Skip to main content
SpringerLink
Log in

Pd embedded in porous carbon (Pd@CMK-3) as an active catalyst for Suzuki reactions: Accelerating mass transfer to enhance the reaction rate

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Heterogeneous catalysts are promising candidates for use in organic reactions due to their advantages in separation, recovery, and environment compatibility. In this work, an active porous catalyst denoted as Pd embedded in porous carbon (Pd@CMK-3) has been prepared by a strategy involving immersion, ammoniahydrolysis, and heating procedures. Detailed characterization of the catalyst revealed that Pd(0) and Pd(II) species co-exist and were embedded in the matrix of the porous carbon (CMK-3). The as-prepared catalyst has shown high activity toward Suzuki reactions. Importantly, if the reaction mixture was homogenized by two minutes of ultrasonication rather than magnetic stirring before heating, the resistance to mass transfer in the pore channels was significantly reduced. As a result, the reactions proceeded more rapidly and a four-fold increase in the turnover frequency (TOF) could be obtained. When the ultrasonication was employed throughout the entire reaction process, the conversion could also exceed 90% even without the protection of inert gas, and although the reaction temperature was lowered to 30 °C. This work provides a method for fabricating highly active porous carbon encapsulated Pd catalysts for Suzuki reactions and proves that the problem of mass transfer in porous catalysts can be conveniently resolved by ultrasonication without any chemical modification being necessary.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 1995, 95, 2457–2483.

    Article  Google Scholar 

  2. Yin, L.; Liebscher, J. Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts. Chem. Rev. 2007, 107, 133–173.

    Article  Google Scholar 

  3. Martin, R.; Buchwald, S. L. Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions employing dialkylbiaryl phosphine ligands. Acc. Chem. Res. 2008, 41, 1461–1473.

    Article  Google Scholar 

  4. Altenhoff, G.; Goddard, R.; Lehmann, C. W.; Glorius, F. An N-heterocyclic carbene ligand with flexible steric bulk allows Suzuki cross-coupling of sterically hindered aryl chlorides at room temperature. Angew. Chem. Int. Ed. 2003, 42, 3690–3693.

    Article  Google Scholar 

  5. Herrmann, W. A.; Öfele, K.; Schneider, S. K.; Herdtweck, E.; Hoffmann, S. D. A carbocyclic carbene as an efficient catalyst ligand for C-C coupling reactions. Angew. Chem. Int. Ed. 2006, 45, 3859–3862.

    Article  Google Scholar 

  6. Uozumi, Y.; Matsuura, Y.; Arakawa, T.; Yamada, Y. Asymmetric Suzuki-Miyaura coupling in water with a chiral palladium catalyst supported on an amphiphilic resin. Angew. Chem. Int. Ed. 2009, 121, 2746–2748.

    Article  Google Scholar 

  7. Snelders, D. J.; van Koten, G.; Klein Gebbink, R. J. Hexacationic dendriphos ligands in the Pd-catalyzed Suzuki-Miyaura cross-coupling reaction: Scope and mechanistic studies. J. Am. Chem. Soc. 2009, 131, 11407–11416.

    Article  Google Scholar 

  8. Tang, W.; Capacci, A. G.; Wei, X.; Li, W.; White, A.; Patel, N. D.; Savoie, J.; Gao, J. J.; Rodriguez, S.; Qu, B. et al. A general and special catalyst for Suzuki-Miyaura coupling Processes. Angew. Chem. Int. Ed. 2010, 49, 5879–5883.

    Article  Google Scholar 

  9. Marck, G.; Villiger, A.; Buchecker, R. Aryl couplings with heterogeneous palladium catalysts. Tetrahedron Lett. 1994, 35, 3277–3280.

    Article  Google Scholar 

  10. Wu, Y.; Wang, D.; Zhao, P.; Niu, Z.; Peng, Q.; Li, Y. D. Monodispersed Pd-Ni Nanoparticles: Composition control synthesis and catalytic properties in the Miyaura-Suzuki reaction. Inorg. Chem. 2011, 50, 2046–2048.

    Article  Google Scholar 

  11. Conlon, D. A.; Pipik, B.; Ferdinand, S.; LeBlond, C. R.; Sowa, J. R.; Izzo, B.; Collins, P.; Ho, G. J.; Williams, J. M.; Shi, Y. J. Suzuki-Miyaura cross-coupling with quasi-heterogeneous palladium. Adv. Synth. Catl. 2003, 345, 931–935.

    Article  Google Scholar 

  12. Mori, Y.; Seki, M. Pd(OH)2/C (Pearlman’s catalyst): A highly active catalyst for Fukuyama, Sonogashira, and Suzuki coupling reactions. J. Org. Chem. 2003, 68, 1571–1574.

    Article  Google Scholar 

  13. Maegawa, T.; Kitamura, Y.; Sako, S.; Udzu, T.; Sakurai, A.; Tanaka, A.; Kobayashi, Y.; Endo, K.; Bora, U.; Kurita, T. Heterogeneous Pd/C-catalyzed ligand-free, room-temperature Suzuki-Miyaura coupling reactions in aqueous media. Chem. Eur. J. 2007, 13, 5937–5943.

    Article  Google Scholar 

  14. Artok, L.; Bulut, H. Heterogeneous Suzuki reactions catalyzed by Pd(0)-Y zeolite. Tetrahedron Lett. 2004, 45, 3881–3884.

    Article  Google Scholar 

  15. Crudden, C. M.; Sateesh, M.; Lewis, R. Mercaptopropyl-modified mesoporous silica: A remarkable support for the preparation of a reusable, heterogeneous palladium catalyst for coupling reactions. J. Am. Chem. Soc. 2005, 127, 10045–10050.

    Article  Google Scholar 

  16. MacQuarrie, S.; Nohair, B.; Horton, J. H.; Kaliaguine, S.; Crudden, C. M. Functionalized mesostructured silicas as supports for palladium catalysts: Effect of pore structure and collapse on catalytic activity in the Suzuki-Miyaura reaction. J. Phys. Chem. C 2009, 114, 57–64.

    Article  Google Scholar 

  17. Chen, Z.; Cui, Z. M.; Li, P.; Cao, C. Y.; Hong, Y. L.; Wu, Z. Y.; Song, W. G. Diffusion induced reactant shape selectivity inside mesoporous pores of Pd@meso-SiO2 nanoreactor in Suzuki coupling reactions. J. Phys. Chem. C 2012, 116, 14986–14991.

    Article  Google Scholar 

  18. Wan, Y.; Wang, H.; Zhao, Q.; Klingstedt, M.; Terasaki, O.; Zhao, D. Ordered mesoporous Pd/silica-carbon as a highly active heterogeneous catalyst for coupling reaction of chlorobenzene in aqueous media. J. Am. Chem. Soc. 2009, 131, 4541–4550.

    Article  Google Scholar 

  19. Choi, M.; Lee, D. H.; Na, K.; Yu, B. W.; Ryoo, R. High catalytic activity of palladium (II)-exchanged mesoporous sodalite and NaA zeolite for bulky aryl coupling reactions: Reusability under aerobic conditions. Angew. Chem. Int. Ed. 2009, 48, 3673–3676.

    Article  Google Scholar 

  20. Yuan, B.; Pan, Y.; Li, Y.; Yin, B.; Jiang, H. A highly active heterogeneous palladium catalyst for the Suzuki-Miyaura and Ullmann coupling reactions of aryl chlorides in aqueous media. Angew. Chem. Int. Ed. 2010, 49, 4054–4058.

    Article  Google Scholar 

  21. Llabrés i Xamena, F. X.; Abad, A.; Corma, A.; Garcia, H. MOFs as catalysts: Activity, reusability and shape-selectivity of a Pd-containing MOF. J. Catal. 2007, 250, 294–298.

    Article  Google Scholar 

  22. Mackintosh, H. J.; Budd, P. M.; McKeown, N. B. Catalysis by microporous phthalocyanine and porphyrin network polymers. J. Mater. Chem. 2008, 18, 573–578.

    Article  Google Scholar 

  23. Li, B.; Guan, Z.; Wang, W.; Yang, X.; Hu, J.; Tan, B.; Li, T. Highly dispersed Pd catalyst locked in knitting aryl network polymers for Suzuki-Miyaura coupling reactions of aryl chlorides in aqueous media. Adv. Mater. 2012, 24, 3390–3395.

    Article  Google Scholar 

  24. Chen, X.; Hou, Y.; Wang, H.; Cao, Y.; He, J. Facile deposition of Pd nanoparticles on carbon nanotube microparticles and their catalytic activity for Suzuki coupling reactions. J. Phys. Chem. C 2008, 112, 8172–8176.

    Article  Google Scholar 

  25. Kitamura, Y.; Sako, S.; Udzu, T.; Tsutsui, A.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Ligand-free Pd/C-catalyzed Suzuki-Miyaura coupling reaction for the synthesis of heterobiaryl derivatives. Chem. Commun. 2007, 47, 5069–5071.

    Article  Google Scholar 

  26. Choi, H. R.; Woo, H.; Jang, S.; Cheon, J. Y.; Kim, C.; Park, J.; Park, K. H.; Joo, S. H. Ordered mesoporous carbon supported colloidal Pd nanoparticle based model catalysts for Suzuki coupling reactions: Impact of organic capping agents. ChemCatChem 2012, 4, 1587–1594.

    Article  Google Scholar 

  27. Wu, Z.; Li, W.; Webley, P. A.; Zhao, D. Y. General and controllable synthesis of novel mesoporous magnetic iron oxide@carbon encapsulates for efficient arsenic removal. Adv. Mater. 2012, 24, 485–491.

    Article  Google Scholar 

  28. Scheuermann, G. M.; Rumi, L.; Steurer, P.; Bannwarth, W.; Mulhaupt, R. Palladium nanoparticles on graphite oxide and its functionalized graphene derivatives as highly active catalysts for the Suzuki-Miyaura coupling reaction. J. Am. Chem. Soc. 2009, 131, 8262–8270.

    Article  Google Scholar 

  29. Sahu, S. C.; Samantara, A. K.; Dash, A.; Juluri, R. R.; Sahu, R. K.; Mishra, B. K.; Jena, B. K. Graphene-induced Pd nanodendrites: A high performance hybrid nano-electrocatalyst. Nano Res. 2013, 6, 635–643.

    Article  Google Scholar 

  30. Metin, Ö.; Ho, S. F.; Alp, C.; Can, H.; Mankin, M. N.; Gültekin, M. S.; Chi, M.; Sun, S. Ni/Pd core/shell nanoparticles supported on graphene as a highly active and reusable catalyst for Suzuki-Miyaura cross-coupling reaction. Nano Res. 2013, 6, 10–18.

    Article  Google Scholar 

  31. Zhi, J.; Song, D.; Li, Z.; Lei, X.; Hu, A. Palladium nanoparticles in carbon thin film-lined SBA-15 nanoreactors: Efficient heterogeneous catalysts for Suzuki-Miyaura cross coupling reaction in aqueous media. Chem. Commun. 2011, 47, 10707–10709.

    Article  Google Scholar 

  32. Cravotto, G.; Cintas, P. Power ultrasound in organic synthesis: Moving cavitational chemistry from academia to innovative and large-scale applications. Chem. Soc. Rev. 2006, 35, 180–196.

    Article  Google Scholar 

  33. Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 1998, 279, 548–552.

    Article  Google Scholar 

  34. Jun, S.; Joo, S. H.; Ryoo, R.; Kruk, M.; Jaroniec, M.; Liu, Z.; Ohsuna, T.; Terasaki, O. Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure. J. Am. Chem. Soc. 2000, 122, 10712–10713.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Zhejiang Key Laboratory of Carbon Materials, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, 325027, China

    Zhencai Wang, Wei Chen, Zhenliang Han, Jie Zhu, Na Lu, Yun Yang, Dekun Ma & Shaoming Huang

  2. ARC Centre of Excellence for Functional Nanomaterials, Institute for Frontier Materials, Deakin University, Waurn Ponds, Victoria, 3216, Australia

    Ying Chen

Authors
  1. Zhencai Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wei Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhenliang Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jie Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Na Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yun Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Dekun Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ying Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Shaoming Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Wei Chen or Shaoming Huang.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Z., Chen, W., Han, Z. et al. Pd embedded in porous carbon (Pd@CMK-3) as an active catalyst for Suzuki reactions: Accelerating mass transfer to enhance the reaction rate. Nano Res. 7, 1254–1262 (2014). https://doi.org/10.1007/s12274-014-0488-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-014-0488-x

Keywords

Search

Navigation