Published on Web 12/13/2007

Superparamagnetic High-Magnetization Microspheres with an Fe3O4@SiO2

Core and Perpendicularly Aligned Mesoporous SiO2 Shell for Removal of
Microcystins
Yonghui Deng, Dawei Qi, Chunhui Deng,* Xiangmin Zhang, and Dongyuan Zhao*
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and AdVanced Materials Laboratory,
Fudan UniVersity, Shanghai 200433, China
Received October 9, 2007; E-mail: [email protected]; [email protected]

Core-shell structured microspheres have recently been subject Scheme 1. The Formation of Fe3O4@nSiO2@mSiO2
to extensive research for the combined functionalities of cores and Microspheres
shells which endow them with great application potentials in various
fields.1-6 Magnetic microspheres consisting of an iron oxide core
and silica shell have attracted particular attention7 for their unique
magnetic responsivity, low cytotoxicity, and chemically modifiable
surface. The core-shell magnetic silica microspheres have shown
great potential in bioseparation,8 enzyme immobilization,9 diagnostic
analysis,10 and so on. ∼15 nm (Figure 1a and inset). Selected-area electron diffraction
Since the first discovery in 1992,11 ordered mesoporous materials reveals that the particles have a polycrystalline feature (Figure S1).
have gained much attention for the applications in catalysis, After coated with a nonporous silica layer, core-shell Fe3O4@nSiO2
adsorption, and separation. The integration of mesoporous silica microspheres with a thin silica layer of ∼20 nm in thickness were
obtained (Figure 1b). The second surfactant-templating process
with magnetic particles to form core-shell composite microspheres
results in a CTAB/SiO2 mesophase coated on the Fe3O4@nSiO2
is undoubtedly of great interest for practical applications. Up to
microsphere surface. The subsequent treatment with refluxing
now, several papers have reported the synthesis of magnetic
acetone could remove CTAB templates and lead to a uniform
mesoporous silica nanocomposites.12 However, these materials
mesoporous silica shell (ca. 70 nm in thickness) (Figure 1c). FT-
either show poor magnetic response due to the difficulty in
IR analysis (Figure S2) shows that CTAB templates can be
increasing Fe3O4 mass fraction12a-c or possess irregular core-shell
successfully removed by the 3× mild acetone extraction. A typical
structures,12b and they could not be readily dispersed in water due
sandwich structure with a magnetite core, a nonporous silica layer
to the sintering caused by the calcination for the removal of organic
in the middle layer, and an ordered mesoporous silica phase with
templates.12d Furthermore, these composites possess randomly
cylindrical channels in the outer layer can be clearly observed
aligned mesochannels or disordered mesopores12d that are difficult
(Figure 1d). Interestingly, the mesopore channels are found to be
to access. As a result, these magnetic mesoporous silicas are limited
perpendicular to the microsphere surface (Figure 1e). The SEM
in the applications, particularly, in biosystems and biomedicine. image shows that the microspheres are very uniform in both size
Therefore, core-shell magnetic mesoporous silica microspheres and shape (Figure 1f). In our synthesis system, the silica oligomers
with strong magnetic responsivity, orientated and accessible me- interact with the CTAB template via Coulomb forces, and both of
sopores and high dispersibility are highly valuable. them cooperatively assembly on the Fe3O4@silica microspheres’
Herein, we report a novel synthesis of sandwich structured surface, and the ordered mesostructure is formed. The mesopore
mesoporous silica microspheres (∼500 nm) with a silica-coated orientation may result from the preferable alignment fashion of the
magnetite core and ordered mesoporous silica shell with perpen- rod-shaped silicate/CTAB complexes on the carved surface of the
dicularly oriented channels using a surfactant-templating approach. Fe3O4@nSiO2 microspheres, which could effectively decrease the
The obtained microspheres possess superparamagnetism, high surface energy in the synthesis system (Scheme 1). The unique
magnetization (53.3 emu/g), uniform accessible mesochannels (2.3 microstructure of the obtained microspheres would be very useful
nm), high surface area (365 m2/g), and large pore volume (0.29 for many applications. First, the middle nonporous silica layer could
cm3/g). Furthermore, they can be used as efficient adsorbents to protect the magnetite from etching in harsh application occasions.
fast remove large microcystins (1000 Da) in the solution. Second, the mesoporous silica shell not only offers high surface
The synthesis procedure is shown in Scheme 1. First, uniform area for the derivation of numerous functional groups but also
magnetite microspheres were coated with a thin silica layer through provides large accessible pore volume for the adsorption and
a sol-gel approach to obtain nonporous silica-Fe3O4 composites encapsulation of biomacromolecules and even functional nanopar-
(designated Fe3O4@nSiO2). Second, through a surfactant-templating ticles (e.g., quantum dots). Notably, due to their unique perpen-
approach with cetyltrimethylammonium bromide (CTAB) as a dicular orientation, the mesopore channels of the microspheres are
template, a mesostructured CTAB/silica composite was deposited readily accessible, favoring the adsorption and release of large guest
on the Fe3O4@nSiO2 microspheres. Third, CTAB templates were objects triggered by external stimulus.
removed in a mild way by acetone extraction to form a mesoporous The low-angle XRD pattern reveals that the Fe3O4@nSiO2@mSiO2
SiO2 shell, resulting in well-dispersed Fe3O4@nSiO2@mSiO2 microspheres have hexagonal mesopore symmetry (Figure S3).
microspheres. Because the mesopore channels are perpendicular to the surface,
The Fe3O4 particles were prepared via a solvothermal method ethanol can lower the hydrolysis and condensation rate of TEOS
as described previously.8 These particles have a mean diameter of and favor the coating and curving. The microspheres possess short-
about 300 nm and consist of nanoparticles with the diameter of range mesoscopic ordering character. N2 sorption-desorption
28 9 J. AM. CHEM. SOC. 2008, 130, 28-29 10.1021/ja0777584 CCC: $40.75 © 2008 American Chemical Society
 COMMUNICATIONS

viable.15 Here, we attempt to explore the applicability for the

removal of MCs by using our magnetic mesoporous silica spheres.
A low dose (0.05 mg/µg MCs) of the microspheres can be used to
remove MC-RR, MC-LR, and MC-RY from their aqueous solution
with a magnet. The removal efficiencies were analyzed by using
the high-pressure liquid chromatography (HPLC) (see Supporting
Information for experimental details). The results indicate that
95.4% MC-RR, 97.2% MC-YR, and 97.5% MC-LR can fast be
removed in one isolation process within 60 s (Figure S8). Such
high removal efficiency is mainly attributed to the high surface
area from the numerous accessible mesopores. Additionally, after
extraction of the trapped MCs with acetonitrile/water mixture, the
microspheres can be reused with MC removal efficiency higher
than 90% even after used for eight times (Figure S9; see Supporting
Figure 1. TEM images of (a) Fe3O4 particles, (b) Fe3O4@nSiO2, (c-e) Information for experimental details).
Fe3O4@nSiO2@mSiO2 microspheres, and (f) SEM image of Fe3O4@n- In conclusion, we have demonstrated the synthesis of superpara-
SiO2@mSiO2 microspheres.
magnetic microspheres with an Fe3O4@SiO2 core and perpendicu-
larly aligned mesoporous SiO2 shell. The microspheres possess very
high magnetization, high surface area, large pore volume, and
uniform accessible mesopores. It was found that the high-magnetic
mesoporous silica microsphere can be used as a reusable absorbent
for fast, convenient, and highly efficient removal of MCs. Ad-
ditionally, because of the useful magnetic properties and unique
microstructure, the microspheres may provide great promise for
many applications such as magnetically controlled drug delivery
and so on.
Figure 2. (A) The magnetic hysteresis loops of (a) Fe3O4 particles, (b) Acknowledgment. This work was supported by the NSF of
Fe3O4@nSiO2, and (c) Fe3O4@nSiO2@mSiO2 microspheres, and (B) the
separation-redispersion process of Fe3O4@nSiO2@mSiO2 microspheres.
China (20421303 and 20641001), the Agilent Technologies
Foundation (0214), the State Key Basic Research Program of the
isotherms exhibit IV-type curves for the microspheres (Figure S4). PRC (2006CB932302), Shanghai Nanotech Promotion Center
The mesopore size distribution (Figure S4, inset) exhibits a sharp (0652nm024), National Basic Research Priorities Program (2007-
peak centered at the mean value of 2.3 nm, indicating a uniform CB914100/3), and Australian Research Council (Discovery Project
mesopore. The BET surface area and total pore volume are cal- No. DP0879769).
culated to be 365 m2/g and 0.29 cm3/g, respectively. Wide-angle
XRD patterns (Figure S5) show that the microspheres have Supporting Information Available: Experimental procedures, N2
diffraction peaks similar to that of the parent Fe3O4 particles, sorption isotherms, pore size distribution, XRD patterns, chemical
structure of microcystins, and HPLC traces. This material is available
suggesting that the Fe3O4 particles were well retained in the silica
free of charge via the Internet at http://pubs.acs.org.
matrix. Magnetic characterization using a magnetometer at 300 K
indicates that the Fe3O4, Fe3O4@nSiO2, and Fe3O4@nSiO2@mSiO2 References
microspheres have magnetization saturation values of 80.7, 78.0,
(1) Chan, Y.; Zimmer, J. P.; Stroh, M.; Steckel, J. S.; Jain, R. K.; Bawendi,
and 53.3 emu/g (Figure 2A), respectively. Additionally, no rema- M. G. AdV. Mater. 2004, 16, 2092-2097.
nence was detected for all of the samples. The magnified hysteresis (2) Breen, M. L.; Dinsmore, A. D.; Pink, R. H.; Qadri, S. B.; Ratna, B. R.
Langmuir 2001, 17, 903-907.
loops further confirmed the superparamagnetism of the particles (3) Deng, Y. H.; Yang, W. L.; Wang, C. C.; Fu, S. K. AdV. Mater. 2003, 15,
(Figure S6). The Fe3O4 content of Fe3O4@nSiO2@mSiO2 micro- 1729-1732.
spheres is calculated to be 65 wt %, indicating a high magnetization. (4) von Werne, T.; Patten, T. E. J. Am. Chem. Soc. 1999, 121, 7409-7410.
(5) Salgueiriño-Maceira, V.; Correa-Duarte, M. A.; Spasova, M.; Liz-Marzán,
As a result, the microspheres in their homogeneous dispersion show L. M.; Farle, M. AdV. Mater. 2006, 16, 509-514.
fast moment to the applied magnetic field (1000 Oe) and redisperse (6) Caruso, F.; Susha, A. S.; Giersig, M.; Möhwald, H. AdV. Mater. 1999,
11, 950-953.
quickly with a slight shake once the magnetic field is removed (7) (a) Lu, Y.; Yin, Y.; Mayers, B. T.; Xia, Y. Nano Lett. 2002, 2, 183-186.
(Figure 2B). It suggests that the microspheres possess excellent (b) Deng, Y. H.; Wang, C. C.; Hu, J. H.; Yang, W. L.; Fu, S. K. Colloid
Surf. A 2005, 26, 87-93.
magnetic responsivity and redispersibility, which is an advantage (8) Xu, X. Q.; Deng, C. H.; Gao, M. X.; Yu, W. J.; Yang, P. Y.; Zhang, X.
to their applications. M. AdV. Mater. 2006, 18, 3289-329.
(9) Li, Y.; Yan, B.; Deng, C. H.; Yu, W. J.; Xu, X. Q.; Yang, P. Y.; Zhang,
Microcystins, such as MC-RR, MC-YR, and MC-LR, are X. M. Proteomics 2007, 7, 2330-2339.
disocyclic heptapeptides (Figure S7) with molecular weights of (10) Levy, L.; Sahoo, Y.; Kim, K.-S.; Bergey, E. J.; Prasad, P. N. Chem. Mater.
about 1000 Da. Numerous research results have indicated that MCs 2002, 14, 3715-3721.
(11) Dresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S.
are extremely toxic and are produced in cyanobacterial blooms Nature 1992, 359, 710-712.
widely occurring in many eutrophic waters. Conventional ap- (12) Kim, J.; Lee, J. E.; Lee, J.; Yu, J. H.; Kim, B. C.; An, K.; Hwang, Y.;
Shin, C. H.; Park, J. G.; Kim, J.; Hyeon, T. J. Am. Chem. Soc. 2006, 128,
proaches such as coagulation and sand filtration are effective for 688-689. (b) Lin, Y. S.; Wu, S. H.; Hung, Y.; Chou, Y. H.; Chang, C.;
the removal of particulate cyanobacterial cells but not for the Lin, M. L.; Tsai, C. P.; Mou, C. Y. Chem. Mater. 2006, 18, 5170-5172.
(c) Giri, S.; Trewyn, B. G.; Stellmaker, M. P.; Lin, V. S. Y. Angew. Chem.,
dissolved toxins. Activated carbon can be used to remove MCs, Int. Ed. 2005, 44, 5038-5044. (d) Zhao, W. R.; Gu, J. L.; Zhang, L. X.;
but it requires large carbon doses due to deficiency of accessible Chen, H. R.; Shi. J. L. J. Am. Chem. Soc. 2005, 127, 8916-8917.
(13) Lee, J.; Walker, H. W. EnViron. Sci. Technol. 2006, 40, 7336-7342.
mesopores for adsorption of large MCs.13 Chlorination and ozo- (14) Kronberg, L.; Vartiainen, T. Mutat. Res. 1988, 206, 177-1821.
nation could be used for removing MCs, but the required high (15) Angeline, K. Y. L.; Phillip, M. F.; Ellie, E. P. EnViron. Sci. Technol.
dosage may result in the formation of carcinogenic substances.14 1995, 29, 242-246.
Biological methods require a long reaction time and are thus not JA0777584

J. AM. CHEM. SOC. 9 VOL. 130, NO. 1, 2008 29