Journal Home > Volume 3 , Issue 6

Graphene has been successfully modified with palladium nanoparticles in a facile manner by reducing palladium acetate [Pd(OAc)2] in the present of sodium dodecyl sulfate (SDS), which is used as both surfactant and the reducing agent. The palladium nanoparticle–graphene hybrids (Pd–graphene hybrids) are characterized by high-resolution transmission electron microscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and energy dispersive X-ray spectroscopy. We demonstrate that the Pd–graphene hybrids can act as an efficient catalyst for the Suzuki reaction under aqueous and aerobic conditions, with the reaction reaching completion in as little as 5 min. The influence of the preparation conditions on the catalytic activities of the hybrids is also investigated.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Palladium Nanoparticle–Graphene Hybrids as Active Catalysts for the Suzuki Reaction

Show Author's information Yang LiXiaobin Fan( )Junjie QiJunyi JiShulan WangGuoliang ZhangFengbao Zhang
School of Chemical Engineering and TechnologyTianjin UniversityTianjin300072China

Abstract

Graphene has been successfully modified with palladium nanoparticles in a facile manner by reducing palladium acetate [Pd(OAc)2] in the present of sodium dodecyl sulfate (SDS), which is used as both surfactant and the reducing agent. The palladium nanoparticle–graphene hybrids (Pd–graphene hybrids) are characterized by high-resolution transmission electron microscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and energy dispersive X-ray spectroscopy. We demonstrate that the Pd–graphene hybrids can act as an efficient catalyst for the Suzuki reaction under aqueous and aerobic conditions, with the reaction reaching completion in as little as 5 min. The influence of the preparation conditions on the catalytic activities of the hybrids is also investigated.

Keywords: Graphene, catalyst, hybrids, Pd nanoparticles, Suzuki reaction

References(46)

1

Stankovich, S.; Dikin, D. A.; Dommett, G. H. B.; Kohlhaas, K. M.; Zimney, E. J.; Stach, E. A.; Piner, R. D.; Nguyen, S. T.; Ruoff, R. S. Graphene-based composite materials. Nature 2006, 442, 282–286.

2

Ramanathan, T.; Abdala, A. A.; Stankovich, S.; Dikin, D. A.; Herrera-Alonso, M.; Piner, R. D.; Adamson, D. H.; Schniepp, H. C.; Chen, X.; Ruoff, R. S.; Nguyen, S. T.; Aksay, I. A.; Prud'homme, R. K.; Brinson, L. C. Functionalized graphene sheets for polymer nanocomposites. Nat. Nanotechnol. 2008, 3, 327–331.

3

Meyer, J. C.; Geim, A. K.; Katsnelson, M. I.; Novoselov, K. S.; Booth, T. J.; Roth, S. The structure of suspended graphene sheets. Nature 2007, 446, 60–63.

4

Ponomarenko, L. A.; Schedin, F.; Katsnelson, M. I.; Yang, R.; Hill, E. W.; Novoselov, K. S.; Geim, A. K. Chaotic Dirac billiard in graphene quantum dots. Science 2008, 320, 356–358.

5

Novoselov, K. S.; Jiang, Z.; Zhang, Y.; Morozov, S. V.; Stormer, H. L.; Zeitler, U.; Maan, J. C.; Boebinger, G. S.; Kim, P.; Geim, A. K. Room-temperature quantum Hall effect in graphene. Science 2007, 315, 1379.

6

Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666–669.

7

McAllister, M. J.; Li, J. L.; Adamson, D. H.; Schniepp, H. C.; Abdala, A. A.; Liu, J.; Herrera-Alonso, M.; Milius, D. L.; Car, R.; Prud'homme, R. K.; Akasy, I. A. Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chem. Mater. 2007, 19, 4396–4404.

8

Hassan, H. M. A.; Abdelsayed, V.; Khder, A. E. R. S.; AbouZeid, K. M.; Terner, J.; El-Shall, M. S.; Al-Resayes, S. I.; El-Azhary, A. A. Microwave synthesis of graphene sheets supporting metal nanocrystals in aqueous and organic media. J. Mater. Chem. 2009, 19, 3832–3837.

9

Muszynski, R.; Seger, B.; Kamat, P. V. Decorating graphene sheets with gold nanoparticles. J. Phys. Chem. C 2008, 112, 5263–5266.

10

Stoller, M. D.; Park, S. J.; Zhu, Y. W.; An, J. H.; Ruoff, R. S. Graphene-based ultracapacitors. Nano Lett. 2008, 8, 3498–3502.

11

Zhou, X. Z.; Huang, X.; Qi, X. Y.; Wu, S. X.; Xue, C.; Boey, F. Y. C.; Yan, Q. Y.; Chen, P.; Zhang, H. In situ synthesis of metal nanoparticles on single-layer graphene oxide and reduced graphene oxide surfaces. J. Phys. Chem. C 2009, 113, 10842–10846.

12

Yoo, E.; Okata, T.; Akita, T.; Kohyama, M.; Nakamura, J.; Honma, I. Enhanced electrocatalytic activity of Pt subnanoclusters on graphene nanosheet surface. Nano Lett. 2009, 9, 2255–2259.

13

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.

14

Mastalir, A.; Kiraly, Z.; Patzko, A.; Dekany, I.; L'Argentiere, P. Synthesis and catalytic application of Pd nanoparticles in graphite oxide. Carbon 2008, 46, 1631–1637.

15

Javey, A.; Guo, J.; Wang, Q.; Lundstrom, M.; Dai, H. J. Ballistic carbon nanotube field-effect transistors. Nature 2003, 424, 654–657.

16

Blaser, H. U.; Indolese, A.; Schnyder, A.; Steiner, H.; Studer, M. Supported palladium catalysts for fine chemicals synthesis. J. Mol. Catal. A-Chem. 2001, 173, 3–18.

17

Suzuki, A. Recent advances in the cross-coupling reactions of organoboron derivatives with organic electrophiles, 1995–1998. J. Organomet. Chem. 1999, 576, 147–168.

18

Kantam, M. L.; Roy, M.; Roy, S.; Sreedhar, B.; Madhavendra, S. S.; Choudary, B. M.; De, R. L. Polyaniline supported palladium catalyzed Suzuki–Miyaura cross-coupling of bromo- and chloroarenes in water. Tetrahedron 2007, 63, 8002–8009.

19

Lemo, J.; Heuze, K.; Astruc, D. Efficient and recyclable dendritic Buchwald-type catalyst for the Suzuki reaction. Chem. Commun. 2007, 4351–4353.

20

Ishiyama, T.; Kizaki, H.; Hayashi, T.; Suzuki, A.; Miyaura, N. Palladium-catalyzed carbonylative cross-coupling reaction of arylboronic acids with aryl electrophiles: Synthesis of biaryl ketones. J. Org. Chem. 1998, 63, 4726–4731.

21

Corma, A.; Garcia, H.; Leyva, A. Comparison between polyethylenglycol and imidazolium ionic liquids as solvents for developing a homogeneous and reusable palladium catalytic system for the Suzuki and Sonogashira coupling. Tetrahedron 2005, 61, 9848–9854.

22

Fan, X. B.; Peng, W. C.; Li, Y.; Li, X. Y.; Wang, S. L.; Zhang, G. L.; Zhang, F. B. Deoxygenation of exfoliated graphite oxide under alkaline conditions: A green route to graphene preparation. Adv. Mater. 2008, 20, 4490–4493.

23

Lerf, A.; He, H. Y.; Forster, M.; Klinowski, J. Structure of graphite oxide revisited. J. Phys. Chem. B 1998, 102, 4477–4482.

24

Karousis, N.; Tsotsou, G. E.; Evangelista, F.; Rudolf, P.; Ragoussis, N.; Tagmatarchis, N. Carbon nanotubes decorated with palladium nanoparticles: Synthesis, characterization, and catalytic activity. J. Phys. Chem. C 2008, 112, 13463–13469.

25

Lu, J. S. Effect of surface modifications on the decoration of multi-walled carbon nanotubes with ruthenium nanoparticles. Carbon 2007, 45, 1599–1605.

26

Wang, H.; Bash, R.; Lindsay, S. M.; Lohr, D. Solution AFM studies of human Swi–Snf and its interactions with MMTV DNA and chromatin. Biophys. J. 2005, 89, 3386–3398.

27

Nemec, N.; Tomanek, D.; Cuniberti, G. Contact dependence of carrier injection in carbon nanotubes: An ab initio study. Phys. Rev. Lett. 2006, 96, 076802.

28

Yang, D. X.; Velamakanni, A.; Bozoklu, G.; Park, S. J.; Stoller, M.; Piner, R. D.; Stankovich, S.; Jung, I.; Field, D. A.; Ventrice, C. A.; Ruoff, R. S. Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and micro-Raman spectroscopy. Carbon 2009, 47, 145–152.

29

Jasuja, K.; Berry, V. Implantation and growth of dendritic gold nanostructures on graphene derivatives: Electrical property tailoring and Raman enhancement. ACS Nano 2009, 3, 2358–2366.

30

Lin, Y.; Watson, K. A.; Fallbach, M. J.; Ghose, S.; Smith, J. G.; Delozier, D. M.; Cao, W.; Crooks, R. E.; Connell, J. W. Rapid, solventless, bulk preparation of metal nanoparticle-decorated carbon nanotubes. ACS Nano 2009, 3, 871–884.

31

Tong, L. M.; Li, Z. P.; Zhu, T.; Xu, H. X.; Liu, Z. F. Single gold-nanoparticle-enhanced Raman scattering of individual single-walled carbon nanotubes via atomic force microscope manipulation. J. Phys. Chem. C 2008, 112, 7119–7123.

32

Krasheninnikov, A. V.; Lehtinen, P. O.; Foster, A. S.; Pyykkö, P.; Nieminen, R. M. Embedding transition-metal atoms in graphene: Structure, bonding, and magnetism. Phys. Rev. Lett. 2009, 102, 126807.

33

Okamoto, Y. Density-functional calculations of icosahedral M13 (M = Pt and Au) clusters on graphene sheets and flakes. Chem. Phys. Lett. 2006, 420, 382–386.

34

Kudin, K. N.; Ozbas, B.; Schniepp, H. C.; Prud'homme, R. K.; Aksay, I. A.; Car, R. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett. 2008, 8, 36–41.

35

Zeng, H. B.; Cai, W. P.; Li, Y.; Hu, J. L.; Liu, P. S. Composition/structural evolution and optical properties of ZnO/Zn nanoparticles by laser ablation in liquid media. J. Phys. Chem. B 2005, 109, 18260–18266.

36

Mafune, F.; Kohno, J.; Takeda, Y.; Kondow, T. Formation and size control of silver nanoparticles by laser ablation in aqueous solution. J. Phys. Chem. B 2000, 104, 9111–9117.

37

Santra, A. K.; Goodman, D. W. Oxide-supported metal clusters: Models for heterogeneous catalysts. J. Phys. -Condens. Mat. 2003, 15, R31–R62.

38

Turner, M.; Golovko, V. B.; Vaughan, O. P. H.; Abdulkin, P.; Berenguer-Murcia, A.; Tikhov, M. S.; Johnson, B. F. G.; Lambert, R. M. Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters. Nature 2008, 454, 981–983.

39

Zapf, A.; Ehrentraut, A.; Beller, M. A new highly efficient catalyst system for the coupling of nonactivated and deactivated aryl chlorides with arylboronic acids. Angew. Chem. Int. Edit. 2000, 39, 4153–4155.

DOI
40

Littke, A. F.; Dai, C. Y.; Fu, G. C. Versatile catalysts for the Suzuki cross-coupling of arylboronic acids with aryl and vinyl halides and triflates under mild conditions. J. Am. Chem. Soc. 2000, 122, 4020–4028.

41

Goossen, L. J.; Ghosh, K. Palladium-catalyzed synthesis of aryl ketones from boronic acids and carboxylic acids or anhydrides. Angew. Chem. Int. Edit. 2001, 40, 3458–3460.

DOI
42

Xin, B. W.; Zhang, Y. H. Cheng, K. The surfactant-promoted cross-coupling reactions of arylboronic acids with carboxylic anhydrides or acyl chlorides in water. Synthesis–Stuttgart 2007, 1970–1978.

43

Harada, T.; Ikeda, S.; Miyazaki, M.; Sakata, T.; Mori, H.; Matsumura, M. A simple method for preparing highly active palladium catalysts loaded on various carbon supports for liquid-phase oxidation and hydrogenation reactions. J. Mol. Catal. A-Chem. 2007, 268, 59–64.

44

Diallo, A. K.; Ornelas, C.; Salmon, L.; Aranzaes, J. R.; 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. Edit. 2007, 46, 8644–8648.

45

Corma, A.; Garcia, H.; Leyva, A. Catalytic activity of palladium supported on single wall carbon nanotubes compared to palladium supported on activated carbon. Study of the Heck and Suzuki couplings, aerobic alcohol oxidation and selective hydrogenation. J. Mol. Catal. A-Chem. 2005, 230, 97–105.

46

Alonso, F.; Beletskaya, I. P.; Yus, M. Non-conventional methodologies for transition-metal catalysed carbon–carbon coupling: A critical overview. Part 2: The Suzuki reaction. Tetrahedron 2008, 64, 3047–3101.

File
nr-3-6-429_ESM.pdf (1.3 MB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 18 January 2010
Revised: 12 April 2010
Accepted: 22 April 2010
Published: 01 June 2010
Issue date: June 2010

Copyright

© The Author(s) 2010

Acknowledgements

Acknowledgements

The authors would like to acknowledge the support of this work by the National Natural Science Foundation of China (20776095) and the Programme of Introducing Talents of Discipline to Universities (No. B06006).

Rights and permissions

This article is distributed under the terms of the Creative Commons Attribution Noncommercial License which permits any noncommercial use, distribution, and reproduction in any medium, provided the original author(s) and source are credited.

Return