NANO LETTERS

Synthesis of Metal-Loaded Poly(aminohexyl)(aminopropyl)silsesquioxane Colloids and Their Self-Organization into Dendrites

Lyudmila M. Bronstein,*, Christina Linton, Robert Karlinsey, Barry Stein, Dmitri I. Svergun, Josef W. Zwanziger, and Richard J. Spontak|
Departments of Chemistry and Biology, Indiana UniVersity, Bloomington, Indiana 47405, EMBL, Outstation, Notkestr. 85, D-22603 Hamburg, Germany, and Departments of Chemical Engineering and Materials Science & Engineering, North Carolina State UniVersity, Raleigh, North Carolina 27695
Received March 5, 2002; Revised Manuscript Received June 3, 2002

2002 Vol. 2, No. 8 873-876

ABSTRACT
Hydrolytic condensation of N-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS) in water results in the formation of spherical colloids measuring 40 to 190 nm in diameter and composed of a nearly fully condensed poly(aminohexyl)(aminopropyl)silsesquioxane (PAHAPS) nanostructure containing CSiO3/2 species. Interaction of Pt and Pd salts with these PAHAPS colloids, followed by chemical reduction, results in the formation of discrete metal nanoparticles measuring ca. 12 nm in diameter stabilized within the colloids. Dendrites differing in size and shape are observed to form from aqueous solutions containing PAHAPS colloids loaded with metal salts or metal nanoparticles.

Metal or semiconductor nanoparticles grown in nanostructured polymeric environments remain a source of excitement for researchers interested in establishing commercially feasible routes to the production of uniform and stabilized nanoparticles. From pioneering efforts designed to prepare nanoparticles in block copolymer micelles or ordered block copolymer systems to recent attempts aimed at synthesizing nanoparticles,1 nanowires,2 and nanotubes3 in restricted nanoscale environments, this area of research is driven by the unique properties of nanoparticles in catalytic, nonlinear optical, and semiconductor technologies.4,5 For many applications, precise control over particle growth, size distribution, and surface environment constitutes a crucial design consideration. Our recent studies6,7 have focused on the synthesis of noble metal nanoparticles in nanostructured polymer systems wherein the cage effect or specific interactions with functional groups regulate metal nanoparticle formation and yield well-defined nanoparticles exhibiting enhanced catalytic properties. As described elsewhere,8 the siloxy bilayer of polyoctadecylsiloxane (PODS) prepared by the hydrolytic polycon* Corresponding author. E-mail: lybronst@indiana.edu. Department of Chemistry, Indiana University. Department of Biology, Indiana University. EMBL. | North Carolina State University. 10.1021/nl025543g CCC: $22.00 Published on Web 06/14/2002 2002 American Chemical Society

densation of octadecyltrichlorosilane provides excellent control over metal nanoparticle formation, independent of metal species, metal concentration, or reducing agent. Unfortunately, the degree of metal incorporation in PODS is very low due to the absence of active functionality within the polymer. Here we describe the hydrolytic condensation of N-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS), H2N(CH2)6NHCH2CH2CH2Si(OCH3)3, to poly(aminohexyl)(aminopropyl)silsesquioxane (PAHAPS). The highly functionalized nanostructure of this polymer facilitates incorporation of metal compounds. Moreover, the utility of PAHAPS relative to other reported9 materials lies in its unique combination of water solubility, cross-linked structure, and chemical functionalization. These features together provide a robust growth medium that can accommodate exceptionally high loading levels of nanoparticles without undesirable agglomeration. Prior efforts have targeted AHAPS for the covalent functionalization of silica particles or other inorganic surfaces,10 or for noncovalent surface treatment.11 While AHAPS has been previously examined12 as a precursor in the preparation of polysilsesquioxane gels (among other amino-functionalized silanes), no promising results have been reported to date. In the present work, PAHAPS was prepared by adding 2 g of AHAPS to 150 mL water at an initial pH of 2.5 (using

Scheme 1.

Schematic Representation of PAHAPS Structure

Figure 1. Solid-state 29Si CP-MAS NMR spectrum of PAHAPS showing the locations of C-Si(OH)O2 and C-SiO3/2 species denoted by T2 and T3, respectively.

HCl) and cooled by an ice/water bath. Upon addition of AHAPS, the pH was adjusted to 10. The reaction solution was continuously stirred for 1 h while being cooled and then for another hour at ambient temperature, followed by evaporation on a Petri dish for 1 h at 80 C and overnight at 65 C. The final product formed a very strong film that adhered strongly to glass. Solid-state 29Si cross polarization (CP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) of PAHAPS was performed on a Bruker Avance DSX spectrometer using a 7 mm MAS probe at a 5 kHz spinning speed. Differential scanning calorimetry (DSC) was conducted at a heating rate of 10 C/min with a PerkinElmer DSC-7 using hermetically sealed aluminum pans. Specimens for transmission electron microscopy (TEM) were prepared either by placing a drop of solution onto a carboncoated copper grid or sectioning an epoxy-embedded specimen. Images were acquired at accelerating voltages of 60 and 80 kV on JEOL JEM1010 and Zeiss EM902 microscopes, respectively. Small-angle X-ray scattering (SAXS) data of PAHAPS were collected before and after nanoparticle formation on the X33 camera of the EMBL, and anomalous (ASAXS) measurements were performed on the JUSIFA beamline13 at the DESY synchrotron (Hamburg). According to elemental analysis, the PAHAPS consists of 40.64% C, 9.93% H, 10.36% N, 10.98% Si, and 14.50% Cl. In the limit of complete condensation of the AHAPS siloxy groups (C9H21N2SiO1.5), the composition is predicted to be 51.67% C, 10.04% H, 13.39% N, 13.39% Si, and 11.51% O. These results suggest that the HCl used to adjust the pH of the AHAPS solution is consumed by the precursor so that about one amino group per precursor molecule can be protonated. The FTIR spectrum of neat PAHAPS exhibits very broad bands below 3000 cm-1, which is consistent with the formation of NH2+ species.14 The 29Si CP-MAS NMR spectrum of PAHAPS presented in Figure 1 identifies a prominent signal at -69 ppm, which is assigned to T3 (CSiO3/2) groups.15 Considered together, these results indicate that (i) PAHAPS is nearly fully condensed, (ii) the secondary amino group is protonated (this group should have a higher electron density due to the donor influence of two aliphatic substituent groups compared to the terminal amino group), and (iii) one of the amino groups (location unknown) immobilizes a water molecule due to hydrogen bonding (which explains the higher-than-expected oxygen content in the polymer).
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The chemical formula of PAHAPS that is consistent with all these considerations - [(H2O)H2N(CH2)6NH+2ClCH2CH2CH2SiO1.5]n - yields a composition of 40.97% C, 9.11% H, 10.62% N, 10.62% Si, and 13.47% Cl, which agrees well with our experimental findings. It is well established16 that the hydrolytic condensation of monosubstituted silanes can result in numerous products, generally referred to as silsesquioxanes, the molecular structure of which depends on the identity of substituent groups and the reaction conditions employed. Examples of silsesquioxane structures can be described as ladder,17 cage (complete18 and partial19), and/or random.20 In addition to silsesquioxane fragments, these polymers also typically contain polysiloxane units (with T2 substitution due to the presence of C-Si(OH)O2 moieties). The presence of a single, unambiguous T3 peak in the 29Si CP-MAS NMR spectrum of PAHAPS (the signal from T2 sites is barely detectable) provides strong evidence for a three-dimensional silsesquioxane network. Thermograms of PAHAPS obtained by DSC, however, indicate that a glass transition temperature (Tg) occurs at 0 C. Identification of a Tg at such a low temperature for a highly cross-linked polymer is unexpected and reveals that this polymer network possesses substantial molecular freedom, which is inconsistent with (i) a ladderlike structure composed of small cycles or (ii) the presence of a low concentration of T2 Si atoms (in polysiloxane units). On the basis of these results, we conclude that the PAHAPS nanostructure consists primarily of large cycles and fragments of a random network, as depicted in Scheme 1. The stability of large silsesquioxane rings is further supported by quantum mechanical calculations.21 Although PAHAPS forms a three-dimensional network, it is not an insoluble cross-linked polymer gel. In fact, a turbid colloidal solution in water forms after prolonged stirring (12 h) at ambient temperature or 1 h at 35-40 C. Figure 2a displays a TEM image in which large PAHAPS
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Figure 2. Transmission electron micrographs of (a) PAHAPS spread from solution onto a carbon-coated TEM grid, (b) Pt nanoparticles grown in PAHAPS by NaBH4 reduction, (c) crosslinked structures formed by PAHAPS-K2PdCl4 in water, and (d) K2PdCl4-loaded PAHAPS dendrites. The inset in (a) shows an ultrathin semicontinuous PAHAPS film, whereas the inset in (c) corresponds to the same region displayed in (c) after energy filtering at an energy loss (E) of 250 eV. Circled areas in (b) identify illustrative groups of Pt nanoparticles.

Figure 4. (a) Difference ASAXS data (anomalous signal) acquired from Pt nanoparticles grown in PAHAPS by NaBH4 reduction. The solid line denotes the model fit (from the GNOM computer algorithm22) used to extract the volume distribution (Dv) of Pt nanoparticles presented as a function of length scale (R) in (b).

Figure 3. SAXS profile of PAHAPS in which intensity is shown as a function of scattering vector (s) given by 4 sin(/), where 2 is the scattering angle and () 0.15 nm) is the wavelength of the incident radiation.

colloids (or aggregates thereof) ranging in size from 40 to 190 nm across (determined from 300 particles) are visible upon solution casting and drying on a carbon substrate. The SAXS data provided in Figure 3 for PAHAPS display one broad peak, from which the corresponding structural parameters have been computed using the PEAK computer algorithm.8 Unlike PODS, PAHAPS exhibits only short-range order with a spacing of 2.1 nm, which represents the characteristic size of the repetitive motif within the PAHAPS nanostructure. Long-range order measuring 16.2 nm provides an estimate for the size of a coherently scattering colloidal PAHAPS particle packed in the solid state. The large particles observed by TEM cannot be detected by SAXS (since they would scatter at much smaller angles), whereas the smaller particles detected by SAXS are not seen in Figure 2a due to their low contrast. The inset included in Figure 2a shows a specimen region where the PAHAPS forms an ultrathin semicontinuous film on the carbon substrate. Note
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that the contrast in this inset has been significantly enhanced, relative to Figure 2a, even after energy-filtering at an energy loss of 0 eV to facilitate structural identification. When PAHAPS (colloid or powder) is placed in aqueous K2PdCl4 or K2PtCl6 solutions at a molar ratio of Pd(Pt)/N ) 1:4, metal ions are readily absorbed by the polymer due to both ion exchange with Cl- and coordination with NH2 groups.8,22 If the metal ions are incorporated in the presence of a small quantity of water, PAHAPS remains principally insoluble and can be easily isolated. According to elemental analysis, the degree of Pt incorporation in PAHAPS-K2PtCl6 is determined to be 21.5 wt %. Reduction of this sample in the presence of NaBH4 yields the PAHAPS-Pt nanocomposite shown in Figure 2b. Transmission electron microscopy clearly reveals the existence of uniformly distributed Pt nanoparticles measuring 0.8-2.1 nm in diameter, in marked contrast to pure PAHAPS, which is virtually featureless (and not included here for that reason). The generation of Pt nanoparticles is further corroborated by ASAXS analysis of PAHAPS-Pt powder. Figure 4a displays the scattering intensity arising solely from the Pt nanoparticles, and the resultant volume distribution function (Dv) of the Pt nanoparticles computed by the GNOM computer algorithm23 is presented as a function of length scale (R) in Figure 4b. According to this analysis, most of the nanoparticles measure about 1.5 nm. The small population of large particles
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indicated by Figure 4b implies that these nanoparticles reside is such close proximity (due to the high Pt loading level) that they appear as aggregates. If PAHAPS-Pt is prepared in dilute solution (0.05-1.00 wt % PAHAPS), only 5 wt % of the polymer forms a precipitate (according to gravimetric analysis) as a consequence of chemical interaction with the metal salt. The balance of the metal-containing species is soluble in water even after interaction with the metal salts, as well as after metal salt reduction. After solvent evaporation, these metalloaded colloids remain water-soluble. Intercolloidal crosslinking that occurs due to complexation is responsible for the ultimate precipitation of aggregates formed by a relatively small population of colloids that are large or possess extended branches. Examples of precursors of precipitated PAHAPSK2PdCl4 aggregates are shown in Figure 2c. Lace-like structural elements measuring on the order of microns in size, with connecting struts ranging from ca. 10 to 100 nm across, form due to complexation of extended PAHAPS branches with Pd salt. The inset displayed in Figure 2c is a structuresensitive image of Figure 2c obtained at an energy loss of 250 eV and confirming that the PAHAPS-K2PdCl4 aggregate contains non-carbonaceous constituents. In addition, strongly attractive intercolloidal interactions among metal complexes or metal nanoparticles dramatically alter the properties of the polysilsesquioxane colloids. To illustrate this point, we have employed two specimenpreparation strategies. In the first, single drops of dilute solutions of soluble metal-loaded PAHAPS colloids containing either Pd or Pt salts or nanoparticles have been added to carbon-supported grids for TEM analysis. This approach results in the formation of small dendrites differing in size and shape, depending on the type of metal species and the solution concentration. Alternatively, dendrites have been likewise generated from solutions prepared by immersing powdery PAHAPS in metal salt solution. In this case, interaction between PAHAPS and metal compounds occurs before or simultaneously with PAHAPS dissolution, and results in the formation of typically well-defined and large dendrites measuring on the order of several microns in length (as seen in Figure 2d). Note that some spherical colloids (visible in the background of Figure 2d) do not participate in dendrite development. While the formation of dendrites is common in a wide variety of salts or metals,24 it has never been reported for colloidal particles or nanoparticle-loaded colloidal systems. Because the size and shape of the dendrites produced here can be easily controlled, metal-loaded PAHAPS may find immediate use as catalytically active membranes in which select surface coverage is important. Another possible application for PAHAPS loaded with metal nanoparticles is as a conductive layer between two surfaces, as described elsewhere25 for pure Pd dendrite crystals. Unlike pure metals, however, metal-loaded PAHAPS possesses a number of practical advantages, including lower cost and greater structural stability.

Acknowledgment. This work has been supported, in part, by the Kenan Institute for Engineering, Technology & Science at North Carolina State University. References
(1) Bronstein, L. M.; Chernyshov, D. M.; Valetsky, P. M.; Wilder, E. A.; Spontak, R. J. Langmuir 2000, 16, 8221. (b) Lu, Z.; Liu, G.; Philips, H.; Hill, J. M.; Chang, J.; Kydd, R. A. Nano Lett. 2001, 1, 683. (c) Bronstein, L. M.; Polarz, S.; Smarsly, B.; Antonietti, M. AdV. Mater. 2001, 13, 1333. (2) Han, Y.-J.; Kim, J. M.; Stucky, G. D. Chem. Mater. 2000, 12, 2068. (b) Kovtyukhova, N. I.; Martin, B. R.; Mbindyo, J. K. N.; Mallouk, T. E.; Cabassi, M.; Mayer, T. S. Mater. Sci. Eng. 2002, C19, 255. (c) Zhang, D.; Qi, L.; Ma, J.; Cheng, H. Chem. Mater. 2001, 13, 2753. (3) Li, Y.; Wang, J.; Deng, Z.; Wu, Y.; Sun, X.; Yu, D.; Yang, P. J. Am. Chem. Soc. 2001, 123, 9904. (b) Rao, C. N. R.; Govindaraj, A.; Deepak, F. L.; Gunari, N. A.; Nath, M. Appl. Phys. Lett. 2001, 78, 1853. (c) Hoyer, P. AdV. Mater. 1996, 8, 857. (4) Nanoparticles and Nanostructured Films: Preparation, Characterization and Applications; Fendler, J. H., Ed.; Wiley-VCH: New York, 1998. (b) Henglein, A. Chem. ReV. 1989, 89, 1861. (5) Bradley, J. In Clusters and Colloids; Schmid, G., Ed.; Wiley-VCH: New York, 1994. (6) Sidorov, S. N.; Volkov, I. V.; Davankov, V. A.; Tsyurupa, M. P.; Valetsky, P. M.; Bronstein, L. M.; Karlinsey, R.; Zwanziger, J. W.; Matveeva, V. G.; Sulman, E. M.; Lakina, N. V.; Wilder, E. A.; Spontak, R. J. J. Am. Chem. Soc. 2001, 123, 10502. (7) Bronstein, L. M.; Chernyshov, D. M.; Volkov, I. O.; Ezernitskaya, M. G.; Valetsky, P. M.; Matveeva, V. G.; Sulman, E. M. J. Catal. 2000, 196, 302. (8) Svergun, D. I.; Kozin, M. B.; Konarev, P. V.; Shtykova, E. V.; Volkov, V. V.; Chernyshov, D. M.; Valetsky, P. M.; Bronstein, L. M. Chem. Mater. 2000, 12, 3552. (9) Rao, C. N. R.; Cheetham, A. K. J. Mater. Chem. 2001, 11, 2887. (b) Boal, A. K.; Gray, M.; Ilhan, F.; Clavier, G. M.; Kapitzky, L.; Rotello, V. M. Tetrahedron 2002, 58, 765. (c) Dirix, Y.; Bastiaansen, C.; Caseri, W.; Smith, P. AdV. Mater. 1999, 11, 223. (10) Kneuer, C.; Sameti, M.; Haltner, E. G.; Schiestel, T.; Schirra, H.; Schmidt, H.; Lehr, C.-M. Int. J. Pharm. 2000, 196, 257. (b) Kobayashi, H.; Matsunaga, T. J. Colloid Interface Sci. 1991, 141, 505. (11) Hozumi, A.; Yokogawa, Y.; Kameyama, T.; Sugimura, H.; Hayashi, K.; Shirayama, H.; Takai, O. J. Vac. Sci. Technol. A 2001, 19, 1812. (12) Sanchez, A.; Loy, D. A. Polym. Prepr. 2001, 42, 182. (13) Haubold, H.-G.; Gruenhagen, K.; Wagener, M.; Jungbluth, H.; Heer, H.; Pfeil, A.; Rongen, H.; Brandenburg, G.; Moeller, R.; Matzerath, J.; Hiller, P.; Halling, H. ReV. Sci. Instrum. 1989, 60, 1943. (14) Infrared Characteristic Group Frequencies; Socrates, G., Ed.; Wiley: New York, 1994. (b) Abramson, S.; Lasperas, M.; Chiche, B. J. Mol. Catal. A 2001, 165, 231. (15) Templin, M.; Wiesner, U.; Spiess, H. W. AdV. Mater. 1997, 9, 814. (16) Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem. ReV. 1995, 95, 1409. (17) Liu, C.; Liu, Z.; Xie, P.; Dai, D.; Zhang, R. Polym. Int. 2000, 49, 509. (b) Lin, Y.; Kumari, P.; Chen, W.; Chung, T. S.; Zhang, R.-B. Polym. Prepr. 1999, 40, 944. (18) Gravel, M.-C.; Zhang, C.; Dinderman, M.; Laine, R. M. Appl. Organomet. Chem. 1999, 13, 329. (19) Feher, F. J.; Terroba, R.; Jin, R.-Z. Chem. Commun. 1999, 24, 2513. (20) Suzuki, H.; Sasaki, H. Polym. Prepr. 2001, 42, 733. (21) Earley, C. W. J. Phys. Chem. 1994, 98, 8693. (22) Sidorov, S. N.; Bronstein, L. M.; Valetsky, P. M.; Hartmann, J.; Coelfen, H.; Schnablegger, H.; Antonietti, M. J. Colloid Interface Sci. 1999, 212, 197. (23) Svergun, D. I. J. Appl. Crystallogr. 1992, 25, 495. (24) Honjo, H.; Ohta, S. Phys. ReV. A 1992, 45, R8332. (b) Zeng, H. C.; Lim, L. C. J. Mater. Res. 1998, 13, 1426. (25) Bernier, W. E.; Bundga, E. G. U.S. Patent Application, US 99-474912 19991228, 2001.

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