Langmuir 2004, 20, 237-243

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Preparation of PAMAM- and PPI-Metal (Silver, Platinum, and Palladium) Nanocomposites and Their Catalytic Activities for Reduction of 4-Nitrophenol
Kunio Esumi,* Ryoko Isono, and Tomokazu Yoshimura
Department of Applied Chemistry and Institute of Colloid and Interface Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan Received August 6, 2003. In Final Form: October 6, 2003
Dendrimer-metal (silver, platinum, and palladium) nanocomposites are prepared in aqueous solutions containing poly(amidoamine) (PAMAM) dendrimers with surface amino groups (generations 3, 4, and 5) or poly(propyleneimine) (PPI) dendrimers with surface amino groups (generations 2, 3, and 4). The particle sizes of the metal nanoparticles obtained are almost independent of the generation as well as the concentration of the dendrimer for both the PAMAM and the PPI dendrimers; the average sizes of silver, platinum, and palladium nanoparticles are 5.6-7.5, 1.2-1.6, and 1.6-2.0 nm, respectively. It is suggested that the dendrimer-metal nanocomposites are formed by adsorbing the dendrimers on the metal nanoparticles. Studies of the reduction reaction of 4-nitrophenol by these nanocomposites show that the rate constants are very similar between PAMAM and PPI dendrimer-silver nanocomposites, whereas the rate constants for the PPI dendrimer-platinum and -palladium nanocomposites are greater than those for the corresponding PAMAM dendrimer nanocomposites. In addition, it is found that the rate constants for the reduction of 4-nitrophenol involving all the dendrimer-metal nanocomposites decrease with an increase in the dendrimer concentrations, and the catalytic activity of dendrimer-palladium nanocomposites is highest.

Introduction Recently, dendrimer-metal nanocomposites have been intensively prepared and characterized from the standpoint of catalytic properties1-7 and mulitifilm formation8-10 using poly(amidoamine) (PAMAM) dendrimers. In the catalytic reactions, it has been found that the catalytic activity of PAMAM dendrimer-metal nanocomposites depends significantly on the generation of the dendrimer as well as the surface functional groups of the dendrimer. The catalytic activities of PAMAM dendrimer-metal nanocomposites have been characterized by two different nanocomposite structures; one is that metal nanoparticles are formed inside the dendrimers as higher generation dendrimers (G3, G4) with surface hydroxyl groups are used.1,7 The other is that when using dendrimers with amino or carboxyl groups the dendrimer-metal nanocomosites are formed by adsorption of dendrimers on the metal nanoparticles.6 Until now, only the catalytic activities for PAMAM dendrimer-metal (gold, platinum, palladium, platinum-palladium) have been studied.
* Author to whom correspondence should be addressed.
(1) Zhao, M.; Crooks, R. M. Adv. Mater. 1999, 11, 217; Angew. Chem., Int Ed. 1999, 38, 364. (2) Rahim, E. H.; Kamounah, F. S.; Frederiksen, J.; Christensen, J. B. Nano Lett. 2002, 1, 449. (3) Ooe, M.; Murata, M.; Mizugaki, T.; Ebitani, K.; Kaneda, K. Nano Lett. 2002, 2, 999. (4) Scott, R. W.; Datye, A. K.; Crooks, R. M. J. Am. Chem. Soc. 2003, 125, 3708. (5) Esumi, K.; Miyamoto, K.; Yoshimura, T. J. Colloid Interface Sci. 2002, 254, 402. (6) Esumi, K.; Satoh, K.; Suzuki, A.; Torigoe, K. Shikizai Kyokaishi 2000, 73, 434. (7) Li, Y.; El-Sayed, M. A. J. Phys. Chem. B 2001, 105, 8938. (8) He, J.-A.; Valluzzi, R.; Yang, K.; Dolukhanyan, T.; Sung, C.; Kumar, J.; Tripathy, S. K.; Samuelson, L.; Balogh, L.; Tomalia, D. A. Chem. Mater. 1999, 11, 3268. (9) Krasteva, N.; Besnard, I.; Guse, B.; Bauer, R. E.; Mullen, K.; Yasuda, A.; Vossmeyer, T. Nano Lett. 2002, 2, 551. (10) Esumi, K.; Akiyama, S.; Yoshimura, T. Langmuir 2003, 19, 7679.

Like PAMAM dendrimers, poly(propyleneimine) (PPI) dendrimers have interior tertiary amine groups, but they do not contain amide groups. The size of PPI dendrimers with surface amino groups is smaller than that of PAMAM dendrimers of the same generation. These differences will affect the formation of metal nanoparticles as well as the stabilization of metal nanoparticles. Further, thus obtained dendrimer-metal nanocomposites are expected to exhibit different catalytic activities with the different kinds of the dendrimer. In the present study, we report on the preparation of dendrimer-metal nanocomposites such as silver, platinum, and palladium in the presence of PAMAM or PPI dendrimers with surface amino groups. Furthermore, the catalytic reduction of 4-nitrophenol by these dendrimermetal nanocomposites is also investigated. Experimental Section
Materials. PAMAM dendrimers were prepared according to the literature.11 PPI dendrimers were purchased from Aldrich Co. AgNO3, H2PtCl4, and Na2PdCl4 were purchased from Showa Chemical Co., Wako Pure Chemicals Co., and Kanto Chemicals Co., respectively. 4-Nitrophenol was obtained from Kanto Chemicals Co. All other chemicals were of analytical grade. Milli-Q water was used in all experiments. The physical characteristics of the PAMAM and PPI dendrimers are given in Table 1.12 Preparation of Dendrimer-Metal Nanocomposites. The preparation of metal nanoparticles in an aqueous solution was carried out by the chemical reduction of a metal salt-dendrimer mixture with sodium borohydride. For a typical experiment, 0.2 cm3 of freshly prepared 20 mmol dm-3 metal salt was added to 19.7 cm3 of dendrimer aqueous solutions of various concentra(11) Tomalia, D. A.; Baker, H.; Dewald, J. R.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P. Polym. J. 1985, 17, 117. (12) Crooks, R. M.; Chechik, V.; Lemon, B. I.; Sun, Li.; Yeung, L. K.; Zhao, M. In Metal Nanoparticles, Synthesis, Characterization, and Applications; Feldheim, D. L., Foss, C. A., Eds.; Marcel Dekker: New York, 2002; Chapter 11.

10.1021/la035440t CCC: $27.50 2004 American Chemical Society Published on Web 11/19/2003

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Table 1. Physical Properties of PAMAM and PPI Dendrimers Used

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generation 2 3 4 5

surface group 16 32 64 128

molecular weight PAMAM 6909 14 215 28 826 PPI 1687 3514 7168

diameter (nm) PAMAM 3.6 4.5 5.4 PPI 1.9 2.4 2.8

tions, and the solutions were stirred for 1 h. Then, 0.1 cm3 of 0.4 mol dm-3 freshly prepared ice-cold sodium borohydride was quickly added to the solutions under stirring for 30 min. The metal nanoparticles obtained were analyzed by transmission electron microscopy (TEM) and UV-visible absorption spectroscopy. TEM observation was performed for the samples dried on carbon-coated copper grids. A Hitachi H-9000 NAR transmission electron microscope was operated at an accelerating voltage of 200 kV and direct magnification of 200 000. The size distribution of the metal nanoparticles was determined from at least about 200 particles. Catalytic Reduction of 4-Nitrophenol. In the standard quartz cuvette with a 1-cm path length, 1.4 cm3 of water, 0.3 cm3 of dendrimer-metal nanocomposites solution, and 0.3 cm3 of 2 mmol dm-3 4-nitrophenol were taken. Then, addition and proper mixing of 1 cm3 of aqueous 0.03 mol dm-3 sodium borohyride to the reaction mixtures caused the decrease in the intensity of the peak of 4-nitrophenol. The absorption spectra were recorded on a UV-visible spectrophotometer (Hewlett-Packard 8453A) every 5 s in the range of 190-820 nm at 15 C. The concentrations of both the PAMAM and the PPI dendrimers referred to that of the surface amino groups.

Results and Discussion Before reporting the catalytic activity for dendrimermetal nanocomposites, the dendrimer-metal nanocomposites obtained have been characterized. Dendrimer-Silver Nanocomposites. Figure 1 shows representative UV spectra of the PPI dendrimer (G4)AgNO3 aqueous solution before and after reduction with sodium borohydride. The TEM image and particle size distribution of the PPI dendrimer-silver nanocomposites obtained are also shown in Figure 1. After the reduction, a typical plasmon band of silver nanoparticles appears at around 400 nm. All of the other systems for both the PAMAM and the PPI dendrimers show spectra similar to that of the PPI dendrimer (G4). It should be mentioned that the particle sizes of silver nanoparticles obtained using both the PAMAM and the PPI dendrimers range between 5 and 7 nm, despite different generations of the dendrimers. Dendrimer-Platinum Nanocomposites. Figure 2 shows representative UV-visible spectra of the PPI dendrimer (G4)-H2PtCl6 aqueous solution before and after reduction with sodium borohydride. The TEM image and particle size distribution of the PPI dendrimer-platinum nanocomposites are also given in Figure 2. The absorption band at 260 nm, assigned to platinum ions, disappears after the reduction, and a broad band is observed in a wide wavelength region, indicating the formation of platinum nanoparticles. Similar spectra are obtained for all the other systems. The particle sizes of platinum nanoparticles obtained using both the PAMAM and the PPI dendrimers range between 1.2 and 1.6 nm, which is almost independent of the generation as well as the concentration of the dendrimer. It is noteworthy that stable platinum nanoparticles could be obtained using PPI dendrimers (G3 and G4) at their lower concentrations compared to PAMAM dendrimers (G3 and G4). Dendrimer-Palladium Nanocomposites. Figure 3 shows representative UV-visible spectra of the PPI

Figure 1. (a) UV-visible spectra of the PPI dendrimer (G4)AgNO3 aqueous solution before and after reduction with sodium borohydride: [AgNO3] ) 0.2 mmol dm-3; [NaBH4] ) 2 mmol dm-3; [dendrimer] ) 5 mmol dm-3. (b) TEM microgragh and (c) particle size distribution of silver nanoparticles after reduction.

dendrimer (G4)-Na2PdCl4 aqueous solution before and after reduction with sodium borohydride. The TEM image and particle size distribution of the PPI dendrimerpalladium nanocomposites are also given in Figure 3. After the reduction, the intensity of a broad absorption band

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Figure 2. (a) UV-visible spectra of the PPI dendrimer (G4)H2PtCl6 aqueous solution before and after reduction with sodium borohydride: [H2PtCl6] ) 0.2 mmol dm-3; [NaBH4] ) 2 mmol dm-3; [dendrimer] ) 5 mmol dm-3. (b) TEM micrograph and (c) particle size distribution of platinum nanoparticles after reduction.

increases and the solution turns to clear dark brown, suggesting the formation of palladium nanoparticles. The particle sizes of palladium nanoparticles obtained using both PAMAM and PPI dendrimers range between 1.6 and

Figure 3. (a) UV-visible spectra of the PPI dendrimer (G4)Na2PdCl4 aqueous solution before and after reduction with borohydride: [Na2PdCl4] ) 0.2 mmol dm-3; [NaBH4] ) 2 mmol dm-3; [dendrimer] ) 10 mmol dm-3. (b) TEM micrograph and (c) particle size distribution of palladium nanoparticles after reduction.

2.0 nm, which are almost independent of the concentration as well as the generation of the dendrimer. Similarly to the platinum nanoparticles, stable palladium nanopar-

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Table 2. Average Diameter of Metal Nanoparticles Using PAMAM Dendrimers (nm)a

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concn of PAMAM (mmol dm-3) 10 20 30 40 60

a

silver G3.0 6.1 ( 2.3 6.4 ( 2.3 6.9 ( 3.0 5.7 ( 2.0 G4.0 6.5 ( 1.9 6.0 ( 1.5 5.6 ( 1.4 6.0 ( 2.0 G5.0 6.5 ( 2.9 6.2 ( 1.9 5.9 ( 2.2 5.6 ( 1.6 G3.0 1.4 ( 0.24 1.4 ( 0.26 1.3 ( 0.38 1.2 ( 0.24 1.3 ( 0.27

platinum G4.0 1.5 ( 0.35 1.4 ( 0.33 1.4 ( 0.31 1.2 ( 0.23 G5.0 1.4 ( 0.34 1.4 ( 0.34 1.3 ( 0.28 1.3 ( 0.29 1.3 ( 0.27 G3.0 1.9 ( 0.46 1.9 ( 0.54 1.9 ( 0.38 1.9 ( 0.51 -

palladium G4.0 1.8 ( 0.42 1.9 ( 0.39 1.8 ( 0.49 1.7 ( 0.44 G5.0 1.6 ( 0.57 1.7 ( 0.38 1.9 ( 0.53 1.8 ( 0.52 -

The dashes indicate in which cases the experiments were not carried out. Table 3. Average Diameters of Metal Nanoparticles Using PPI Dendrimer (nm)a

concn of PPI (mmol dm-3) 1 2 4 5 10 20

silver G2.0 7.5 ( 2.4 5.9 ( 1.6 6.9 ( 2.5 6.7 ( 2.3 G3.0 6.5 ( 2.2 6.2 ( 2.6 6.1 ( 2.1 G4.0 5.5 ( 1.9 6.9 ( 2.2 6.2 ( 1.3 G2.0 1.6 ( 0.25 1.5 ( 0.23 1.6 ( 0.21

platinum G3.0 1.5 ( 0.28 1.4 ( 0.27 1.6 ( 0.23 1.5 ( 0.25 1.6 ( 0.25 G4.0 1.4 ( 0.26 1.3 ( 0.23 1.3 ( 0.22 1.5 ( 0.23 1.4 ( 0.29 G2.0 2.0 ( 0.45 1.9 ( 0.33

palladium G3.0 2.0 ( 0.41 2.0 ( 0.33 1.9 ( 0.50 G4.0 1.9 ( 0.46 1.6 ( 0.36 1.6 ( 0.30

a The dots indicate in which cases no data were obtained as a result of the instability of the particles; the dashes indicate in which cases the experiments were not carried out.

ticles are obtained using PPI dendrimers (G3 and G4) at their lower concentrations compared to PAMAM dendrimers (G3 and G4). Tables 2 and 3 show the average particle size and the standard deviation of the metal nanoparticles with the dendrimer concentrations. It is found that the average particle sizes of the metal nanoparticles are almost independent of the concentration of the dendrimer as well as the generation for both the PAMAM and the PPI dendrimers. Interestingly, one can see that monodisperse platinum and palladium nanoparticles are obtained using PPI dendrimers rather than PAMAM dendrimers, whereas monodisperse silver nanoparticles are not obtained for both PAMAM and PPI dendrimers. It is essentially important to discuss the structure of dendrimer-metal nanocomposites obtained. In the present study, because the pHs of mixed solutions before reduction are at around 6-7, the surface amino groups of the dendrimers are protonated.13 Accordingly, metal ions such as PtCl62- and PdCl42- are expected to bind preferentially to the surface amino groups, resulting in the formation of the dendrimer-metal complex. By the reduction with sodium borohydride, dendrimer-metal nanocomposites would be formed by adsorbing the dendrimer molecules on the metal nanoparticles. Although the Ag+ ions are not expected to interact strongly with the dendrimer, dendrimer molecules would be covered on the silver nanoparticles to stabilize the silver nanoparticles after the reduction. However, relatively large silver nanoparticles with a large standard deviation are only obtained as a result of a weak interaction of silver nanoparticles with the dendrimers. These structures are also supported from the results of Fourier transform infrared measurements.14 From the size of dendrimer itself shown in Table 1, it is easily understood that the metal nanoparticles could not be formed inside the PPI dendrimers because the dendrimer sizes are similar or smaller than the nanoparticles. Comparison of PAMAM and PPI dendrimers shows that stable platinum and palladium nanoparticles are obtained at lower concentrations when using PPI dendrimers than when using PAMAM dendrimers. From the fact that PPI dendrimers are soluble in water, dimethylformamide, and
(13) Cakara, D.; Kleimann, J.; Borkovec, M. Macromolecules 2003, 36, 4201. (14) Esumi, K.; Suzuki, A.; Yamahira, A.; Torigoe, K. Langmuir 2000, 16, 2604.

Figure 4. Successive UV-visible spectra of the reduction of 4-nitrophenol by the PPI dendrimer (G4)-platinum nanocomposites: [4-nitrophenol] ) 0.1 mmol dm-3; [platinum] ) 0.01 mmol dm-3; [dendrimer] ) 0.25 mmol dm-3; [NaBH4] ) 10 mmol dm-3.

dichloromethane but PAMAM dendrimers are not soluble in dichloromethane, it is suggested that the hydrophobicity of the PPI dendrimers is greater than that of the PAMAM dendrimers. Accordingly, there is a great possibility that the PPI dendrimers could be preferentially adsorbed on the metal nanoparticles compared to PAMAM dendrimers, although a competitive adsorption experiment was not carried out. As a result, stable dendrimer-metal nanocomposites could be obtained at lower concentrations using PPI dendrimers. Catalytic Reduction of 4-Nitrophenol. Figure 4 shows representative successive UV-visible spectra of the reduction of 4-nitrophenol by PPI dendrimer (G4)platinum nanocomposites. Similar spectral changes are also obtained for all the other dendrimer-metal nanocomposite systems. In the absence of any catalysts, the peak due to 4-nitrophenol at 400 nm remains unaltered. Addition and proper mixing of an aliquot of dendrimer-

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Table 4. Rate Constants for 4-Nitrophenol Reduction by PAMAM Dendrimer-Metal Nanocomposites (10-4 s-1)a concn of PAMAM (mmol dm-3) 10 20 30 40 60
a

silver G3.0 5.41 3.75 2.03 1.76 G4.0 5.9 4.02 3.83 3.31 G5.0 5.17 2.91 1.63 0.263 G3.0 17.6 5.24 4.01 6.82 2.39

platinum G4.0 26.2 12.6 11.9 9.39 G5.0 25 13.6 9.25 34.78 4.05 G3.0 35.9 13.2 20.5 20.2 -

palladium G4.0 17.9 13.3 12.2 12.0 G5.0 32.5 34.3 25.3 22.7 -

The dashes indicate in which cases the experiments were not carried out. Table 5. Rate Constants for 4-Nitrophenol Reduction by PPI Dendrimer-Metal Nanocomposites (10-4 s-1)a

concn of PPI (mmol dm-3) 1 2 4 5 10 20

silver G2.0 12.2 9.73 6.41 3.92 G3.0 3.07 1.50 0.493 G4.0 5.60 4.67 4.13 G2.0 141 125 114

platinum G3.0 601 585 357 279 166 G4.0 582 504 229 147 33.9 G2.0 2165 1763

palladium G3.0 4074 336 37.0 G4.0 3637 1153 902

a The dots indicate in which cases no data were obtained as a result of the instability of the particles; the dashes indicate in which cases the experiments were not carried out.

platinum nanocomposites to the reaction mixture cause the fading and ultimate bleaching of the yellow color of the 4-nitrophenol solution. Because the amount of the dendrimer-platinum nanocomposites added is very small, the absorption spectra of 4-nitrophenol is hardly interfered with by the dendrimer-platinum nanocomposites. The reduction can be visualized by the disappearance of the 400-nm peak with the concomitant appearance of a new peak at 290 nm. This peak has been attributed to 4-aminophenol.15 The concentration of the borohydride ion greatly exceeds that of 4-nitrophenol and the catalysis particles. The excess of sodium borohydride used increases the pH of the reacting system, thereby retarding the degradation of the borohydride ions, and the liberated hydrogen purged out air, thereby checking the aerial oxidation of the reduced product of 4-nitrophenol. Furthermore, as the concentration of sodium borohydride is very high, it remains essentially constant during the reaction. Therefore, in this case pseudo-first-order kinetics with respect to 4-nitrophenol could be used to evaluate the catalytic rate. A good linear correlation with time, that is, log A versus time plot, is obtained for all the systems studied (Figure 5). Here, A stands for absorbance at any time t. The values of the pseudo-first-order rate constant (k) determined from these plots are given in Tables 4 and 5. Also, the values of the rate constant with the concentration of dendrimer are plotted in Figure 6. One can see that the rate constants for all the systems are decreased with an increase in the concentration of the dendrimer for both the PAMAM and the PPI dendrimers. It is noteworthy16 that the dendrimers transform from starlike to spherelike entities where there is a gradual transition from G3 to G10 and the distribution of the dendrimer surface groups is not uniform throughout the interior of the dendrimer. Accordingly, it seems that the shape of the dendrimer is an important factor in stabilizing the metal nanoparticles and affects the catalytic reaction. That is, the early generations of PAMAM and PPI dendrimers (G2 and G3) possess a highly asymmetric, open, hemispherical shape, while the later generations (G > 4) possess a nearly spherical shape with dense-packed surfaces. These dendrimer shapes would provide different dendrimer adsorption layers on the metal particles, which
(15) Pradhan, N.; Pal, A.; Pal, T. Colloids Surf., A 2002, 196, 247. (16) Caminati, G.; Turro, N. J.; Tomalia, D. A. J. Am. Chem. Soc. 1990, 112, 8515.

Figure 5. Plots of ln A versus time for the reduction of 4-nitrophenol by the PPI dendrimer (G4)-platinum nanocomposites obtained: (a) [dendrimer] ) 5 mmol dm-3; (b) [dendrimer] ) 10 mmol dm-3; (c) [dendrimer] ) 20 mmol dm-3.

affect the catalytic reaction. However, in the present study, a distinct correlation between the rate constants and the generation of both the PAMAM and the PPI dendrimers is not observed. It is interesting to note that the rate constants for PPI (G3 and G4)-palladium nanocomposites and -platinum nanocomposites are greater than those for the corresponding PAMAM (G3, G4, and G5) nanocomposites at the same dendrimer concentration. The rate of electron transfer at the metal surface can be influenced by two steps: (1) diffusion of 4-nitrophenol to the metal surfaces and (2) interfacial electron transfer and diffusion of 4-aminophenol away from the surface. The observed rate constant may be expressed as17

1/kobs ) [1/(4R2)][(1/ket) + (R/D)]

(1)

where R is the radius of the metal particles, D is the

(17) Gratzel, M.; Frank, A. J. J. Phys. Chem. 1982, 86, 2964.

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Figure 6. Plots of the rate constant for the reduction of 4-nitrophenol by dendrimer-metal nanocomposites against the concentration of the surface amino group of the dendrimers: (a) dendrimer-silver nanocomposites; (b) dendrimer-platinum nanocomposites; (c) dendrimer-palladium nanocomposites.

diffusion coefficient, and ket is the rate constant for electron transfer. When heterogeneous charge transfer is faster than diffusion, eq 1 reduces to the Smoluchowski expression:

kobs ) 4DR

(2)

This assumption could be attributed to the higher driving force for particle-mediated electron transfer caused by their large Fermi level shift in the presence of highly electron injecting species such as borohydride ions. It is supposed that the diffusion of 4-nitrophenol and the particle size mainly control the rate of the reduction. Because PAMAM or PPI dendrimers with surface amino groups are considered to adsorb on the metal nanoparticles, the adsorbing dendrimers would affect the diffusion of 4-nitrophenol to the metal nanoparticle surface. Accordingly, it is suggested that the rate constants depend on the coverage of the dendrimer on the metal particle

surface under almost the same particle size. This idea provides that as the coverage by the dendrimer increases with an increase in the concentration of the dendrimer the rate constants should be reduced with the dendrimer concentration. In addition, because the size of the PPI dendrimer is smaller than that of the PAMAM dendrimer at the same generation the diffusion of 4-nitrophenol to the metal nanoparticle surface would be much faster for the PPI dendrimer than the PAMAM dendrimer, resulting in the higher rate constants for the PPI dendrimerplatinum and -palladium nanocomposites. Thus, for the dendrimer-platinum and -palladium nanocomposites it seems that the size of the dendrimer (PAMAM or PPI) adsorbed on the metal nanoparticles controls predominantly the reduction of 4-nitrophenol. Finally, it is interesting to compare the catalytic activities for the reduction of 4-nitrophenol by the kind of metal of the dendrimer-metal nanocomposites. The order of the rate constants for both the PAMAM and the

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PPI dendrimers is palladium > platinum > silver. Thus, the origin of this order clearly lies in the different natures of the dendrimer-metal nanocomposites employed because the resulting particle sizes and surface compositions are different. The reason suggested for the low activity of the dendrimer-silver nanocomposites is that the silver nanoparticles are often easily oxidized and their particle sizes are larger than the other metal nanoparticles. Conclusions Silver, platinum, and palladium nanoparticles are prepared in the presence of PAMAM or PPI dendrimers with various generations and concentrations. The particle sizes of the metal nanoparticles thus obtained are almost unaltered with the dendrimer generation as well as the dendrimer concentration. The particle sizes and particle size distributions of the platinum and palladium nanoparticles are much smaller and narrower than those of

the silver nanoparticles for both the PAMAM and the PPI dendrimers. From the studies of the reduction reaction of 4-nitrophenol, it is found that the change in the rate constants for the dendrimer-silver nanocomposites is not clearly observed by the kind of the dendrimer as well as the generation, while the rate constants for the PPI dendrimer-platinum and -palladium nanocomposites are significantly greater than those for the PAMAM dendrimer-platinum and -palladium nanocomposites. In addition, the rate constants for all the systems decrease with increasing dendrimer concentration. This decrease is attributed to the increase of the dendrimer adsorption on the metal nanoparticles. Among the three different metal nanocomposites, the PPI dendrimer-palladium nanocomposites show the highest catalytic activity for the reduction of 4-nitrophenol.
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