VOLUME 2, NUMBER 11, NOVEMBER 2002

Copyright 2002 by the American Chemical Society

Self-Organization of Spherical Aggregates of Palladium Nanoparticles with a Cubic Silsesquioxane

Kensuke Naka,* Hideaki Itoh, and Yoshiki Chujo*
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto UniVersity, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
Received July 22, 2002

ABSTRACT
Uniform spherical aggregates of palladium nanoparticles with a mean diameter of 70 nm were produced by stirring of palladium(II) acetate with octa(3-aminopropyl)octasilsesquioxane octahydrochloride (1) as a cubic-linker in methanol at room temperature via self-organized spherical templates of palladium ions and 1. Transmission electron microscopy investigation showed that the highly ordered spherical aggregates were composed of the palladium nanoparticles with a size of 4.0 nm.

Metal particles in the nanometer range exhibit quantum mechanical properties that make them promising candidates for applications in nanotechnology.1 The building and patterning of the metal nanoparticles into organized structures is a potential route to chemical, optical, magnetic, and electronic devices with useful properties.2 Development of simple methods for the fabrication of controlled organized structures is indispensable for preparing new nanodevices. Several approaches have been used to obtain threedimensional aggregates of the metal nanoparticles.3 One of the efficient methodologies for the organization involves the utilization of chemical cross-linking by organic ligands. However, the combination of the metal nanoparticles with bifunctional linking molecules having rigid or flexible structures usually results in the formation of insoluble and uncontrollable aggregates in solutions.3a
* Corresponding author. E-mail: ken@chujo.synchem.kyoto-u.ac.jp; chujo@chujo.synchem.kyoto-u.ac.jp 10.1021/nl025713p CCC: $22.00 Published on Web 09/21/2002 2002 American Chemical Society

Here, we describe a new concept for assembling metal nanoparticles into spherical aggregates via self-organized spherical templates in solution. Our key strategy is to use octa(3-aminopropyl)octasilsesquioxane octahydrochloride (1)4 as a cubic linker for the self-organization of metal nanoparticles. The rationales for the selection of 1 are as follows. First, the cubic silca core is rigid and completely defined, and the eight organic functional groups are appended to the vertexes of the cube via spacer linkage. All eight functional groups of 1 are unable to attach to the same nanoparticle due to the steric hindrance of the cubic structure. Thus, 1 should act as a cubic linker for the nanoparticles. Second, the combination of 1 and metal ions in solution forms stable and spherical colloids,5 which would act as a template for the formation of metal nanoparticles. Third, unlike the bifunctional linking molecules, we expected stronger bonding of the cubic linker to the metal nanoparticles due to the chelate effect. Many papers have been published on the preparation of nanocomposites based on cubic silsesquiox-

Figure 1. TEM images of (a) spherical aggregates composed of palladium nanoparticles stabilized by 1, and (b) enlarged image. The weight ratio of palladium(II) acetate to 1 was 2.0. (c) Size distribution histogram of palladium nanoparticles. (d) Size distribution histogram of spherical aggregates.

anes.6 However, few studies have been successful in controling their shape on the nanometer size. To our knowledge, this is the first observation not only of aggregates of metal nanoparticles with the cubic silsesquioxane as a cross-linker but also of nanocomposites with nanometer sized uniform shape based on the cubic silsesquioxane. It is worth pointing out that the spherical aggregates of the metal nanoparticles were formed spontaneously without any external force.

When a methanol solution (50 mL) of 1 (10 mg, 8.5 10-3 mmol) and palladium(II) acetate (20 mg, 8.9 10-2 mmol) was stirred at room temperature, the solution immediately became turbid, which suggested aggregate formation. The turbid solution gradually turned from yellow to black with increasing the reaction time, indicating the
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reduction of the palladium ions. The resulting black colloidal solution was stable and neither precipitated nor flocculated over a period of several months. One drop of the turbid solution containing the obtained product was placed on a copper grid and allowed to evaporate the solvent under atmospheric pressure at room temperature. Transmission electron microscopy (TEM) showed that spherical aggregates with a mean diameter of 70 nm were obtained (Figure 1). These spherical aggregates were clearly composed of dark spots. These dark spots were individual palladium nanoparticles. Every nanoparticle, with a size of 4.0 ( 0.8 nm, appeared as a discrete entity in the nanosphere. Observation by scanning electron microscopy (SEM) also indicated the formation of spherical aggregates of size 80 ( 20 nm (Figure 2). To confirm the formation of metal nanoparticles, X-ray diffraction (XRD) analysis was used (Figure 3). The XRD pattern of the obtained product showed the characteristic diffraction peaks of the palladium face-centered cubic (fcc) phase, indicating the formation of metallic Pd.7 The average size of the particles was 4.0 nm calculated by the Scherrer formula. The calculated value from the XRD pattern is in good agreement with the result by the TEM image. The spherical aggregates were isolated by centrifugation and washed with methanol several times to remove unbound 1 that was not involved in the aggregates. The content of 1 in the spherical aggregates was 52.4 wt %, determined by thermogravimetric analysis (TGA). Based on the fact that
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Figure 2. SEM image of spherical aggregates composed of palladium nanoparticles stabilized by 1.

Figure 3. XRD pattern of spherical aggregates composed of palladium nanoparticles stabilized by 1.

the average particle size was 4.0 nm, the amount of 1 adsorbed on the surface of each nanoparticle was calculated to be 108. When 1,8-diaminooctane dihydrochloride (7.2 mg, 3.4 10-2 mmol) as a linear bifunctional linker instead of 1 was stirred in a methanol solution of palladium(II) acetate, stable colloids were not formed.8 Although palladium nanoparticles were formed, a subsequent cross-linking reaction between the nanoparticles proceeded to form insoluble aggregates. When octahydrooctasilsesquioxane, which has no ligand at the corner, was used instead of 1 under the same condition, only insoluble black precipitates were observed, indicating that the ammonium group contributed to the stability of the obtained product. These results suggest that the structure and the functionality of 1 may play a predominant role for the formation of the spherical aggregates. The formation of the spherical aggregates was monitored by TEM (see Supporting Information). After addition of 1 (10 mg, 8.5 10-3 mmol) into a methanol solution of palladium(II) acetate (20 mg, 8.9 10-2 mmol) and stirring at room temperature for 5 min, one drop of the solution was placed on a carbon grid. TEM analysis showed the formation of spherical aggregates with diameters between 30 and 70
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nm and no individual palladium nanoparticles identified as black dots. After the reaction mixture was stirred for 12 h, uniform spherical aggregates were also observed. A careful look at the aggregates allows one to distinguish individual palladium nanoparticles as black dots, indicating that reduction of the palladium ions proceeded in the spherical aggregates. These results indicate that the spherical colloids consisted of palladium ions and 1 was formed at the early stage of the reaction. Then, the reduction of the palladium ions by methanol proceeded slowly in the spherical colloids. The spherical shape of the colloids was kept during the reduction process of palladium ions. Consequently, the palladium nanoparticles were incorporated into the spherical colloid composed of 1. Addition of NaBH4 as a strong reducing agent to a freshly prepared methanol solution of palladium(II) acetate and 1 resulted in the immediate change of color from yellow to black, which is characteristic for formation of palladium nanoparticles. The TEM investigation of the obtained product showed no aggregates but monodispersed palladium nanoparticles with a size of 2.0 nm. These results indicate that a weak reducing agent such as methanol is a prerequisite for the formation of the spherical aggregates of the metal nanoparticles. The effect of different concentrations of palladium(II) acetate to 1 with constant concentration (10 mg) was studied. The weight ratio of palladium(II) acetate to 1 was varied from 0.1 to 10. When a weight ratio of palladium(II) acetate to 1 reduced to 1.0 or 0.1, no reduction of palladium ion proceeded. However spherical aggregates were observed by TEM analysis under these conditions. These results suggest that an excess amount of 1 might inhibit the reduction of palladium ion by methanol as a weak reducing agent because the greatest amount of palladium ions might be coordinated with 1. When a weight ratio of palladium(II) acetate to 1 increased higher than 1.0, spherical aggregates consisting of palladium nanoparticles with a diameter size of 70 ( 30 nm were observed by TEM. The concentration of palladium(II) acetate does not have much influence on the average size of the spherical aggregates. TGA results showed that increasing the concentration of palladium(II) acetate led to decreasing contents of the organic moiety. Based on the fact that the size of the spherical aggregates is the same under these conditions, the amount of palladium in each spherical aggregate increased with increasing the weight ratio of palladium(II) acetate to 1. Although the formation mechanism of the self-organized spherical templates consisting of palladium ions and 1 is not fully understood, coordination between the amine groups of 1 and palladium ions might be a major factor in the formation of the spherical templates in solution. The growth of microspheres in a water/oil mixture solution is influenced strongly by the variation of the surface energy with size. The particles tend to grow into a spherical shape in order to minimize their surface energy.9 The shape of the selforganized spherical templates in the present case also became spherical to minimize their surface energy by the same reason. Thus, the size distribution becomes narrower with growth of the self-organized spherical templates.
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In conclusion, we have demonstrated the new concept for the self-organization of the metal nanoparticles into the spherical aggregates by the cubic linker. The present method offers unique possibilities for designing new synthetic routes of controlled organized structures based on the metal nanoparticles and the cubic silsesquioxanes. Further mechanistic studies and applications are underway. Acknowledgment. We thank Professor T. Fukuda, Dr. M. Tsuji, and Dr. S. Yamamoto (Kyoto University) for the TEM micrographs. We also thank Dr. T. Yazawa and Dr. K. Kuraoka at Osaka National Research Institute for the XRD analysis. Supporting Information Available: TEM images of the reaction mixture after 5 min and 12 h from addition of 1 (PDF). This material is available free of charge via the Internet at http://pubs.acs.org. References
(1) (a) Schmid, G. Clusters and Colloids from Theory to Application; VCH: Weinheim, 1992. (b) Simon, U.; Schon, G.; Schmid, G. Angew. Chem., Int. Ed. Engl. 1993, 32, 250. (2) (a) Andres, R. P.; Bielefeld, J. D.; Henderson, J. I.; Janes, D. B.; Kolagunta, V. R.; Kubiak, C. P.; Mahoney, W. J.; Osifchin, R. G. Science 1996, 273, 1690. (b) Peschel, S.; Schmid, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1442. (c) Selvan, S. T.; Spatz, J. P.; Klok, H. A.; Moller, M. AdV. Mater. 1998, 10, 132. (d) Heath, J. R.;

(3)

(4) (5) (6)

(7) (8) (9)

Knobler, C. M.; Leff, D. V. J. Phys. Chem. B. 1997, 101, 189. (e) Vidoni, O.; Philippot, K.; Amiens, C.; Chaudret, B.; Balmes, O.; Malm, J. O.; Bovin, J. O.; Senocq, F.; Casanove, M. J. Angew. Chem., Int. Ed. Engl. 1999, 38, 3736. (f) Mirkin, C. A.; Letsinger, R. L.; Mucic, R. C.; Storhoff, J. J. Nature 1996, 382, 607. (g) Beecroft, L. L.; Ober, C. K. Chem. Mater. 1997, 9, 1302. (a) Brust, M.; Bethell, D.; Schiffrin, D. J.; Kiely, C. J. AdV. Mater. 1995, 7, 795. (b) Boal, A. K.; Ilhan, F.; DeRouchey, J. E.; ThurnAlbrecht, T.; Russell, T. P.; Rotello, V. M. Nature 2000, 404, 746. (c) Adachi, E. Langmuir 2000, 16, 6460. (d) Peng, X. G.; Wilson, T. E.; Alivisatos, A. P.; Schultz, P. G. Angew. Chem., Int. Ed. Engl. 1997, 36, 145. (e) Chang, S. Y.; Liu, L.; Asher, S. A. J. Am. Chem. Soc. 1994, 116, 6739. For the synthesis of 1, see: Feher, F. J.; Wyndham, K. D. Chem. Commun. 1998, 323. Spherical colloid formation was also observed when silver nitrate was mixed with 1 in dimethyl sulfoxide solution. (a) Choi, J.; Harcup, J.; Yee, A. F.; Zhu, Q.; Laine, R. M. J. Am. Chem. Soc. 2001, 123, 11420. (b) Zhang, C. X.; Babonneau, F.; Bonhomme, C.; Laine, R. M.; Soles, C. L.; Hristov, H. A.; Yee, A. F. J. Am. Chem. Soc. 1998, 120, 8380. (c) Haddad, T. S.; Lichtenhan, J. D. Macromolecules 1996, 29, 7302. (d) Mather, P. T.; Jeon, H. G.; Rome-Uribe, A. Macromolecules 1999, 32, 1194. Joint Committee on Powder Diffraction Standards, Diffraction Data File, JCPDS International Center for Diffraction Date, Pensylvania, 1991. The formation of spherical colloids with a mean diameter of 70 nm was observed by TEM analysis. However, the precipitate was formed within 24 h. (a) Sugimoto, T.; Matijevic, E. J. J. Colloid Interface Sci. 1980, 74, 227. (b) Peng, X. G.; Wickham, J.; Alivisatos, A. P. J. Am. Chem. Soc. 1998, 120, 5343.

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