NANO LETTERS

Synthesis, Characterization, and Catalytic Applications of a Palladium-Nanoparticle-Cored Dendrimer

Karical R. Gopidas, James K. Whitesell,* and Marye Anne Fox*
Department of Chemistry, North Carolina State UniVersity, Campus Box 8204, Raleigh, North Carolina 27695
Received October 1, 2003

2003 Vol. 3, No. 12 1757-1760

ABSTRACT
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A palladium-nanoparticle-cored G-3 dendrimer, characterized by TEM, TGA, absorption, and IR spectroscopies, has approximately 300 Pd atoms in the metallic core and an average diameter of 2.0 nm, to which are attached fourteen G-3 dendrons. Nearly 90% of the metal nanoparticle surface is unpassivated and available for catalysis. The dendrons inhibit metal agglomeration without adversely affecting chemical reactivity. Thus, preliminary investigations have shown that Pd-G-3 can efficiently catalyze Heck and Suzuki reactions.

Nanosized metal particles are effective catalysts for chemical transformations because of their large surface areas.1 Metal nanoparticles for catalytic applications are usually prepared by the evaporation/condensation of the metal or by the chemical/ electrochemical reduction of a metal salt. Since metal nanoparticles tend to lose reactivity as they precipitate or aggregate, stabilizers such as polymers, ligands or surfactants are used in these preparations to prevent agglomeration and to control the particle size. This process may result, however, in strong adsorption of the stabilizers on the active sites of the metal nanoparticles, leading to a loss of catalytic activity. Hence, there is a need for new nanoparticle technologies that provide the improved protection with minimal surface deactivation. In the last several years, several studies dealing with the synthesis and catalytic applications of transition metal nanoparticles stabilized in various microenvironments have appeared in the literature.2 In a recent paper, we have described the synthesis and characterization of gold-nanoparticle-cored dendrimers (AuNCDs),3 Scheme 1. Reduction of hydrogen tetrachloroaurate (HAuCl4), phase transferred into toluene using tetraoctylammonium bromide (TOAB) in the presence of polyaryl ether disulfide dendrons, resulted in the formation of Au-NCDs. The Au-NCDs have a 2-4 nm diameter gold core, to which dendrons are attached radially via Au-S bonds. In stabilizing metal nanoparticles for catalytic applications, the NCDs present a unique opportunity. The nanoparticle cores in NCDs are very stable and do not exhibit discernible aggregation after prolonged periods. The number of dendrons bound to the metallic core decreased as the wedge size increased. Thus,
* Corresponding author: E-mail: mafox@ncsu.edu Permanent address: Photosciences and Photonics Division, Regional Research Laboratory, Trivandrum - 695 019, India. 10.1021/nl0348490 CCC: $25.00 Published on Web 10/29/2003 2003 American Chemical Society

Scheme 1. Synthesis of Pd-G-3, in Which Seven of the Fourteen G-3 Wedges Are Shown (see text)

in higher generation NCDs there are only very few Au-S bonds and most (> 90%) of the nanoparticle surface remains unpassivated. The dendrimer parts of the NCD, which consists mainly of aryl ether moieties, have no specific interaction with the metal core. Thus, the dual requirements of nanoparticle stabilization and nonpassivation of the metal surface are achieved in NCDs of larger dendron generations. In addition, the dendritic interiors of the NCDs have container/scaffolding properties and envelope small organic molecules as guests. Once the small molecules penetrate the dendritic exterior, they can be accommodated in the large void spaces near the metal surface of the metallic core. Because of these properties, we have proposed that the NCDs should be good transition metal catalysts. To prove this proposition, we have now prepared a palladium-nanoparticlecored dendrimer of generation 3 (abbreviated as Pd-G-3) and investigated its catalytic properties. Preliminary results of our studies are presented here. Pd-G-3 was prepared by the Brust reaction (Scheme 1).4 K2PdCl4 was phase transferred into toluene using TOAB. Frechet-type dendritic polyaryl ether disulfide3 of generation

Figure 2. UV-vis absorption spectrum of Pd-G-3 in CH2Cl2. [PdG-3] was 1 mg/10 mL.

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Figure 1. TEM image and core-size histogram of Pd-G-3.

3 (G-3S) was then added. The mixture was cooled in ice (0-2 C) and excess of NaBH4 was added. The resulting black solution was stirred for 2 days and worked up as previously reported for Au-NCD.3 The Pd-G-3 thus obtained was a black powder, freely soluble in methylene chloride, chloroform, toluene and THF, but insoluble in ether and alcohol. Pd-G-3 was stable for several months both as a powder and as a dilute solution in CH2Cl2. FT-IR and TGA experiments showed that Pd-G-3 incorporated some amount of TOAB and this could not be removed by the standard purification procedure. Figure 1 shows a high-resolution TEM image of Pd-G-3 and the corresponding core-size histogram. It can be seen from Figure 1 that the particles exhibit a relatively wide size distribution (1-5 nm). The mean core diameter obtained from the histogram plot was 2.0 nm. Figure 2 shows the absorption spectrum of Pd-G-3 in methylene chloride. There is no obvious surface plasmon band and the spectrum consisted of a smoothly increasing absorption at increasing energy. The spectrum obtained was similar to those of the palladium monolayer protected clusters (Pd-MPCs) reported by Murray and co-workers.5 Figure 3 shows the IR spectrum of Pd-G-3. The spectrum is identical with that of the G-3 dendron3 except for the increased intensity of the band in the 2800-2900 cm-1 region. This band, which arises from C-H stretching vibrations, is attributed to the CH2 groups in TOAB, which is present as an impurity in the NCD. A similar situation was observed in Au-NCDs, as has been reported earlier.3 Thermogravimetric analysis was carried out to estimate the total organic content of Pd-G-3 (see Supporting Information). The volatilization occurred in two stages. The first
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Figure 3. FTIR spectrum of Pd-G-3 films dropcast on a KBr salt plate. Table 1. Average Physical Parameters for Pd-G-3
average core diameter no. of Pd atoms in the core no. of G-3 dendrons attached to the Pd core no. of atoms on the surface of Pd core passivated Pd surface area unpassivated Pd surface area
a

2.0 nm 300 14 150a 9% 91%

Assumes that 50% of atoms are on the surface of a 2 nm Pd particle.

stage, which contributed approximately 8% of the weight loss, was attributed to the removal of trapped solvent and TOAB. The second decomposition step, which started at about 250 C, was attributed to the volatilization of the G-3 dendron. The weight percentage of Pd remaining at the end of thermal decomposition was 54%. Thus, the weight percentage of G-3 dendron in Pd-G-3 is given by 100 - (54 + 8) ) 38%. A physical picture of the Pd-G-3 nanostructure can be postulated from the TEM and TGA data. From TEM size distributions, one can obtain the average diameter of the nanoparticle. The density of bulk face-centered cubic palladium is 12.03 g/cm3. Assuming the same density for Pd nanoparticles, we calculate the density of the metal nanoparticle as 68 atoms/nm3. The approximate number of Pd atoms in a nanoparticle can then be calculated using the equation NPd ) (68 nm-3)(/6)(D3), where D is the average diameter of the nanoparticle in nanometers. The weight of the Pd core is then given by WPd ) NPd 106.4 (106.4 )
Nano Lett., Vol. 3, No. 12, 2003

Scheme 2.

Heck Reactions with Pd-G-3 as a Homogeneous Catalyst (reported yields unoptimized)

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Scheme 3.

Suzuki Reactions with Pd-G-3 Used as a Heterogeneous Catalyst (yields are unoptimized)

atomic weight of Pd). WPd corresponds to 54% of Pd-G-3 weight (from TGA). Using this value, the weight of the dendritic fraction (WG-3S), which corresponds to 38% of PdG-3 weight, can be calculated. WG-3S thus obtained was divided by the molecular weight of the G-3S dendron (1607) to obtain the number of dendrons attached to the core. Average Pd-G-3 parameters that we obtained from these calculations are given in Table 1. A Pd nanoparticle of 1.6 nm diameter has 63% of its atoms on the surface.6 If we assume that 50% of atoms in a 2.0 nm cluster are on the surface, then Pd-G-3 will have approximately 150 Pd atoms on the surface. Of these, only 14 (9% of surface atoms or area) are involved in Pd-S bond formation. Figure 1 showed a distribution of Pd particle sizes, and as a result, the number of dendrons attached to the Pd core of a given size may also vary because of steric constraints. Thus, the numbers reported
Nano Lett., Vol. 3, No. 12, 2003

in Table 1 are averages, obtained by averaging TEM results. In an alkanethiolate MPC, most of the surface atoms are linked via thiolate groups. For example, a Pd-MPC with 459 Pd atoms has 198 C12-thiolate units attached to it.5 Hence, MPCs, lacking many surface-accessible sites, are not good catalysts. In Pd-G-3, only about 9% of the surface Pd atoms are involved in bonding to the dendrons, and the remaining 91% of the surface sites are exposed. Thus, Pd-G-3 can be a good catalyst if (1) most of the (unpassivated) surface atoms are available for catalysis and (2) the required reagents can penetrate the dendritic exterior to reach the metal surface. We have therefore employed Pd-G-3 as catalyst in two very important C-C bond-forming reactions, the Heck and Suzuki reactions.7 These reactions are normally carried out on Pd-phosphine catalysts. Because of the adverse environmental effects associated with phosphines, phosphine-free
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reaction conditions for Pd catalyzed reactions are desirable, and some stabilized Pd nanoparticles have been shown to be catalytically active under phosphine-free conditions.2 We have used Pd-G-3 as catalyst in the Heck reactions shown in Scheme 2. Typically, 10 mM each of the reactants and 20 mM triethylamine were taken up in toluene and the mixture was heated to reflux for 24 h in the presence of 10 mg (2 10-3 mol %) Pd-G-3. Pd-G-3 is soluble in toluene and, hence, reactions 1 and 2 occur under homogeneous catalytic conditions. After the reaction, toluene was removed in a rotavapor and the residue extracted with ether. The Pd-G-3 catalyst and triethylammonium salt, being insoluble in ether, could be easily removed from the reaction mixture by this procedure. GC-MS of the ether extract (see Supporting Information) did not show any peaks other than those for starting materials, products, and solvents. The turnover numbers (TON ) mol product/mol catalyst) and turnover frequencies (TOF ) mol product/mol catalyst/hour) given in Scheme 2 were calculated from isolated product yields. The reaction with ethyl acrylate proceeded with good yield, although that with styrene was low. The TON and TOF, however, are very high for both reactions. This, coupled with the absence of side products, indicates that the yields could be improved by using slightly higher amounts of Pd-G-3. In most Pd catalyzed reactions, 0.5-2 mol % catalyst is generally used and this is 100-1000 times higher than what we have employed here.2,7 We have also used Pd-G-3 as catalyst in the Suzuki reaction, Scheme 3. Since Pd-G-3 is not soluble in ethanol, Pd-G-3 acts as a heterogeneous catalyst in these reactions. The products were isolated by decanting the reaction mixture into water and extracting with hexane. GC-MS of hexane extract showed only products and staring materials. The yields shown are not optimized but the TON and TOF are very high. These schemes show that coupling reactions with Pd-G-3 can be performed under homogeneous or heterogeneous conditions. In both instances, separation of the reactants and products from the catalyst is easy, and the Pd-G-3 recovered from the reactions was freely soluble in CH2Cl2, indicating that the Pd core had not agglomerated under the reaction conditions. The TON and TOF reported here are among the highest reported for stabilized Pd nanoparticles.2 Unfortunately, Pd-G-3 cannot be employed as catalyst for hydrogenation reactions. A solution of Pd-G-3 (10 mg) in toluene (25 mL) in fact absorbs > 200 mL hydrogen gas, but upon stirring for 3-4 h, the Pd metal gradually precipitated. Likely, the carbon-sulfur bonds in Pd-G-3 undergo hydrogenolysis under these conditions, leading to loss of the dendritic cap from the NCD. Once the capping agent has been removed, the core nanoparticles aggregate, leading ultimately to precipitation of the metal. Thus, NCDs are good catalysts in selected organic coupling reactions. They combine the high efficiency of homogeneous catalysis with the ease of separation associated with heterogeneous catalysis. Since the solubility of a NCD is determined by the solubility of the dendritic shell, our
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previous work with gold NCDs8 indicates that it should be possible to synthesize catalytically active water-soluble PdNCDs. Because water is cheap, readily available, nontoxic, and nonflammable, it has clear advantages as a solvent for industrial scale reactions.9 And since reactions can be carried out under phosphine-free conditions, these Pd-NCDs may be promising candidates for other catalytic applications employing zerovalent metals. Acknowledgment. This work was supported by the Chemistry Division, Office of Basic Energy Sciences, U. S. Department of Energy under grant number DE-FG0201ER15280. K.R.G. thanks the Regional Research Laboratory (CSIR), Trivandrum, India for a one-year sabbatical leave. Supporting Information Available: Synthesis and purification for Pd-G-3, TGA data, procedures for Heck and Suzuki reactions, and corresponding GC-MS data. This material is available free of change via the Internet at http:// pubs.acs.org. References
(1) Schmidt, G., Ed. Clusters and Colloids; VCH: Weinheim, 1994. (b) Hayat, M. A., Ed. Colloidal Gold: Principles, Methods and Applications; Academic Press: San Diego, 1989; Vols 1 and 2. (c) Metal Nanoparticles: Synthesis, Characterization and Applications; Feldheim, D. L., Foss, C. A. Jr., Eds.; Marcel Dekker: New York, 2002. (2) Scott, R. W. J.; Datye, A. K.; Crooks, R. M. J. Am. Chem. Soc. 2003, 125, 3708. (b) Chung, M.-K.; Orlova, G.; Goddard, J. D.; Schlaf, M.; Harris, R.; Beveridge, T. J.; White, G.; Hallett, F. R. J. Am. Chem. Soc. 2002, 124, 10508. (c) Schauermann, S.; Hoffmann, J.; Johanek, V.; Hartman, J.; Libuda, J.; Freund, H.-J. Angew. Chem., Int. Ed. 2002, 41, 2532. (d) Galow, T. H.; Drechsler, U.; Hanson, J. A.; Rotello, V. M. Chem. Commun. 2002, 1076. (e) Ramarao, C.; Ley, S. V.; Smith, S. C.; Shirley, I. M.; DeAlmeida, N. Chem. Commun. 2002, 1132. (f) Li, Y.; Boone, E.; El-Sayed, M. A. Langmuir 2002, 18, 4921. (g) Rocaboy, C.; Gladysz, J. A. Org. Lett. 2002, 4, 1993. (h) Park, K. H.; Son, S. U.; Chung, Y. K. Org. Lett. 2002, 4, 4361. (i) Nagaveni, K.; Gayen, A.; Subbanna, G. N.; Hedge, M. S. J. Mater. Chem. 2002, 12, 3147. (j) Ohde, H.; Wai, C. M.; Kim, H.; Kim, J.; Ohde, M. J. Am. Chem. Soc. 2002, 124, 4540. (k) Moreno-Manas, M.; Pleixats, R.; Villarroya, S. Organometallics 2001, 20, 4524. (l) Rahim, E. H.; Kamounah, F. S.; Frederiksen, J.; Christensen, J. B. Nano Lett. 2001, 1, 499. (m) Li, Y.; El-Sayed, M. A. J. Phys. Chem. B 2001, 105, 8938. (n) Niu, Y.; Yeung, L. K.; Crooks, R. M. J. Am. Chem. Soc. 2001, 123, 6840. (o) Yeung, L. K.; Lee, C. T., Jr.; Johnston, K. P.; Crooks, R. M. Chem. Commun. 2001, 2290. (p) Yeung, L. K.; Crooks, R. M. Nano Lett. 2001, 1, 14. (q) Crooks, R. M.; Zhao, M.; Sun, L.; Chechik, V.; Yeung, L. K. Acc. Chem. Res. 2001, 34, 181, and references therein. (3) Gopidas, K. R.; Whitesell, J. K.; Fox, M. A. J. Am. Chem. Soc. 2003, 125, 6491. (4) Brust, M.; Walker, M.; Bethel, D.; Schiffrin, D. J.; Whyman, R. J. Chem. Soc., Chem. Commun. 1994, 801. (5) Zamborini, F. P.; Gross, S. M.; Murray, R. W. Langmuir 2001, 17, 481. (6) Chechik, V.; Crooks, R. M. J. Am. Chem. Soc. 2000, 122, 1243. (7) Tsuji, J. Palladium Reagents and Catalysts: InnoVations in Organic Synthesis; Wiley: New York, 1995. (8) Gopidas, K. R.; Whitesell, J. K.; Fox, M. A. J. Am. Chem. Soc., submitted for publication. (9) Organic Synthesis in Water; Grieco, P. A., Ed.; Klewer Acedamic: Dordrecht, 1998. (b) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous Media; Wiley: New York, 1997. (c) Aqueous-Phase Organometallic Catalysis, Concepts and Applications; Cornils, B.; Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, 1998.

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NL0348490
Nano Lett., Vol. 3, No. 12, 2003