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
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E-mail address: yilongwang@tongji.edu.cn (Y. Wang). Journal of Colloid and Interface Science 386 (2012) 129134 Contents lists available at SciVerse ScienceDirect Journal of Colloid and Interface Science www. el sevi er . com/ l ocat e/ j ci s 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