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Preparation of SiO2@Au@TiO2 core-shell nanostructures and their photocata lytic activities under visible light irradiation Miaomiao Ye, Huihui Zhou, Tuqiao Zhang, Yiping Zhang, Yu Shao PII: DOI: Reference: To appear in: Received Date: Revised Date: Accepted Date: S1385-8947(13)00542-1 http://dx.doi.org/10.1016/j.cej.2013.04.064 CEJ 10679 Chemical Engineering Journal 19 January 2013 13 April 2013 15 April 2013

Please cite this article as: M. Ye, H. Zhou, T. Zhang, Y. Zhang, Y. Shao, Preparation of SiO2@Au@TiO2 core-shell nanostructures and their photocatalytic activities under visible light irradiation, Chemical Engineering Journal (2013), doi: http://dx.doi.org/10.1016/j.cej.2013.04.064

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Preparation of SiO2@Au@TiO2 core-shell nanostructures and their photocatalytic activities under visible light irradiation
Miaomiao Ye, Huihui Zhou, Tuqiao Zhang, Yiping Zhang, Yu Shao* Institute of Municipal Engineering, Zhejiang University, Hangzhou, 310058, P R China *Corresponding author. Tel.: +86-571-88206759; Fax: +86-571-88208721. Email address: shaoyu1979@zju.edu.cn (Y. Shao)

Abstract SiO2@Au@TiO2 core-shell nanostructures with tunable decoration amount of Au nanoparticles have been successfully synthesized by combining three individual synthesis steps with calcination. The as-prepared samples were characterized by

X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), N2 adsorptiondesorption, X-ray photoelectron emission spectroscopy (XPS), and UV-vis diffuse reflectance spectroscopy. The photocatalytic activities of the samples were evaluated by

photocatalytic degradation of naproxen in aqueous solution under visible light irradiation. Results show that the as-obtained core-shell nanostructure is composed

of a SiO2 core with an average diameter of ~337 nm, tunable content of Au nanoparticles adsorbed on the surface of SiO2 core, and an outer layer of TiO2 with an average thickness of ~7.0 nm. Photocatalysis experiments indicate that the

SiO2@Au@TiO2 core-shell nanostructures with Au decoration amount of 0.1 wt%

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(denotes as SiAuTi-2) exhibit the highest photocatalytic activity since it has the suitable decoration amount of Au nanoparticles for harvesting the visible-light energy and for prohibiting the recombination of free excitons. For fast separation of the

catalysts, superparamagnetic cores of Fe3O4 were embedded in the SiO2@Au@TiO2 core-shell nanostructures and hence they can be separated from aqueous solution by an external magnetic eld within 10 min. Keywords: Core-shell nanostructures; Plasmonic effects; Photocatalysis; Titania; Naproxen 1. Introduction Heterogeneous photocatalysis using nanosized TiO2 catalyst under UV light irradiation is a potential technique for elimination of organic pollutants in aqueous solution [1,2]. However, there are two major barriers limit the widespread use of

TiO2 in the practical photocatalytic process. One is its relatively large optical band gap (Eg = 3.2 eV), which limits its photo-response to visible light [3,4]; the other is its small particle size, which makes the separation and recovery of those photocatalysts from the treated solution very difficult [5]. To overcome its first limitation,

strategies including mental-ion doping [6], noble metal doping [7], nonmetal doping [8], and compositing with other semiconductors [9] have been developed to extend the absorption of TiO2 to visible light spectrum. Among them, it has been found that

noble metal (such as Au and Ag nanoparticles) doping can enhance the photocatalytic activity in visible light because it not only can promote the photocatalytic activity by slowing down the recombination of photogenerated electrons and holes but also can

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induce a visible-light-driven photocatalysis due to their plasmonic effects [10-13]. To overcome its second limitation, nanosized TiO2 is usually being immobilized on supporting materials such as sand, glass, zeolite, and etc. to improve its separation efficiency. Unfortunately, the overall photocatalytic activity will be significantly In some case, TiO2

decreased due to lowering of the surface-to-volume ratio [5].

nanoparticles may easily detach from the support since the immobilization is typically realized through physical adhesion. Therefore, it is still scientific challenges to

prepare TiO2-based photocatalysts both with high photocatalytic activity under visible light irradiation and with easy recovery. In this paper, we report the preparation of SiO2@Au@TiO2 core-shell nanostructures with tunable decoration amount of Au nanoparpticles. The synthesis

process can be divided into the following three steps: firstly, monodisperse SiO2 cores were synthesized through a classic Stber method; secondly, tunable amount of Au nanoparticles were absorbed on the surface of SiO2 cores under sonication; finally, the as-prepared SiO2@Au collides were coated with a thin TiO2 layer through the sol-gel method, followed by calcination at 500 oC for 2h which converts the amorphous TiO2 layer into anatase phase (as shown in Fig. 1). This concept was first proposed by

Yin [16], who has reported the fabrication of the sandwich-structured SiO2/Au/TiO2 photocatalysts with high photocatalytic activity both under UV and visible light irradiation. The designed core-shell nanostructures will possess a number of

important features: 1) a thin outer layer of anatase titania and a well-defined SiO2/TiO2 interface can enhance the photocatalytic activity [17,18]; 2) the decoration

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of Au nanoparticles can harvest the visible-light energy by their plasmonic effects, and also can enhance charge separation by serving as an electron reservoir [10]; 3) the titania outer layer can prevent the loss of Au nanoparticles from the nanostructures after use [16, 19]; 4) the large size of the core-shell nanostructures can enhance the separation efficiency by filtration or sedimentation. In addition, for fast magnetic

separation of the catalyst, highly field-responsive superparamagnetic cores of Fe3O4 were embedded in the center of the SiO2@Au@TiO2 nanocomposites to get the Fe3O4@SiO2@Au@TiO2 core-shell nanostructures. Naproxen was selected as a

model pollutant for evaluation of the photodegradation process since it is a representative of pharmaceutical and personal care products (PPCPs) that has been newly detected in the aquatic environment in the past decade [20,21]. 2. Experimental 2.1. Chemicals All reagents were directly used as received without further purification. Tetraethyl orthosilicate (TEOS, 98%), 2-propanol (99.9%), tetrabutyl orthotitanate (TBOT, 99%), and 3-aminopropyl-triethoxysilane (APTES, 99%) were obtained from Sigma-Aldrich. Anhydrous ethyl alcohol, sodium citrate tribasic dihydrate (99%)

and ammonia (28%) were obtained from Sinopharm Chemical Reagent Co., Ltd (China). Naproxen (99%) and hydrogen tetrachloroaurate (III) trihydrate Hydroxypropyl cellulose

(HAuCl43H2O, 99.99%) were purchased from Alfa Aesar. (HPC, Mw = 100,000) were obtained from Acros. 2.2. Synthesis of SiO2 cores

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The spherical SiO2 cores were prepared through the classic Stber method [22]. Typically, 2 mL of TEOS was rapidly injected into a mixture of 8 mL of deionized H2O, 2 mL of ammonia and 40 mL of 2-propanol under magnetic stirring rate of 800 rpm. After reacting for 4 hours, the colloidal spheres were collected by

centrifugation, washed with ethanol three times and re-dispersed in 40 mL of 2-propanol. 2.3 Synthesis of SiO2@Au Firstly, 40 mL of above SiO2 aqueous solution was mixed with 0.5 mL of APTES and heated to 80 C for 2 hours to functionalize the silica surface with amino (-NH2) groups[16]. The -NH2 treated SiO2 were washed with ethanol twice and dried in In a

vacuum at 60 C overnight, then re-dispersed in 80 mL of deionized water.

separate process, Au nanoparticles with average diameter of ~ 15 nm were synthesized by using the Turkevich process [23]. Finally, the SiO2@Au were

prepared by adding different amount of Au nanoparticles to the -NH2 modified SiO2 aqueous solution (20 mL) under sonication [24]. The collected samples were denoted as Si, SiAu-1, SiAu-2, SiAu-3, and SiAu-4 with the addition of 0, 1, 2, 5, and 10 mL of Au sols, respectively. All of the SiO2@Au colloids were centrifuged and re-dispersed in 25 mL of ethanol. 2.4 Synthesis of SiO2@Au@TiO2 core-shell nanostructures Typically, the above SiO2@Au aqueous solution with different amount of Au nanoparticles (25 mL) were mixed with deionized water (0.12 mL), and HPC (80 mg) under vigorous magnetic stirring. 0.25 mL of TBOT dissolved in ethanol (5 mL)

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was introduced to the system drop by drop, followed by reuxing the solution at 80 C for 90 min [25]. The final products were washed with ethanol three times, dried Therefore, the five new

at 60 C for 8 h, and finally calcined in air at 500 C for 2 h.

samples were denoted as SiTi, SiAuTi-1, SiAuTi-2, SiAuTi-3 and SiAuTi-4, which contains 0, ~0.05, ~0.10, ~0.25, ~0.50 wt% of the Au nanoparticles, respectively. The content of the Au in the nanocomposites was calculated on the basis of all of the precursors were completely convert to the final product. 2.5 Synthesis of Fe3O4@SiO2@Au@TiO2 core-shell nanostructures The synthesis procedure of Fe3O4@SiO2@Au@TiO2 core-shell nanostructures is similar to that of the SiO2@Au@TiO2 core-shell nanostructures except using the Fe3O4@SiO2 core-shell nanostructures instead of the SiO2 spheres. The detailed

synthesis procedure of Fe3O4@SiO2 have been reported in our previous work [26,27]. 2.6. Characterization The morphologies of the as-prepared samples were analyzed using a Phillips Tecnai 10 transmission electron microscope (TEM) with an accelerating voltage of 100 kV. Elemental mapping was performed using STEM and EDX on a Tecnai G2 F20 S-TWIN transmission electron microscope with an accelerating voltage of 200 kV. The crystalline structures of all samples were evaluated by Xray diffraction (XRD) analyses, carried out on a Rigaku D/maxrA diffractometer with Cu Ka radiation ( 1.5405 ). The BET surface area and pore size distribution of the

products were measured by N2 adsorptiondesorption test on a Quantachrome, ASIC-2 measuring instrument. The UVvisible diffuse reflectance spectra were

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measured on a TU1901 spectrophotometer equipped with a labsphere diffuse reflectance accessory. The X-ray photoelectron spectroscopy (XPS) measurements

were carried out using a VG ESCA Lab Mark II system with Mg K excitation. 2.7. Measurement of photocatalytic activity Photocatalytic reactions for degradation of naproxen were carried out in a batch photoreactor. The schematic illustration and the digital photo of the photoreactor are shown in Fig. 2 and Fig. S1, respectively. The aqueous slurry with initial volume of

50 mL, prepared with a given amount of catalyst 1.0 g/L (in which the active TiO2 dosage is ~0.30 g/L) and naproxen in concentration of 1.0105 mol/L, was stirred in the dark for 1.0 h to ensure that the naproxen was adsorbed to saturation on the catalysts. A 250 W xenon lamp (as shown in Fig. S2, Supporting Information) was

used as the light source, the wavelength spectrum and intensity of the xenon lamp used in our experiment are shown in Fig. S3 Supporting Information, and a cutoff filter was used to block the UV light (< 420 nm). The reaction flask was put in a Agitation was

cooling water system to keep the reaction at room temperature. provided by magnetic stirrer at a stirring rate of 800 rpm.

6 mL of suspension was

collected at timed intervals with a 10 mL syringe, then the sample was immediately filtrated through a 0.22 m filter for analysis of naproxen concentration. The

concentration of naproxen were determined by HPLC (Agilent 1200, USA) provided with a UVVis detector. A 4.6 mm 250 mm (5 m) XDBC18 column was used.

The analysis was carried out with a 70/30 (v/v) acetonitrile/water mobile phase and the flow rate was set at 1.0 mL/min.

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3. Results and discussion 3.1. Characterization of SiO2@Au@TiO2 core-shell nanostructures 3.1.1 TEM and STEM analysis Firstly, the monodisperse spherical SiO2 cores with an average diameter ~337 nm were synthesized by using the classical Stber process (as shown in Fig. 3a), then the Au nanoparticles were adsorbed onto the 3-aminopropyl-triethoxysilane (APTES) modified SiO2 cores under sonication (see Fig. 3b). Comparing Fig. 3b with Fig. 3c, the smooth surface of the SiO2 spheres become rough, suggesting the successful coating with a thin TiO2 layer outside the SiO2@Au particles. After calcination at

500 C for 2 h, the surface roughness of the SiO2@Au@TiO2 further increases (as can be seen in Fig. 4d), indicating the crystallization of the TiO2 layer. It should be

noted that no apparent aggregations of the calcinated core-shell nanostructures have been observed. The thickness of the TiO2 layer was estimated by calculating the

mean diameters of the SiO2@Au, SiO2@Au@TiO2, and calcined SiO2@Au@TiO2 core-shell nanostructures. In typical samples (as shown in Fig. 3), the average

diameter is ~337 nm for SiO2@Au, ~352 nm for SiO2@Au@TiO2, and ~351 nm for calcined SiO2@Au@TiO2, suggesting the average thickness of the TiO2 layer is 7.5 and 7.0 nm before and after calcination, respectively. The thin thickness of the TiO2

layer will promote the photocatalytic acivtivy since our previous work and a number of other researchers works have pointed out that the optimal size of anatase nanocrystals for photocatalysis is around 10 nm [27-29]. The morphologies of other

samples decoration with different amount of Au nanoparticles can be found in Fig. S4,

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Supporting Information.

The structures of the SiO2@Au@TiO2 core-shell

nanostructures were further studied by scanning transmission electron microscope (STEM) and the energy dispersive x-ray (EDX) silicon drift detector (SDD) elemental mapping. The results are shown in Fig. 4, from which one can clearly see the Si, O, Ti, and Au elements distribution of the selected particle. The EDX elemental

mapping results also can confirm the core-shell nanostructure of the selected sample. 3.1.2 XRD and XPS analysis The XRD patterns of the calcined SiO2@Au@TiO2 core-shell nanostructures with different decoration amount of Au nanoparticles are shown in Fig. 5. Take sample

SiAuTi-4 for an example, all diffraction peaks at 2 value of 38.3, 44.6, 64.8, and 77.6 can be indexed to the metallic gold (JCPDS 1-1172), suggesting the successful decoration of Au nanoparticles in the SiO2@Au@TiO2 core-shell nanostructures. As

it can be observed, the intensity of the diffraction peaks increase with the increasing decoration amount of Au nanoparticles. The diffraction peak at 2 value of 25.2 The relatively weak

can be indexed to the anatase phase of TiO2 (JCPDS 21-1272).

diffraction peak is partly because of the small portion of the titania in the nanocomposites and partly because of the influence from the amorphous phase of the silica. To further confirm the chemical compositions of the surface of the

SiO2@Au@TiO2 core-shell nanostructures, X-ray photoelectron spectroscopy (XPS) measurements were carried out. The results are shown in Fig. S5. In the spectrum,

elements of Si, Ti, C, Ag and O can be observed.

The C 1s at 284.6 eV is due to the The Ag 3d5/2 and

adventitious hydrocarbon originated from the instrument itself.

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Ag 3d3/2 is due to the high purity silver paint that has been used during XPS sample preparation. All samples present binging energies for Ti 2p3/2 peaks at 458.2 eV

which can be assigned to Ti4+ in the TiO2 lattice [30], indicating the successful titania coating outside the SiO2@Au colloids. Fig. 6 gives the high resolution XPS spectra Au 4f

of Au 4f regions from the surface of the sample SiAuTi-3 and SiAuTi-4.

region is characterized by a doublet of two spin orbit components corresponding to Au 4f7/2 and Au 4f5/2 with a separation of about ~3.6 eV. The position of Au 4f7/2 peak at value of lower than 84 eV confirms the fact that Au is found as metallic Au [31,32]. Noticeably, No Au 4f7/2 and Au 4f5/2 peaks were found in sample SiAuTi-1 and SiAuTi-2 may not only due to the low loading of the Au nanoparticles but also due to the titania layer coated on the outside of the SiO2@Au collides (as shown in the TEM and STEM images). 3.1.3 N2 adsorptiondesorption analysis The surface areas and pore structures of the as-prepared samples with and without Au nanoparticles decoration were investigated by N2 adsorptiondesorption analysis. Fig. S6 shows the N2 adsorptiondesorption isotherms and the corresponding pore size distribution curves of the calcined SiO2@Au@TiO2 core-shell nanostructures with and without Au nanoparticles decoration. Without Au nanoparticles decoration,

the isotherms are of the typical type IV pattern with distinct H2 and H3 hysteretic loops in the range of 0.50.9 P/P0 and 0.91.0 P/P0, respectively, indicating the existence of ink-bottle- and slit-shaped pores according to the IUPAC classification [33]. It is believed that the bimodal pore structures are beneficial to the

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enhancement of photocatalytic performance due to the faster diffusion of various reactants and byproducts and the increased harvesting of exciting light by multiple scattering within the porous framework [34,35]. However, with Au nanoparticles decoration, the hysteresis loop 1 disappeared and the hysteresis loop 2 shift to a higher relative pressure (P/P0) range, which indicate that the increase of average pore size (disappearance of the mesopores) and the decrease of total pore volume [36]. The corresponding pore size distributions of all samples were determined using the BarrettJoynerHalenda (BJH) method from the desorption branch of the isotherm. Data concerning the BET surface area, average pore size and pore volume of the calcined SiO2@Au@TiO2 core-shell nanostructures with and without Au

nanoparticles decoration are gathered in Table 1.

The BET surface area and total

pore volume decreased with the increasing of decoration amount of Au nanoparticles. This is mainly because a part of pores of the SiO2@Au@TiO2 core-shell nanostructures may be blocked by the loaded Au nanoparticles. It has been reported

that the larger surface area and pore volume are beneficial to offer more active adsorption sites and photocatalytic reaction centers result in improving the photocatalytic activity [37]. Moreover, it is also believed that the developed pore structures are beneficial to fast diffusion of the target pollutant and various byproducts, thus improving the photocatalytic activity [38]. Therefore, the excessive decoration of Au nanoparticles will lead to the decrease of the photocatalytic activity. 3.1.4 UVvis absorbance spectra analysis UVvis absorbance spectra in the range from 200 to 800 nm of the calcined

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SiO2@Au@TiO2 core-shell nanostructures with and without Au nanoparticles decoration are shown in Fig. 7. It can be clearly observed that the samples with Au

nanoparticles decoration have stronger absorptions in the visible light region compared with the sample without Au nanoparticles decoration, which is due to the surface plasma resonance of Au nanoparticles decoration in the SiO2@Au@TiO2 core-shell nanostructures. With increasing the doping amount of Au, the absorption

intensity of Au surface plasma resonance peak at wavelength of ~560 nm [39] would be gradually enhanced. This ensures that the SiO2@Au@TiO2 core-shell In addition, the UV

nanostructures can be worked under visible light irradiation.

part of the spectra were very similar for all the samples, indicating that Au nanoparticles only deposits on surface of titania layer [10,30]. 3.2. Photocatalytic activity The photocatalytic activities in visible light of the as-prepared samples were evaluated by employing the photodegradation of naproxen as a model reaction. Herein, the naproxen was selected as a model pollutant since it is a representative of the PPCPs that has been newly and widely detected in the aquatic environment over the past decade. Fig. 8a shows the photocatalytic oxidation of naproxen in the It can be found in Fig.

presence of different samples under visible light irradiation.

8a that visible light irradiation has no effect on the naproxen removal, no more than 2.2% of naproxen could be decomposed even after 6 h irradiation. As compared

with direct photolysis, 14% and 29.7% of naproxen could be removed in the presence of the TiO2 spheres (denote as Ti) and SiO2@TiO2 core-shell nanostructures (denote

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as SiTi), respectively. Supporting Information.

The synthesis process of TiO2 spheres can be found in Moreover, a higher removal rate was obtained when the

SiTi was replaced by SiO2@Au@TiO2 core-shell nanostructures (SiAuTi-2), thus indicating the Au decoration on the interface of SiO2/TiO2 can enhance the photocatalytic activity. It has been reported that Au nanopartilces decoration can

enhance the photocatalytic activity in visible light due to the following two reasons. One is to help harvest the visible-light energy by their plasmonic effects, and the other is to enhance charge separation by serving as an electron reservoir [40,41]. Therefore, the photocatalytic activity under visible light irradiation enhanced with the increasing decoration amount of Au nanoparticles. As shown in Fig. 8b, the However,

photocatalytic activity of SiAuTi-2 is higher than that of the SiAuTi-1.

with further increase in the decoration amount of Au, the photocatalytic activity decrease dramatically. This is because excessive amounts of Au nanoparticles can

deteriorate the photocatalytic activity by increasing the occurrence of exciton recombination [42]. Moreover, excessive decoration of the Au nanoparticles may

also break the connection of the TiO2 and SiO2 thus leading to decrease of the photocatalytic activity. Therefore, sample SiAuTi-2 (Au content 0.1 wt%) in our In addition, the

case processes the best photocatalytic activity for naproxen removal.

visible light photocatalytic activities the of the as-prepared SiAuTi core-shell nanostructures with different Au decoration amounts are higher than that of the well-known commercial photocatalyst Degussa P25. 3.3. Recycling of the photocatalysts

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Importantly, in order to prevent additional contamination, the nanosized catalysts should be completely removed from the treated solution. It has been reported that

three-dimensional (3D) hierarchical structures have taken an advantage over powder catalysts for separating the catalyst from solution by filtration or sedimentation [43]. In our experimental, the SiO2@Au@TiO2 core-shell nanostructures can be separated from an aqueous suspension in less than 4 h by sedimentation. For faster recycle of

the catalysts, highly field-responsive superparamagnetic magnetite (Fe3O4) cores were embedded in the SiO2@Au@TiO2 core-shell nanostructures (see Fig. 9ac). Our

previous work have already demonstrate that this superparamagnetic magnetite can be easily separated from solution in a low magnetic field gradient since it has a high saturation magnetization [27]. A typical Fe3O4@SiO2@Au@TiO2 core-shell

nanostructure (denote as FeSiAuTi, see Fig. 9c) is composed of a central Fe3O4 core with an average diameter of ~115 nm, an interlayer of SiO2 with an average thickness of ~31 nm, tunable content of Au nanoparticles adsorbed on the surface of SiO2 shell, and an outer layer of TiO2 with an average thickness of ~21.0 nm. Herein, we have

demonstrated that the majority of the superparamagnetic photocatalysts can be rapidly collected within 2 min by using an external magnetic field (a 0.8 cm 1.8 cm 2.8 cm quadrate NdFeB magnet, as shown in Fig. 9d and Fig. 9f), and all of the Fe3O4@SiO2@Au@TiO2 core-shell nanostructures can be completely removed after 10 min collection. The photocatalytic activity of the as-prepared superparamagnetic

photocatalyst was also evaluated by photocatalytic degradation of naproxen in visible light under the same reaction condition as mentioned above. The result is shown in

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Fig. 8b, from which one can see that the FeSiAuTi also has photocatalytic activity in visible light. It is because the superparamagnetic magnetite in the core-shell

nanostructure just serve as the magnetic core for separation of the catalyst. Unfortunately, the photocatalytic activity of FeSiAuTi is lower than that of the SiAuTi-2 because of the lights scattering and screening effect [44,45] origin from the turbid suspension of FeSiAuTi (as shown in Fig. 9d). It has been proved that when

the catalyst dose exceeds the optimum amount, the photocatalytic activity decreased with the increasing dosage of the catalyst due to light scattering and screening effect [44]. Many literature studies also pointed out that the catalyst amount beyond 1.0

g/L will result in the deterioration of the degradation [46]. In our experiment, in order to keep the same amount of TiO2 (0.3 g/L) in each photocatalytic oxidation, about 1.3 g/L of FeSiAuTi nanocomposites were used in the experiment. This may

be one of the reason to explain why the FeSiAuTi nanocomposites show lower efficiency than the SiAuTi nanocomposites. Moreover, compare to the SiAuTi

suspension, the darker of the FeSiAuTi suspension may also lead to screening effect. 4. Conclusions In summary, SiO2@Au@TiO2 core-shell nanostructures, with high photocatalytic activities under visible light irradiation, were synthesized by combining three individual synthesis steps with calcination. Sample SiAuTi-2 (with Au content of

0.1 wt%) possesses the highest photocatalytic activity since it has the suitable decoration amount of Au nanoparticles for harvesting the visible-light energy by their plasmonic effects and for prohibiting the recombination of free excitons by serving as

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an electron reservoir.

In addition, the as-prepared magnetic photocatalysts

(Fe3O4@SiO2@Au@TiO2 core-shell nanostructures) can be collected from aqueous solution within 10 min by an external magnetic eld. The high photocatalytic

activity under visible light irradiation and the fast separation by magnetic separation will make the application of these core-shell nanostructures in practice possible. Acknowledgments This work was financially supported by the National Natural Science Foundation of China (No. 51108406 and No.51208457) and the Fundamental Research Funds for the Central Universities (No. 2013QNA4026), to whom we are grateful. We also thank

Ms. Mao and Ms. Wu, the technician of 985-Institute of Agrobiology and Environmental Sciences of Zhejiang University, for help with N2

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Figure Captions: Fig. 1. Schematic illustration and typical TEM images of the synthesis process of the SiO2@Au@TiO2 core-shell nanostructures Fig. 2. Schematic of experimental apparatus for photocatalysis. (1) water out, (2) water in, (3) xenon lamp, (4) quartz cold trap, (5) lamp protection sleeve, (6) cutoff filter, (7) water out, (8) sample tube, (9) water in, (10) magnetic stirrer, (11) water bath, (12) mechanical stirrer, (13) power switch. Fig. 3. TEM images of (a) SiO2 spheres, (b) SiO2@Au, (c) SiO2@Au@TiO2, and calcined SiO2@Au@TiO2 core-shell nanostructures at the same magnification. Fig. 4. STEM image of a typical SiO2@Au@TiO2 core-shell nanostructure and the corresponding EDX elemental mappings. Fig. 5. XRD patterns of the calcined SiO2@Au@TiO2 core-shell nanostructures with different doping amount of Au nanoparticles. Fig. 6. High resolution XPS spectra of the Au 4f region taken on the sample SiAuTi-3 and SiAuTi-4. Fig. 7. UVvis diffuse reflectance spectra of the calcined SiO2@Au@TiO2 core-shell nanostructures with different doping amount of Au nanoparticles. Fig. 8. a) Photocatalytic degradation of naproxen in the presence of TiO2, SiO2@TiO2, and SiO2@Au@TiO2 under visible light irradiation; b) Influence of Au loading (0.05, 0.01, 0.25, 0.50 wt%, and FeSiAuTi) on the naproxen removal. Fig. 9. TEM images of (a) Fe3O4@SiO2, (b) Fe3O4@SiO2@Au, (c) Fe3O4@SiO2@Au @TiO2; (d) and (e) separation process of by using a quadrate NdFeB magnet.

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Table 1

Table 1 BET surface areas and pore structures of the SiO2@Au@TiO2 core-shell nanostructures with different doping amount of Au nanoparticles Au content Samples (wt%) SiTi SiAuTi-1 SiAuTi-2 SiAuTi-3 SiAuTi-4 0 0.05 0.1 0.5 1.0 (m2/g) 14.6 12.0 10.2 8.9 9.4 (nm) 12.8 20.9 28.5 36.2 35.8 volume (cm3/g) 0.029 0.031 0.027 0.027 0.026 BET surface area Average pore size Total pore

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 9

Figure 8

SiO2@Au@TiO2 nanostructures with tunable amount of Au nanoparticles were prepared.

SiO2@Au@TiO2 with 0.1 wt% Au content exhibit the highest photocatalytic activity. Magnetic core was embedded in the nanostructure for fast separation of the catalyst.