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DOI: 10.1002/adma.200700357

Double-Walled SnO2 Nano-Cocoons with Movable Magnetic Cores**

By Xiong Wen Lou, Chongli Yuan, and Lynden A. Archer*
As a unique class of structured materials, hollow colloidal particles have attracted growing research efforts owing to their technological importance in a wide range of applications.[15] Templating against colloidal particles is probably the most effective and general method for preparation of hollow particles, especially for studies in which a narrow size distribution is required, for example, self-assembly and photonic crystals. Monodisperse latex and silica spheres are commonly used as colloidal templates because they are readily available in a wide range of sizes.[610] The apparent advantage of templating method is that the shape and cavity size of formed hollow structures are directly determined by the template.[11] In principle, template method is very versatile for producing hollow nanostructures with various shapes. However, in practice, one often encounters difficulty in coating a layer of designed material (or its precursors) on the template surface primarily due to materials incompatibility, and in fact prior surface modification is usually required in template synthesis.[2,12] For the coating step, various methods have been exploited, including sol-gel coating,[7,8] surface adsorption,[12,13] chemical vapor deposition,[11] atomic layer deposition,[14] and the powerful layer-by-layer adsorption technique utilizing electrostatic interaction.[6] Among them, sol-gel coating is commonly used for preparation of oxide hollow particles. Templating sol-gel precursors with three-dimensional latex arrays or their replicas (the lost-wax approach) have been demonstrated for preparation of hollow TiO2 and SnO2 colloids.[1517] However, most works in this area have focused on spherical shape, and the resulting hollow spheres are generally singleshelled. Reports on preparation of hollow particles with other shapes (e.g., ellipsoidal shape), are relatively few, partly because of the paucity of nonspherical templates and difficulty in forming a uniform coating around surfaces with large variation in curvature.[17,21a] Previously, xia and co-workers prepared micrometer-sized egg-shell-like TiO2 hollow particles by sol-gel templating against ellipsoidal polystyrene template,[17] and double-walled metal oxide structures were prepared by adsorption on both inner and outer surfaces of hollow latex spheres.[18] To fully exploit these tiny vesicles, it is desirable to have extra functionalities in the interior space as explored by several groups.[5,9,19] Here, we report a simple synthesis of double-walled SnO2 ellipsoidal hollow particles with movable a-Fe2O3 cores. These particles bear some resemblance to silkworm cocoons, and are hereafter termed nano-cocoons. The method is based on hydrothermal shell-by-shell deposition of polycrystalline SnO2 on ellipsoidal a-Fe2O3/SiO2 nanotemplates. Remarkably, no prior surface modification is required. Figure 1 illustrates the procedure for generating nano-cocoons. Step 1 involves the uniform coating of a-Fe2O3 spindles with a layer of SiO2 to produce ellipsoidal a-Fe2O3/SiO2 core

Figure 1. Schematic procedure used for fabrication of three nano-architectures (IIII): 1) silica coating on a-Fe2O3 spindles; 2) and 3) hydrothermal deposition of SnO2 shell; 4) and 5) silica removal in 1.0 M NaOH solution; 6) one-step deposition of porous SnO2 double-shells.

[*] Prof. L. A. Archer, X. W. Lou, C. Yuan School of Chemical and Biomolecular Engineering, Cornell University Ithaca, NY 14853-5201 (USA) E-mail: laa25@cornell.edu [**] We thank Mr. Yasuyuki and Prof. H. D. Abrua for useful discussions, Mr. Chris Orilall for BET measurement. We are grateful to the National Science Foundation (DMR 0404278) for supporting this study. Facilities available through the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR 0079992) were used for this study. Supporting Information is available online from Wiley InterScience or from the authors.

shell particles. This silica coating step by modified Stbers process is highly reproducible. Indeed, free silica particles formed due to homogeneous nucleation are only occasionally observed during TEM examination if they do exist (see Supporting Information). Silica coating not only reduces the surface curvature but also modifies the surface properties, which are beneficial to subsequent hydrothermal deposition of polycrystalline SnO2 forming uniform shells (step 2, see Supporting Information). Interestingly, this deposition step can be repeated to form double-walled structures (see supporting information), as shown in step 3. After annealing at 550 C, the sandwiched silica layer is dissolved in sodium hydroxide solution (step 4 and 5) to produce double-walled (particle I) 1

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or single-walled SnO2 nano-cocoons (particle II). When less amount of ellipsoidal a-Fe2O3/SiO2 nanotemplates is used keeping the deposition solution unchanged, another interesting doubleshelled nanostructure (particle III) is generated with a dense inner wall and loose outer shell (step 6). The crystallographic structure of asdeposited SnO2 is determined by X-ray powder diffraction (XRD) to be tetragonal rutile phase (JCPDS card no. 41-1445, space group: P42/mnm, ao = 4.738 , co = 3.187 ), although the diffraction intensity is relatively low with pronounced peak broadening (see Supporting Information). The collective mean crystallite size of SnO2 estimated from the Scherrers formula is about 2 nm only based on (110), (101), and (211) peaks.[4,9a] XRD analysis also indicates that post-annealing at 550 C does not increase the crystallinity of SnO2 appreciably, but it does improve the structural integrity. Figure 2A shows a low magnification transmission electron microscopy (TEM) image displaying double-walled SnO2 nano-cocoons corresponding to particle I in Figure 1. As can be seen from the image, most nanococoons encapsulate only one a-Fe2O3 spindle which is usually not located in the center of the cocoon. It is therefore believed that the encapsulated a-Fe2O3 spindle is free to move within each cocoon at least when filled with liquid.[19a] From the high magnification TEM image (Fig. 2C), the thickness of inner and outer walls is estimated to be ca. 12 and 20 nm, respectively. Shown in Figure 2D is a high resolution TEM image Figure 2. A) TEM image and B) SEM image of double-walled SnO2 nano-cocoons with movable taken from the edge of the wall in Figa-Fe2O3 spindles; C) high-magnification TEM image of double-wall structure; D) high-resolution TEM image showing lattice fringes taken around the edge of the double-wall shown in C; E) darkure 2C. It clearly shows lattice fringes field TEM image of a single nano-cocoon with two spots indicated by white squares; F) and with crystallite size of a few nm only, G) EDX spectra taken from spots 1 and 2 in E), respectively. which is in good agreement with the above XRD analysis. The morphology of these nano-cocoons is also examined by scanning electron microscopy (SEM). As shown in Figreveals that formation of well-defined double-walled structure ure 2B, the hollow double-walled structure is clearly revealed in the present study could be understood by recognizing the from a broken nano-cocoon indicated by a white arrow. subtle structural heterogeneity. Specifically, amorphous SnO2 At a first glance, formation of such interesting doubleis initially deposited on the polycrystalline SnO2 shell, which walled structures composed of the same material is perhaps is kinetically favored. As the supersaturation drops with time, unexpected since there is no apparent structural heterogenea thermodynamically stable thin shell of crystalline SnO2 ity. In general, one would expect the formation of a homogeforms on the outer surface of amorphous SnO2, which is in neous shell when the shell material is deposited on substrate equilibrium with respect to the surrounding solution. Howwith exactly identical chemical nature. Further investigation ever, unlike this polycrystalline shell, the inner amorphous

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layer remains out of equilibrium with the surrounding solution. Hence, there exists a strong tendency for these amorphous SnO2 to dissolve, especially around the interface region between polycrystalline substrate and initially formed amorphous layer, followed by diffusion through the shell and recrystallization. As a consequence, some void space between the two SnO2 walls is anticipated. This idea is similar to the localized insideout Ostwald ripening mechanism or so-called chemically induced self-transformation proposed recently for addressing template-free formation of hollow nanospheres.[4,20] The elemental composition is analyzed by energy-dispersive X-ray (EDX) microanalysis at the single nano-cocoon level,[21a,b] as shown in Figure 2EG. Specifically, EDX spectra are collected from different locations within the nano-cocoon (Fig. 2E, indicated by white squares with numbers inside). From the EDX spectrum (Fig. 2F) corresponding to spot 1 (Fig. 2E), a strong Fe signal is observed in addition to Sn, confirming that the spindle-like particle encapsulated inside the douFigure 3. A) and B) TEM images of single-walled SnO2 nano-cocoons with movable ble-walled cocoon is iron oxide. If the X-ray beam a-Fe2O3 spindles; C) and D) TEM images of porous double-shelled SnO2 nano-cocoons. is positioned on the double-wall (i.e., spot 2 in Fig. 2E), the EDX spectrum (Fig. 2G) shows no Fe signal, thus indicating that the wall is composed ca layer is largely dissolved during the hydrothermal deposiprincipally of SnO2. It should be noted that a trivial Si signal tion performed under basic conditions. The high porosity of is detected in both spectra, which probably arises from trace the shell wall is confirmed by BrunauerEmmettTeller amount of tin silicate formed during annealing.[21c] (BET) surface area measurement and corresponding adsorpThe present template strategy also allows synthesis of other tion and desorption isotherms. As shown in Figure 4, these types of architecture. For example, single-walled SnO2 nanoparticles have type IV nitrogen adsorption and desorption isococoons can be prepared as shown in Figure 3A and B corretherms, indicating the presence of mesopores which contribsponding to particle II in Figure 1. However, the structure of utes to a relatively high BET surface area of 82 m2 g1 (the tothese single-walled nano-cocoons is not as robust as that of double-walled cocoons. The effect of SnO2 precursor concentration and amount of a-Fe2O3/SiO2 nanotemplate on the de250 position behavior is also investigated. When the precursor concentration is too high (e.g., 20 mM), we find that the SnO2 coating is not uniform, and even hollow SnO2 nanospheres 200 are formed.[4] On the other hand, when it is too low (e.g., 10 mM), SnO2 is hardly deposited on the templates. An opti150 mal precursor concentration of around 16 mM was identified in this way. All experiments reported in the article were there0 20 40 60 80 100 fore carried out under this condition. Interestingly, when the 100 Pore Diameter (nm) amount of ellipsoidal a-Fe2O3/SiO2 nanotemplates is reduced, different SnO2 deposition behavior is observed, giving rise to 50 a double-shelled architecture with dense inner shell and porous outer shell as shown in Figure 3C and D (particle III from step 6, Fig. 1). The fact that the inner shell is similar to 0 the previous single-wall (step 2, Fig. 1) suggests that once 0 0.2 0.4 0.6 0.8 1 some critical thickness (about 25 nm from TEM images) is Relative Pressure (P/P o ) reached, further deposition of excess constituent material to produce a thicker homogeneous wall is not favored. Rather, Figure 4. Nitrogen adsorption and desorption isotherms and pore-size formation of a second shell is initiated through continuous distribution (inset) of porous double-shelled SnO2 nano-cocoons shown in Figure 3C and D. Ostwald ripening. From the TEM images, the sandwiched sili-

Volume Adsorbed (cm /g)

dV/dD

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tal pore volume is about 0.3 cm3 g1).[20] It should be noted that the a-Fe2O3 spindles have a relatively low surface area (ca. 1020 m2 g1), therefore the real specific surface area of SnO2 could be much higher than 82 m2 g1. However, as expected from the TEM images (Fig. 3C and D), the pore size distribution is very broad (Fig. 4, inset) due to irregular packing of small crystallites. Both SnO2 and a-Fe2O3 are widely studied semiconductor materials for applications in gas sensors, photocatalysis and lithium-ion batteries.[4,2224] A trend in the field is to make composite nanomaterials for improved properties. As an example, SnO2 nanorods have been assembled on a-Fe2O3 nanotubes.[25] In this regard, the a-Fe2O3-encapsulating SnO2 nano-cocoons reported here represent another novel composite nanoarchitecture. Recent studies on rattletype nanoparticles have focused on spherical polymer or SiO2 shell with movable metal nanoparticles.[9b,19] The Figure 5. A) TEM image of particles obtained by reducing a-Fe2O3/SiO2 with H2 at 300 C for 5 h; metal oxide/metal oxide combination B) XRD patterns of a-Fe2O3/SiO2 a) and particles shown in (A) (b), pattern b) can be perfectly infurther expands the gallery of this dexed to Fe3O4 (JCPDS card no. 19-0629); C) particle III obtained using Fe3O4/SiO2 nanotemplates unique type of nanostructure. These shown in (A); D) attraction of particle III shown in (C) by a magnet. non-spherical hollow colloids with movable magnetic cores are expected to find tially re-oxidized to a-Fe2O3 by oxygen during hydrothermal new applications, such as magnetically separable photocatatreatment simply judging from the colors (Fe3O4 is black, lyst, self-assembled photonic crystals with controlled banda-Fe2O3 is orange). To avoid this problem, we also investigaps, model particles for fundamental studies in colloidal gated post-reduction of particle I and III with H2. The initial science. results indicate that the complete a-Fe2O3 Fe3O4 converLastly, we will address the magnetic functionality arising sion in particle I and III requires longer reduction time due to from the a-Fe2O3 cores. It is well known that iron oxide in hediffusion limitation of the SnO2 double-shell, and the strucmatite (a-Fe2O3) phase is not a good magnetic material. Howture of the particles remains essentially unaltered during the ever, hematite can be converted to other important magnetic reduction process (see Supporting Information). Nonetheless, phases, such as magnetite (Fe3O4) by reduction with H2 at with only 3 hs reduction, the partially reduced particles al300 C, or even maghemite (c-Fe2O3) by reduction with H2 ready show strong attraction by a magnet (see Supporting Inand re-oxidation with O2.[27] The apparent advantage of formation). Current effort is directed to develop an efficient adopting such two-step process of introducing magnetic funcmagnetically separable SnO2/TiO2 photocatalyst based on tionality is that among iron oxides only hematite colloids can particle III. be routinely synthesized in large amount with a wide range of In summary, double-walled SnO2 nano-cocoons with movsizes and shapes. We have carried out some preliminary experable a-Fe2O3 cores have been prepared by hydrothermal iment to achieve magnetic functionality. First, we attempted shell-by-shell deposition of polycrystalline SnO2 on ellipsoidal to reduce the a-Fe2O3 cores in the coreshell a-Fe2O3/SiO2 a-Fe2O3/SiO2 coreshell nanotemplates followed by removal nanotemplates. XRD analysis (Fig. 5B) indicates that of SiO2. The formation mechanism of these novel nanostruca-Fe2O3 can be completely converted to magnetite (Fe3O4) tures is addressed in terms of a localized inside-out Ostwald phase with 5 hs H2 reduction at 300 C. As shown in Figripening process. The present templating approach also leads ure 5A, although some pores are formed in the cores due to to two other nano-architectures, namely single-walled and pocrystal re-construction during a-Fe2O3 Fe3O4 conversion, rous double-shelled nano-cocoons. The a-Fe2O3 cores can be the ellipsoidal shape is unaltered. Using the resultant ellipsoiconverted to magnetic Fe3O4 by reduction with H2. Possible dal Fe3O4/SiO2 nanotemplates, magnetic particle III has been new applications of these nonspherical hollow colloids with synthesized as shown in Figure 5C which can be separated by magnetic functionality are also discussed. a magnet (Fig. 5D). It should be pointed out that Fe3O4 is par-

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Experimental
The a-Fe2O3 spindles were prepared by aging a solution of 0.02 M FeCl3 and 0.45 mM NaH2PO4 at 105 C for 48 h [26]. For SiO2 coating, 63 mg a-Fe2O3 spindles was first dispersed by ultrasonication in a mixture consisting 650 mL of 2-propanol and 65 mL of deionized water, followed by 60 mL of ammonia (29.6 %). Under magnetic stirring, 4 mL of tetraethylorthosilicate (TEOS) in 2-propanol (10 vol %) was added followed by another 3.5 mL after 2 h, then the reaction was continued for 18 h. The a-Fe2O3/SiO2 particles were harvested by centrifugation, and washed with ethanol and water several times before vacuum-dried at room temperature. For hydrothermal SnO2 deposition, 118 mg a-Fe2O3/SiO2 particles were dispersed in 25 mL of ethanol/water (37.5 vol % ethanol) mixed solvent. To this suspension, urea (0.75 g) and potassium stannate trihydrate (113 mg; K2SnO3 3H2O, Aldrich, 99.9 %) were added. After shaking by hand for about 5 min until the salts dissolved, the suspension was transferred to a 40 mL Teflon-lined stainless-steel autoclave, which was then heated in an air flow electric oven at 170 C for 36 h. After the autoclave cooled down naturally, the particles were washed with ethanol/water once before the same hydrothermal deposition was repeated. For synthesis of porous double-shelled nano-cocoons, about 34 mg a-Fe2O3/SiO2 particles were used. After annealing the particles at 550600 C for 8 h, the silica was dissolved in 1 M NaOH solution at 50 C for about 2 d (note that SnO2 could be dissolved partially in NaOH solution, the alternative way is to dissolve silica in a very diluted HF solution). Products were characterized with X-ray powder diffraction (XRD; Scintag PAD X, Cu Ka, k = 1.5406 ), transmission electron microscopy (TEM/SAED; JEOL-1200EX, 120 kV), ultra-high vacuum scanning transmission electron microscopy (UHV-STEM, 100 kV) equipped with energy dispersive X-ray analysis (EDX), and field emission scanning electron microscopy (FE-SEM; LEO 1550). Nitrogen adsorption and desorption isotherms were measured using Micromeritics ASAP 2020. Received: February 10, 2007 Revised: April 9, 2007 Published online:

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Inorganic Nanostructures X. W. Lou, C. Yuan, L. A. Archer* .............................. Double-Walled SnO2 Nano-Cocoons with Movable Magnetic Cores Double-walled SnO2 nano-cocoons with movable a-Fe2O3 cores have been prepared by hydrothermal shell-by-shell deposition of polycrystalline SnO2 on ellipsoidal a-Fe2O3/SiO2 core/shell nanotemplates followed by removal of SiO2. The present templating approach also leads to two other nanoarchitectures, namely single-walled and porous double-shelled nano-cocoons. The a-Fe2O3 cores can be reduced to magnetic Fe3O4 post-synthesis.

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