Abstract
The effects of the ligand used for fabricating palladium (Pd)-incorporated porous polymer composites on their catalytic performances were examined from the perspective of catalysis sustainability. To perform this research, poly(amidoamine) (PAMAM) dendrimers, which were generation zero (G0) and higher, up to G6, the breakdown structure of G0 (that is, the half (G0h) and quarter (G0q)) and a typical small molecule (that is, N,N-dimethyl ethylenediamine (DMEn)) were utilized as ligands. The catalytic performances of the polymer composites were investigated using the aqueous Suzuki–Miyaura carbon cross-coupling reaction as a model reaction. Concerning the efficiency, recyclability and Pd-leaching behavior of the catalytic reaction, polymer composites that were fabricated with PAMAM dendrimers (that is, G1 and higher generations) proved to possess the potential for application as sustainable heterogeneous catalysts.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Scott, R. W. J., Wilson, O. M . & Crooks, R. M. Synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles. J. Phys. Chem. B 109, 692–704 (2005).
Chandler, B. D . & Gilbertson, J. D. Dendrimer-encapsulated bimetallic nanoparticles: synthesis, characterization, and applications to homogeneous and heterogeneous catalysis. Top. Organomet. Chem. 20, 97–120 (2006).
Astruc, D., Boisselier, E . & Ornelas, C. Dendrimers designed for functions: from physical, photophysical, and supramolecular properties to applications in sensing, catalysis, molecular electronics, photonics, and nanomedicine. Chem. Rev. 110, 1857–1959 (2010).
Bronstein, L. M . & Shifrina, Z. B. Dendrimers as encapsulating, stabilizing, or directing agents for inorganic nanoparticles. Chem. Rev. 111, 5301–5344 (2011).
Myers, V. S., Weir, M. G., Carino, E. V., Yancey, D. F., Pande, S . & Crooks, R. M. Dendrimer-encapsulated nanoparticles: new synthetic and characterization methods and catalytic applications. Chem. Sci. 2, 1632–1646 (2011).
Scott, R. W. J., Wilson, O. M . & Crooks, R. M. Titania-supported Au and Pd composites synthesized from dendrimer-encapsulated metal nanoparticle precursors. Chem. Mater. 16, 5682–5688 (2004).
Kahat, T., Goren, K . & Portnoy, M. Dendrons on insoluble supports: synthesis and applications. New J. Chem. 31, 1218–1242 (2007).
Scott, R. W. J., Sivadinarayana, C., Wilson, O. M., Yan, Z., Goodman, D. W . & Crooks, R. M. Titania-supported PdAu bimetallic catalysts prepared from dendrimer-encapsulated nanoparticle precursors. J. Am. Chem. Soc. 127, 1380–1381 (2005).
Gil-Moltó, J., Karlström, S . & Nájera, C. Di(2-pyridyl)methylamine–palladium dichloride complex covalently anchored to a styrene-maleic anhydride co-polymer as recoverable catalyst for C–C cross-coupling reactions in water. Tetrahedron 61, 12168–12176 (2005).
Inasaki, T., Ueno, M., Miyamoto, S . & Kobayashi, S. Polymer-incarcerated palladium with active phosphine as recoverable and reusable Pd catalyst for the amination of aryl chlorides. Synlett. 20, 3209–3213 (2007).
Ranganath, K. V. S., Kloesges, J., Schäfer, A. H . & Glorius, F. Asymmetric nanocatalysis: N-heterocyclic carbenes as chiral modifiers of Fe3O4/Pd nanoparticles. Angew. Chem. Int. Ed. 49, 7786–7789 (2010).
Kong, L., Lu, X., Bian, X., Zhang, W . & Wang, C. Constructing carbon-coated Fe3O4 microspheres as antiacid and magnetic support for palladium nanoparticles for catalytic applications. ACS Appl. Mater. Interfaces 1, 35–42 (2011).
Jin, M.-J . & Lee, D.-H. A practical heterogeneous catalyst for the Suzuki, Sonogashira, and Stille coupling reactions of unreactive aryl chlorides. Angew. Chem. Int. Ed. 49, 1119–1122 (2010).
Diallo, A. K., Ornelas, C., Salmon, L., Ruiz Aranzaes, J . & Astruc, D. "Homeopathic" catalytic activity and atom-leaching mechanism in Miyaura-Suzuki reactions under ambient conditions with precise dendrimer-stabilized Pd nanoparticles. Angew. Chem. Int. Ed. 46, 8644–8648 (2007).
Esumi, K., Isono, R . & Yoshimura, T. Preparation of PAMAM- and PPI-metal (silver, platinum, and palladium) nanocomposites and their catalytic activities for reduction of 4-nitrophenol. Langmuir 20, 237–243 (2004).
Gaikwad, A. V., Holuigue, A., Thathagar, M. B., ten Elshof, J. E . & Rothenberg, G. Ion- and atom-leaching mechanisms from palladium nanoparticles in cross-coupling reactions. Chem. Eur. J. 13, 6908–6913 (2007).
Fang, P.-P., Jutand, A., Tian, Z.-Q . & Amatore, C. Au-Pd core-shell nanoparticles catalyze Suzuki–Miyaura reactions in water through Pd leaching. Angew. Chem. Int. Ed. 50, 12184–12188 (2011).
Ogasawara, S . & Kato, S. Palladium nanoparticles captured in microporous polymers: a tailor-made catalyst for heterogeneous carbon cross-coupling reactions. J. Am. Chem. Soc. 132, 4608–4613 (2010).
Yang, Y., Ogasawara, S., Li, G . & Kato, S. Water compatible Pd nanoparticle catalysts supported on microporous polymers: their controllable microstructure and extremely low Pd-leaching behaviour. J. Mater. Chem. A 1, 3700–3705 (2013).
Yang, Y., Ogasawara, S., Li, G . & Kato, S. Critical effects of ligand integration in creating palladium-incorporated porous polymer composites. J. Phys. Chem. C 118, 5872–5880 (2014).
O’Connor, N. A., Paisner, D. A., Huryn, D . & Shea, K. J. Screening of 5-HT1A receptor antagonists using molecularly imprinted polymers. J. Am. Chem. Soc. 129, 1680–1689 (2007).
Urraca, J. L., Aureliano, C. S. A., Schillinger, E., Esselmann, H., Wiltfang, J . & Sellergren, B. Polymeric complements to the Alzheimer's Disease biomarker β-amyloid isoforms A β 1-40 and A β 1-42 for blood serum analysis under denaturing conditions. J. Am. Chem. Soc. 133, 9220–9223 (2011).
Hasegawa, G., Kanamori, K., Nakanishi, K . & Yamago, S. Fabrication of highly crosslinked methacrylate-based polymer monoliths with well-defined macropores via living radical polymerization. Polymer 52, 4644–4647 (2011).
Nakao, Y. Preparation and characterisation of noble metal solid sols in poly(methyl methacrylate). J. Chem. Soc. Chem. Commun. 826–828 (1993).
Yanagihara, N., Uchida, K., Wakabayashi, M., Uetake, Y . & Hara, T. Effect of radical initiators on the size and formation of silver nanoclusters in poly(methyl methacrylate). Langmuir 15, 3038–3041 (1999).
Zhang, Z . & Han, M. One-step preparation of size-selected and well-dispersed silver nanocrystals in polyacrylonitrile by simultaneous reduction and polymerization. J. Mater. Chem. 13, 641–643 (2003).
Aymonier, C., Bortzmeyer, D., Thomann, R . & Mülhaupt, R. Poly(methyl methacrylate)/palladium nanocomposites: synthesis and characterization of the morphological, thermomechanical, and thermal properties. Chem. Mater. 15, 4874–4878 (2003).
Gatard, S., Liang, L., Salmon, L., Ruiz, J., Astruc, D . & Bouquillon, S. Water-soluble glycodendrimers: synthesis and stabilization of catalytically active Pd and Pt nanoparticles. Tetrahedron Lett. 52, 1842–1846 (2011).
Ornela, C., Ruiz, J., Salmon, L . & Astruc, D. “Click” dendrimers: synthesis, redox sensing of Pd(OAc)2, and remarkable catalytic hydrogenation activity of precise Pd nanoparticles stabilized by 1,2,3-triazole-containing dendrimers. Chem. Eur. J. 14, 50–64 (2008).
Astruc, D., Ornelas, C., Diallo, A. K . & Ruiz, J. Extremely efficient catalysis of carbon-carbon bond formation using click dendrimer-stabilized palladium nanoparticles. Molecules 5, 4947–4960 (2010).
Zhao, M., Sun, L . & Crooks, R. M. Preparation of Cu nanoclusters within dendrimer templates. J. Am. Chem. Soc. 120, 4877–4878 (1998).
Balogh, L . & Tomalia, D. A. Poly(amidoamine) dendrimer-templated nanocomposites. 1. synthesis of zerovalent copper nanoclusters. J. Am. Chem. Soc. 120, 7355–7356 (1998).
Esumi, K., Suzuki, A., Aihara, N., Usui, K . & Torigoe, K. Preparation of gold colloids with UV irradiation using dendrimers as stabilizer. Langmuir 14, 3157–3159 (1998).
Yamamoto, K., Imaoka, T., Chun, W.-J., Enoki, O., Katoh, H., Takenaga, M . & Sonoi, A. Size-specific catalytic activity of platinum clusters enhances oxygen reduction reactions. Nat. Chem. 1, 397–402 (2009).
Kibata, T., Mitsudome, T., Mizugaki, T., Jitsukawa, K . & Kaneda, K. Investigation of size-dependent properties of sub-nanometer palladium clusters encapsulated within a polyamine dendrimer. Chem. Commun. 49, 167–169 (2013).
Tomalia, D. A., Baker, H., Dewald, J., Hall, M., Kallos, G., Martin, S., Roeck, J., Ryder, J . & Smith, P. A new class of polymers: starburst-dendritic macromolecules. Polym. J. 17, 117–132 (1985).
Heigl, N., Bachmann, S., Petter, C.H., Marchetti-Deschmann, M., Allmaier, G., Bonn, G.K . & Huck, C.W. Near-infrared spectroscopic study on guest-host interactions among G0-G7 amine-terminated poly(amidoamine) dendrimers and porous silica materials for simultaneously determining the molecular weight and particle diameter by multivariate calibration techniques. Anal. Chem. 81, 5655–5662 (2009).
Agostini, G., Pellegrini, R., Leofanti, G., Bertinetti, L., Bertarione, S., Groppo, E., Zecchina, A . & Lamberti, C. Determination of the particle size, available surface area, and nature of exposed sites for silica-alumina-supported Pd nanoparticles: a multitechnical approach. J. Phys. Chem. C 113, 10485–10492 (2009).
Agostini, G., Groppo, E., Piovano, A., Pellegrini, R., Leofanti, G . & Lamberti, C. Preparation of supported Pd catalysts: from the Pd precursor solution to the deposited Pd2+ phase. Langmuir 26, 11204–11211 (2010).
Yamada, Y. M. A., Sarkar, S. M . & Uozumi, Y. Self-assembled poly(imidazole-palladium): highly active, reusable catalyst at parts per million to parts per billion levels. J. Am. Chem. Soc. 134, 3190–3198 (2012).
Ornelas, C., Ruiz, J., Salmon, L . & Astruc, D. Sulphonated “click” dendrimer-stabilized palladium nanoparticles as highly efficient catalysts for olefin hydrogenation and Suzuki coupling reactions under ambient conditions in aqueous media. Adv. Synth. Catal. 350, 837–845 (2008).
Mejías, N., Pleixats, R., Shafir, A., Medio-Simón, M . & Asensio, G. Water-soluble palladium nanoparticles: click synthesis and applications as a recyclable catalyst in Suzuki cross-couplings in aqueous media. Eur. J. Org. Chem. 2010, 5090–5099 (2010).
Fujii, S., Matsuzawa, S., Nakamura, Y., Ohtaka, A., Teratani, T., Akamatsu, K., Tsuruoka, T . & Nawafune, H. Synthesis and characterization of polypyrrole-palladium nanocomposite-coated latex particles and their use as a catalyst for Suzuki coupling reaction in aqueous media. Langmuir 26, 6230–6239 (2010).
Balanta, A., Godard, C . & Claver, C. Pd nanoparticles for C-C coupling reactions. Chem. Soc. Rev. 40, 4973–4985 (2011).
Astruc, D. Palladium nanoparticles as efficient green homogeneous and heterogeneous carbon-carbon coupling precatalysts: a unifying view. Inorg. Chem. 46, 1884–1894 (2007).
Cho, J. K., Najman, R., Dean, T. W., Ichihara, O., Muller, C . & Bradley, M. Captured and cross-linked palladium nanoparticles. J. Am. Chem. Soc. 128, 6276–6277 (2006).
Shin, J. Y., Lee, B. S., Jung, Y., Kim, S. J . & Lee, S. Palladium nanoparticles captured onto spherical silica particles using a urea cross-linked imidazolium molecular band. Chem. Commun. 2007, 5238–5240 (2007).
Okamoto, K., Akiyama, R., Yoshida, H., Yoshida, T . & Kobayashi, S. Formation of nanoarchitectures including subnanometer palladium clusters and their use as highly active catalysts. J. Am. Chem. Soc. 127, 2125–2135 (2005).
Wang, S., Zhao, Q., Wei, H., Wang, J.-Q., Cho, M., Cho, H. S., Terasaki, O . & Wan, Y. Aggregation-free gold nanoparticles in ordered mesoporous carbons: toward highly active and stable heterogeneous catalysts. J. Am. Chem. Soc. 135, 11849–11860 (2013).
GC analysis for the filtrates indicated that the water-insoluble substances and the reaction product could also be filtered out completely
Davies, I. W., Matty, L., Hughes, D. L . & Reider, P. J. Are heterogeneous catalysts precursors to homogeneous catalysts? J. Am. Chem. Soc. 123, 10139–10140 (2001).
Cassol, C. C., Umpierre, A. P., Machado, G., Wolke, S. I . & Dupont, J. The role of Pd nanoparticles in ionic liquid in the Heck reaction. J. Am. Chem. Soc. 127, 3298–3299 (2005).
Phan, N. T. S., Van der Sluys, M . & Jones, C. W. On the nature of the active species in palladium catalyzed Mizoroki-Heck and Suzuki-Miyaura couplings-homogeneous or heterogeneous catalysis, a critical review. Adv. Synth. Catal. 348, 609–679 (2006).
Durand, J., Teuma, E . & Gómez, M. An overview of palladium nanocatalysts: surface and molecular reactivity. Eur. J. Inorg. Chem. 2008, 3577–3586 (2008).
de Vries, J. G. A unifying mechanism for all high-temperature Heck reactions. The role of palladium colloids and anionic species. Dalton Trans. 2006, 421–429 (2006).
Bernechea, M., de Jesús, E., López-Mardomingo, C . & Terreros, P. Dendrimer-encapsulated Pd nanoparticles versus palladium acetate as catalytic precursors in the Stille reaction in water. Inorg. Chem. 48, 4491–4496 (2009).
Acknowledgements
Some of the transmission electron microscopy (TEM) images were obtained at the Graduate School of Materials Science, Nara Institute of Science and Technology, with the support of Kyoto-Advanced Nanotechnology Network. We thank Professor Atsushi Ikeda for helpful discussions. We also thank Dr Masafumi Uota for helpful discussions and technical support. We gratefully acknowledge analytical support from the Analysis Center at the DIC Corporation. This research was partially supported by a Grant-in-Aid for Scientific Research (C) (No. 23550172) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.
Author information
Authors and Affiliations
Corresponding author
Additional information
Supplementary Information accompanies the paper on Polymer Journal website
Supplementary information
Rights and permissions
About this article
Cite this article
Yang, Y., Ogasawara, S., Li, G. et al. Dendrimer-stabilized Pd polymer composites: drastic suppression of Pd leaching and fine catalysis sustainability. Polym J 47, 340–347 (2015). https://doi.org/10.1038/pj.2014.133
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2014.133
This article is cited by
-
Visualization of Nanomechanical Properties of Polymer Composites Using Atomic Force Microscopy
Polymer Journal (2023)
-
Preparation of metal-polymer nanocomposites by chemical reduction of metal ions: functions of polymer matrices
Journal of Polymer Research (2018)
-
Thermo-responsive Ruthenium Dendrimer-based Catalysts for Hydrogenation of the Aromatic Compounds and Phenols
Journal of Inorganic and Organometallic Polymers and Materials (2016)
