig. 4a. The saturation magnetization value of the resultant MHMS
spheres is 8.5 emu/g, a little lower than that value 12.5 emu/g of
the template due to the relative low mass ratio of Fe
3
O
4
nanopar-
ticles. No detectable coercivity is observed, indicating their super-
paramagnetic characteristic. In addition, the separation ability is
further studied through a separation and redispersion process un-
der external magnetic eld (as shown in Fig. 4b). The magnetic
nanoparticles were attracted towards the magnet within a short
period of time, and once the external magnet is removed, they will
redisperse in the solution with slight shake.
3.4. Nitrogen sorption isotherm
The nitrogen adsorptiondesorption isotherm of the magnetic
hollow mesoporous silica microspheres and corresponding BJH
pore size distribution are presented in Fig. 5. The isotherm is clas-
sied as type-IV and displayed a hysteresis loop within the relative
pressure range of 0.50.9, indicating the presence of mesoporous
pores. MHMS spheres had a BET specic surface area of
204.6 m
2
/g and a total pore volume of 0.264 cm
3
/g. The hollow
mesoporous spheres had a mean pore diameter of 4.78 nm (Fig. 5
inset).
3.5. Adsorption property
The adsorption and separation ability of MHMS spheres was
investigated by the adsorption of Rhodamine B at the concentra-
tion of 100 mg/L. After being sonicated at 400 W for 30 s, the
MHMS microspheres were separated from the solution in the con-
dition of an external magnetic eld, and residual Rhodamine B in
the supernatant was measured by UVVis Spectrum. Fig. 6 shows
the UVVis spectra of the Rhodamine B solution at 100 mg/L con-
centration before and after being adsorbed by the MHMS spheres.
The UVVis absorption intensity of initial and residual dye solution
are 2.463 and 0.513, respectively, at 552 nm which indicated that
nearly 79% of Rhodamine B was adsorbed by the MHMS micro-
spheres according to Eq. (1). The adsorption ability of the MHMS
microspheres was a little better than the rattle-type mesoporous
silica spheres reported by Wu et al. [27].
Fig. 3. XRD spectra of oleic acid coated Fe
3
O
4
nanoparticles and magnetic hollow
mesoporous silica microspheres.
Fig. 4. (a) The magnetic hysteresis loops of (a) yolk-shell composite template and (b) magnetic hollow mesoporous silica microspheres measured at 300 K; (b) the magnetic
separation of magnetic hollow mesoporous silica microspheres.
F. Wang et al. / Journal of Colloid and Interface Science 386 (2012) 129134 133
4. Summary
Magnetic hollow mesoporous silica microspheres were pre-
pared via a multi-step process using yolk-shell magnetic compos-
ite spheres as the template. This synthetic methodology featured
a number of advantages compared to other template-mediated
syntheses. The instinct space of the yolk-shell template endowed
MHMS sphere with simultaneously formed mesoporous layers
both in inner and outer sides of the magnetic moiety. The silica
coating on the Fe
3
O
4
nanoparticles of the templates prevented
Fe
3
O
4
from leaking out or blocking the mesoporous channels as
well. In the conclusion, the prepared MHMS spheres characterize
the preferable superparamagnetic property as well as the distinct
mesoporous structure, which has the ability of contributing to
the efcient adsorption of the uorescent dye Rhodamine B.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (No. 51003077), Program for Young Excellent Tal-
ents in Tongji University (2009KJ074), and partial fund of State
Key Laboratory of Pollution Control and Resource Reuse Founda-
tion (Nos. PCRRY11011, PCRRF11003).
References
[1] X. Du, J.H. He, Nanoscale 3 (2011) 3984.
[2] T. Liu, L. Li, X. Teng, X. Huang, H. Liu, D. Chen, J. Ren, J. He, F. Tang, Biomaterials
32 (2011) 1657.
[3] Z. Li, J.L. Nyalosaso, A.A. Hwang, D.P. Ferris, S. Yang, G. Derrien, C. Charnay, J.-O.
Durand, J.I. Zink, J. Phys. Chem. C 115 (2011) 19496.
[4] G.G. Qi, Y.B. Wang, L. Estevez, A.K. Switzer, X.N. Duan, X.F. Yang, E.P. Giannelis,
Chem. Mater. 22 (2010) 2693.
[5] J. Kecht, A. Schlossbauer, T. Bein, Chem. Mater. 20 (2008) 7207.
[6] Z.G. Feng, Y.S. Li, D.C. Niu, L. Li, W.R. Zhao, H.R. Chen, L. Li, J.H. Gao, M.L. Ruan,
J.L. Shi, Chem. Commun. (2008) 2629.
[7] C.E. Fowler, D. Khushalani, S. Mann, Chem. Commun. (2001) 2028.
[8] H.P. Hentze, S.R. Raghavan, C.A. McKelvey, E.W. Kaler, Langmuir 19 (2003)
1069.
[9] Y.F. Zhu, J.L. Shi, H.R. Chen, W.H. Shen, X.P. Dong, Micropor. Mesopor. Mater. 84
(2005) 218.
[10] H. Djojoputro, X.F. Zhou, S.Z. Qiao, L.Z. Wang, C.Z. Yu, G.Q. Lu, J. Am. Chem. Soc.
128 (2006) 6320.
[11] M.H. Yu, H.N. Wang, X.F. Zhou, P. Yuan, C.Z. Yu, J. Am. Chem. Soc. 129 (2007)
14576.
[12] W.J. Li, X.X. Sha, W.J. Dong, Z.C. Wang, Chem. Commun. (2002) 2434.
[13] Y.S. Li, J.L. Shi, Z.L. Hua, H.R. Chen, M.L. Ruan, D.S. Yan, Nano Lett. 3 (2003) 609.
[14] J.G. Wang, Q. Xiao, H.J. Zhou, P.C. Sun, Z.Y. Yuan, B.H. Li, D.T. Ding, A.C. Shi, T.H.
Chen, Adv. Mater. 18 (2006) 3284.
[15] R.K. Rana, Y. Mastai, A. Gedanken, Adv. Mater. 14 (2002) 1414.
[16] J.G. Wang, F. Li, H.J. Zhou, P.C. Sun, D.T. Ding, T.H. Chen, Chem. Mater. 21 (2009)
612.
[17] T. Sen, G.J.T. Tiddy, J.L. Casci, M.W. Anderson, Chem. Mater. 16 (2004) 2044.
[18] X.F. Wu, Y.J. Tian, Y.B. Cui, L.Q. Wei, Q. Wang, Y.F. Chen, J. Phys. Chem. C 111
(2007) 9704.
[19] T. Sen, I.J. Bruce, T. Mercer, Chem. Commun. 46 (2010) 6807.
[20] L.Y. Xia, M.Q. Zhang, C.E. Yuan, M.Z. Rong, J. Mater. Chem. 21 (2011) 9020.
[21] Y. Zhu, E. Kockrick, T. Ikoma, N. Hanagata, S. Kaskel, Chem. Mater. 21 (2009)
2547.
[22] J. Zhou, W. Wu, D. Caruntu, M.H. Yu, A. Martin, J.F. Chen, C.J. OConnor, W.L.
Zhou, J. Phys. Chem. C 111 (2007) 17473.
[23] W. Zhao, J. Gu, L. Zhang, H. Chen, J. Shi, J. Am. Chem. Soc. 127 (2005) 8916.
[24] W. Zhao, H. Chen, Y. Li, L. Li, M. Lang, J. Shi, Adv. Funct. Mater. 18 (2008) 2780.
[25] L. Shen, P.E. Laibinis, T.A. Hatton, Langmuir 15 (1999) 447.
[26] Y. Wang, F. Wang, B. Chen, H. Xu, D. Shi, Chem. Commun. 47 (2011) 10350.
[27] Y. Yin, S. Zhou, M. Chen, L. Wu, J. Colloid Interface Sci. 361 (2011) 527.
Fig. 5. Nitrogen sorption isotherm at 77 K for magnetic hollow mesoporous silica
microspheres and corresponding pore size distribution (inset).
Fig. 6. UVVis absorption spectra of 100 mg/L Rhodamine B solution (a) and
residual Rhodamine B solution after adsorption by the magnetic hollow mesopor-
ous silica microspheres (b).
134 F. Wang et al. / Journal of Colloid and Interface Science 386 (2012) 129134