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 Contents lists available at ScienceDirect Ultrasonics Sonochemistry 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. References [1] J. Liu, S.Z. Qial, Q.H. Hu, G.Q. Lu, Magnetic nanocomposites with mesoporous structures: synthesis and applications, Small 7 (2011) 425443. [2] Y.H. Deng, Y. Cai, Z.K. Sun, D.Y. Zhao, Magnetically responsive ordered mesoporous materials: a burgeoning family of functional composite nanomaterials, Chem. Phys. Lett. 510 (2011) 113. [3] W.R. Zhao, J.L. Gu, L.X. Zhang, H.R. Chen, J.L. Shi, Fabrication of uniform magnetic nanocomposite spheres with a magnetic core/mesoporous silica shell structure, J. Am. Chem. Soc. 127 (2005) 89168917. [4] Y.H. Deng, D.W. Qi, C.H. Deng, X.M. Zhang, D.Y. Zhao, Superparamagnetic high- magnetization microspheres with an Fe 3 O 4 @SiO 2 core and perpendicularly aligned mesoporous SiO 2 shell for removal of microcystins, J. Am. Chem. Soc. 130 (2008) 2829. [5] S.L. Gai, P.P. Yang, C.X. Li, W.X. Wang, Y.L. Dai, N. Niu, J. Lin, Synthesis of magnetic, up-conversion luminescent, and mesoporous coreshell-structured nanocomposites as drug carriers, Adv. Funct. Mater. 20 (2010) 11661172. [6] P.P. Yang, Z.W. Quan, Z.Y. Hou, C.X. Li, X.J. Kang, Z.Y. Cheng, J. Lin, A magnetic, luminescent and mesoporous coreshell structured composite material as drug carrier, Biomaterials 30 (2009) 47864795. [7] Y.H. Deng, Y. Cai, Z.K. Sun, J. Liu, C. Lin, J. Wei, W. Li, C. Liu, Y. Wang, D.Y. Zhao, Multifunctional mesoporous composite microspheres with well-designed nanostructure: a highly integrated catalyst system, J. Am. Chem. Soc. 132 (2010) 84668473. [8] F. Dang, K. Kato, H. Imai, S. Wada, H. Haneda, M. Kuwabara, Oriented aggregation of BaTiO 3 nanocrystals and large particles in the ultrasonic- assistant synthesis, CrystEngComm. 12 (2010) 34413444. [9] S.E. Skrabalak, K.S. Suslick, Porous MoS 2 synthesized by ultrasonic spray pyrolysis, J. Am. Chem. Soc. 127 (2005) 99909991. [10] L.P. Jiang, S. Xu, J.M. Zhu, J.R. Zhang, J.J. Zhu, H.Y. Chen, Ultrasonic-assisted synthesis of monodisperse single crystalline silver nanoplates and gold nanorings, Inorg. Chem. 43 (2004) 58775883. [11] Q.C. Ruan, Y.C. Zhu, Y. Zeng, H.F. Qian, J.W. Xiao, F.F. Xu, L.L. Zhang, D.H. Zhao, Ultrasonic-irradiation-assisted oriented assembly of ordered monetite nanosheets stacking, J. Phys. Chem. B 113 (2009) 11001106. [12] A.L. Morel, S.E. Nikitenko, K. Gionnet, A. Wattiaux, J.L.K. Him, C. Labrugere, B. Chevalier, G. Deleris, C. Petibois, A. Brisson, M. Simonoff, Sonochemical approach to the synthesis of Fe 3 O 4 @SiO 2 coreshell nanoparticles with tunable properties, ACS Nano 2 (2008) 847856. [13] B.Y. Wang, J.M. Wu, Z.Y. Yuan, N. Li, S.H. Xiang, Synthesis of MCM-22 zeolite by an ultrasonic-assisted aging procedure, Ultrason. Sonochem. 15 (2008) 334 338. [14] M. Chareonpanich, A. Nanta-ngern, J. Limtrakul, Short-period synthesis of ordered mesoporous silica SBA-15 using ultrasonic technique, Mater. Lett. 61 (2007) 51535156. [15] M.T. Run, X.Z. Wu, G. Wu, Ultrasonic synthesis of mesoporous molecular sieve, Microporous Mesoporous Mater. 74 (2004) 3747. [16] C.L. Wang, H. Zhang, J.H. Zhang, M.J. Li, H.Z. Shu, B. Yang, Application of ultrasonic irradiation in aqueous synthesis of highly uorescent CdTe/CdS coreshell nanocrystals, J. Phys. Chem. C 111 (2007) 24652469. [17] N. Ghows, M.H. Entezari, Sono-synthesis of coreshell nanocrystal (CdS/TiO 2 ) without surfactant, Ultrason. Sonochem. 19 (2012) 10701078. [18] S.C. Tang, Y.F. Tang, S.P. Zhu, H.M. Lu, X.K. Meng, Synthesis and Characterization of silica-silver coreshell composite particles with uniform thin silver layers, J. Solid State Chem. 180 (2007) 28712876. [19] J.F. Baneld, S.A. Welch, H.Z. Zhang, T.T. Ebert, R.L. Penn, Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products, Science 289 (2000) 751754. [20] S. Shylesh, V. Schnemann, W.R. Thiel, Magnetically separable nanocatalysts: bridegs between homogeneous and heterogeneous catalysis, Angew. Chem. Int. Ed. 49 (2010) 34283459. [21] K.S. Rao, K.E. Hami, T. Kodaki, K. Matsushige, K. Makino, A novel method for synthesis of silica nanoparticles, J. Colloid Interface Sci. 289 (2005) 125131. [22] Y. Mizukoshi, T. Fujimoto, Y. Nagata, R. Oshima, Y. Maeda, Characterization and catalytic activity of coreshell structured gold/palladium bimetallic nanoparticles synthesized by the sonochemical method, J. Phys. Chem. B 104 (2000) 60286032. [23] P.R. Gogate, V.S. Sutkar, A.B. Pandit, Sonochemical reactor: important design and scale up considerations with a special emphasis on heterogeneous systems, Chem. Eng. J. 166 (2011) 10661082. [24] P.R. Gogate, R.K. Tayal, A.B. Pandit, Cavitation: a technology on the horizon, Curr. Sci. India 91 (1) (2006) 3546. 512 H. Liu et al. / Ultrasonics Sonochemistry 21 (2014) 505512
ChatGPT Money Machine 2024 - The Ultimate Chatbot Cheat Sheet to Go From Clueless Noob to Prompt Prodigy Fast! Complete AI Beginner’s Course to Catch the GPT Gold Rush Before It Leaves You Behind