Polyvinylpyrrolidone - Reduced Graphene Oxide - Pd Nanoparticles as an Efficient Nanocomposite for Catalysis Applications in Cross-Coupling Reactions

*Hany A. Elazab scopus  -  1Department of Chemical Engineering, Faculty of Engineering, The British University in Egypt, Egypt
Tamer T. El-Idreesy  -  Department of Chemistry, Faculty of Science, Cairo University, Egypt
Received: 23 Oct 2018; Revised: 14 Mar 2019; Accepted: 20 Mar 2019; Published: 1 Dec 2019; Available online: 30 Sep 2019.
Open Access Copyright (c) 2019 Bulletin of Chemical Reaction Engineering & Catalysis
License URL: http://creativecommons.org/licenses/by-sa/4.0

Citation Format:
Cover Image

This paper reported a scientific approach adopting microwave-assisted synthesis as a synthetic route for preparing highly active palladium nanoparticles stabilized by polyvinylpyrrolidone (Pd/PVP) and supported on reduced Graphene oxide (rGO) as a highly active catalyst used for Suzuki, Heck, and Sonogashira cross coupling reactions with remarkable turnover number (6500) and turnover frequency of 78000 h-1. Pd/PVP nanoparticles supported on reduced Graphene oxide nanosheets (Pd-PVP/rGO) showed an outstanding performance through high catalytic activity towards cross coupling reactions. A simple, reproducible, and reliable method was used to prepare this efficient catalyst using microwave irradiation synthetic conditions. The synthesis approach requires simultaneous reduction of palladium and in the presence of Gaphene oxide (GO) nanosheets using ethylene glycol as a solvent and also as a strong reducing agent. The highly active and recyclable catalyst has so many advantages including the use of mild reaction conditions, short reaction times in an environmentally benign solvent system. Moreover, the prepared catalyst could be recycled for up to five times with nearly the same high catalytic activity. Furthermore, the high catalytic activity and recyclability of the prepared catalyst are due to the strong catalyst-support interaction. The defect sites in the reduced Graphene oxide (rGO) act as nucleation centers that enable anchoring of both Pd/PVP nanoparticles and hence, minimize the possibility of agglomeration which leads to a severe decrease in the catalytic activity. Copyright © 2019 BCREC Group. All rights reserved


Keywords: Graphene; Cross-Coupling; Microwave–assisted synthesis; Heterogeneous catalysis; Catalyst recycling

Article Metrics:

  1. Chen, S., Cheng, B., Ding, C. (2006). Synthesis and Characterization of Poly(vinyl pyrrolidone)/Reduced Graphene Oxide Nanocomposite. Journal of Macromolecular Science, Part B, 54(4): 481-491.
  2. De Souza, A.L.F. (2008). Microwave- and ultrasound-assisted Suzuki Miyaura cross-coupling reactions catalyzed by Pd/PVP. Tetrahedron Letters, 49(24): 3895-3898.
  3. Durap, F. (2009). New route to synthesis of PVP stabilized palladium(0) nanoclusters and their enhanced catalytic activity in Heck and Suzuki cross coupling reactions. Applied Organometallic Chemistry, 23(12): 498-503.
  4. Gniewek, A. (2005). Pd-PVP colloid as catalyst for Heck and carbonylation reactions: TEM and XPS studies. Journal of Catalysis, 229(2): 332-343.
  5. Ananikov, V.P. (2007). New approach for size- and shape-controlled preparation of pd nanoparticles with organic ligands. Synthesis and application in catalysis, Journal of the American Chemical Society, 129(23): 7252-7260.
  6. Ashfield, L. (2007). Reductive car-bonylation - an efficient and practical catalytic route for the conversion of aryl halides to aldehydes. Organic Process Research & Development, 11(1): 39-43.
  7. Guillen, E. (2009). Pd-activated carbon catalysts for hydrogenation and Suzuki reactions. Applied Catalysis A: General, 368(1-2): 113-120.
  8. Karousis, N. (2008). Carbon nanotubes decorated with palladium nanoparticles: Synthesis, characterization, and catalytic activity. Journal of Physical Chemistry C, 112(35): 13463-13469.
  9. Leonhardt, S.E.S. (2006). Chitosan as a support for heterogeneous Pd catalysts in liquid phase catalysis. Applied Catalysis A: General, 379(1-2): 30-37.
  10. Li, Y. (2006). Palladium nanoparticle-graphene hybrids as active catalysts for the Suzuki reaction. Nano Research, 3(6): 429-437.
  11. Elazab, H. (2014). Microwave-assisted synthesis of Pd nanoparticles supported on FeO, CoO, and Ni(OH) nanoplates and catalysis application for CO oxidation. Journal of Nanoparticle Research, 16(7): 1-11.
  12. Elazab, H. (2017). The Effect of Graphene on Catalytic Performance of Palladium Nanoparticles Decorated with FeO, CoO, and Ni (OH): Potential Efficient Catalysts used for Suzuki Cross-Coupling. Catalysis Letters, 147(6): 1510-1522.
  13. Elazab, H.A. (2017). The continuous synthesis of Pd supported on Fe3O4 nanoparticles: A highly effective and magnetic catalyst for CO oxidation. Green Processing and Synthesis, 6(4): 413-424.
  14. Elazab, H.A., Sadek, M.A., El-Idreesy, T.T. (2018). Microwave-assisted synthesis of palladium nanoparticles supported on copper oxide in aqueous medium as an efficient catalyst for Suzuki cross-coupling reaction, Adsorption Science & Technology, 36(5-6): 1352-1365.
  15. Elazab, H.A. (2015). Highly efficient and magnetically recyclable graphene-supported Pd/Fe3O4 nanoparticle catalysts for Suzuki and Heck cross-coupling reactions. Applied Catalysis A: General, 491: 58-69.
  16. Mohsen, W., Sadek, M.A., Elazab, H. (2017). Green synthesis of copper oxide nanoparticles in aqueous medium as a potential efficient catalyst for catalysis applications. International Journal of Applied Engineering Research, 12(24): 14927-14930.
  17. Bondioli, F. (2008). Synthesis of Zirconia Nanoparticles in a Continuous-Flow Microwave Reactor. Journal of the American Ceramic Society, 91(11): 3746-3748.
  18. Fukui, K. (2012). Mechanism of synthesis of metallic oxide powder from aqueous metallic nitrate solution by microwave denitration method. Chemical Engineering Journal, 211: 1-8.
  19. Glasnov, T.N., Findenig, S., Kappe, C.O. (2009). Heterogeneous versus Homogeneous Palladium Catalysts for Ligandless Mizoroki-Heck Reactions: A Comparison of Batch/Microwave and Continuous-Flow Processing. Chemistry - A European Journal, 15(4): 1001-1010.
  20. Kirschning, A., Kupracz, L., Hartwig, J. (2012). New Synthetic Opportunities in Miniaturized Flow Reactors with Inductive Heating. Chemistry Letters, 41(6): 562-570.
  21. Malewicz, M. (2009). Synthesis of Zinc Oxide Nanotiles by Wet Chemical Route Assisted by Microwave Heating. Electronics Technology, 15(3): 47-50.
  22. Pourmortazavi, S.M. (2012). Synthesis, structure characterization and catalytic activity of nickel tungstate nanoparticles. Applied Surface Science, 263: 745-752.
  23. Elazab, H.A., Sadek, M.A., El-Idreesy, T.T. (2018). Microwave-assisted synthesis of palladium nanoparticles supported on copper oxide in aqueous medium as an efficient catalyst for Suzuki cross-coupling reaction. Adsorption Science & Technology, 36(5-6): 1352-1365.
  24. Yu, X.H. (2006). Research Progress of Nanostructured Materials for Heterogeneous Catalysis. Current Nanoscience, 7(4): 576-586.
  25. Horikoshi, S. (2006). On the Generation of Hot-Spots by Microwave Electric and Magnetic Fields and Their Impact on a Microwave-Assisted Heterogeneous Reaction in the Presence of Metallic Pd Nanoparticles on an Activated Carbon Support. Journal of Physical Chemistry C, 115(46): 23030-23035.
  26. Falcon, H. (2010). Large-scale synthesis of porous magnetic composites for catalytic applications, in Scientific Bases for the Preparation of Heterogeneous Catalysts: Proceedings of the 10th International Symposium, E.M. Gaigneaux, 347-350.
  27. Chen, S.T. (2012). Synthesis of Pd/Fe3O4 Hybrid Nanocatalysts with Controllable Interface and Enhanced Catalytic Activities for CO Oxidation. Journal of Physical Chemistry C, 116(23): 12969-12976.
  28. Moussa, S., Abdelsayed, V., El-Shall, M.S. (2011). Laser synthesis of Pt, Pd, CoO and Pd-CoO nanoparticle catalysts supported on graphene. Chemical Physics Letters, 510(4-6): 179-184.
  29. Qiu, G.H. (2011). Microwave-Assisted Hydrothermal Synthesis of Nanosized alpha-Fe2O3 for Catalysts and Adsorbents. Journal of Physical Chemistry C, 115(40): 19626-19631.
  30. Wang, H.L. (2010). Ni(OH)2 Nanoplates Grown on Graphene as Advanced Electrochemical Pseudocapacitor Materials. Journal of the American Chemical Society, 132(21): 7472-7477.
  31. Wang, H.L. (2010). Nanocrystal Growth on Graphene with Various Degrees of Oxidation. Journal of the American Chemical Society, 132(10): 270-285.
  32. Kalbasi, R.J., Negahdari, M. (2006). Synthesis and characterization of mesoporous poly(N-vinyl-2-pyrrolidone) containing palladium nanoparticles as a novel heterogeneous organocatalyst for Heck reaction. Journal of Molecular Structure, 1063: 259-268.
  33. Martins, D.d.L. (2009). Heck reactions catalyzed by Pd(0)-PVP nanoparticles under conventional and microwave heating. Applied Catalysis A: General, 408(1): 47-53.
  34. Sheng, L. (2006). PVP-coated graphene oxide for selective determination of ochratoxin A via quenching fluorescence of free aptamer. Biosensors and Bioelectronics, 26(8): 3494-3499.
  35. Zhang, J. (2010). Microwave-assisted synthesis of Pd nanoparticles and their catalysis application for Suzuki cross-coupling re-actions. Inorganic and Nano-Metal Chemistry, 47(5): 672-676.
  36. Zhang, X. (2006). Polyvinyl pyrrolidone modified graphene oxide for improving the mechanical, thermal conductivity and solvent resistance properties of natural rubber. RSC Advances, 6(60): 54668-54678.
  37. Zhang, Y. (2011). One-step synthesis of Polyvinylpyrrolidone-reduced graphene oxide-Pd nanoparticles for electrochemical sensing. Journal of Materials Science, 51(13): 6497-6508.
  38. Nicolaou, K.C., Bulger, P.G., Sarlah, D. (2005). Palladium-catalyzed cross-coupling reactions in total synthesis. Angewandte Chemie-International Edition, 44(29): 4442-4489.
  39. Ashraf, B., Elazab, H. (2018). Preparation and characterization of decorative and heat insulating floor tiles for buildings roofs. International Journal of Engineering and Technology (UAE), 7(3): 1295-1298.
  40. Elazab H.A. (2018). Laser vaporization and controlled condensation (LVCC) of graphene supported Pd/Fe3O4 nanoparticles as an efficient magnetic catalysts for Suzuki Cross Coupling. Biointerface Research in Applied Chemistry, 8(3): 3314-3318.
  41. Elazab, H.A. (2018). The catalytic activity of copper oxide nanoparticles towards carbon monoxide oxidation catalysis: microwave assisted synthesis approach, Biointerface Research in Applied Chemistry, 8(3): p. 3278-3281.
  42. Elazab, H.A., Radwan, M.A., El-Idreesy, T.T. (2018). Facile Microwave-Assisted Synthetic Approach to Palladium Nanoparticles Supported on Copper Oxide as an Efficient Catalyst for Heck and Sonogashira Cross-Coupling Reactions, International Journal of Nanoscience, 17(3): 1850032-1850040.
  43. Ceylan, S. (2011). Inductive Heating with Magnetic Materials inside Flow Reactors. Chemistry - A European Journal, 17(6): 1884-1893.
  44. Gupta, A. (2011). Synthesis and Ink-Jet Printing of Highly Luminescing Silicon Nanoparticles for Printable Electronics. Journal of Nanoscience and Nanotechnology, 11(6): 5028-5033.
  45. Nishioka, M. (2011). Continuous synthesis of monodispersed silver nanoparticles using a homogeneous heating microwave reactor system. Nanoscale, 3(6): 2621-2626.
  46. Shviro, M., Zitoun, D. (2013). Nickel nanocrystals: fast synthesis of cubes, pyramids and tetrapods. RSC Advances, 3(5): 1380-1387.
  47. Beckert, M. (2015). Nitrogenated graphene and carbon nanomaterials by carbonization of polyfurfuryl alcohol in the presence of urea and dicyandiamide. Green Chemistry, 17(2): 1032-1037.
  48. Kumar, S. (2015). Graphene, carbon nanotubes, zinc oxide and gold as elite nanomaterials for fabrication of biosensors for healthcare. Biosensors & Bioelectronics, 70: 498-503.
  49. Neri, G. (2015). Engineering of carbon based nanomaterials by ring-opening reactions of a reactive azlactone graphene platform. Chemical Communications, 51(23): 4846-4849.
  50. Mankarious, R.A., Elazab, H. (2017). Bulletproof vests/shields prepared from composite material based on strong polyamide fibers and epoxy resin. Journal of Engineering and Applied Sciences, 12(10): 2697-2701.
  51. Mostafa, A.R., Omar, H.A.-S., Elazab, H.A. (2017). Preparation of Hydrogel Based on Acryl Amide and Investigation of Different Factors Affecting Rate and Amount of Absorbed Water. Agricultural Sciences, 8(2): 11-18.
  52. Radwan, M.A., Elazab, H.A. (2017). Mechanical characteristics for different
  53. composite materials based on commercial epoxy resins and different fillers, Journal of Engineering and Applied Sciences, 12(5): 1179-1185.
  54. Samir, N.S., Elazab, H.A. (2018). Preparation and characterization of bullet-proof vests based on polyamide fibers. International Journal of Engineering and Technology (UAE), 7(3): 1290-1294.
  55. Tang, Y., Yang, Z. (2011). Trapping of metal atoms in the defects on graphene. Journal of Chemical Physics, 13(5): 22-32.
  56. Wang, Q. (2012). Adsorption of oxygen-containing functional groups on free and supported graphene using point contact. Physical Review B, 85(8), 85-96.
  57. Wu, S.X. (2012). Synthesis of Fe3O4 and Pt nanoparticles on reduced graphene oxide and their use as a recyclable catalyst. Nanoscale, 4(7): 2478-2483.
  58. Xi, P.X. (2012). Surfactant free RGO/Pd nanocomposites as highly active heterogeneous catalysts for the hydrolytic dehydrogenation of ammonia borane for chemical hydrogen storage. Nanoscale, 4(18): 5597-5601.
  59. Zhou, M. (2011). Adsorption of gas molecules on transition metal embedded graphene: a search for high-performance graphene-based catalysts and gas sensors. Nanotechnology, 22(38): 124-134.
  60. Botas, C. (2013). Graphene materials with different structures prepared from the same graphite by the Hummers and Brodie methods. Carbon, 65: 156-164.
  61. Hummers, W.S., Offeman, R.E. (1958). Preparation of Graphitic Oxide. Journal of the American Chemical Society, 80(6): 1339-1339.
  62. Rovnick, N. (2002). Scottish anti-lawyer group mounts political challenge, Lawyer, 16(37): 4-14.
  63. You, S. (2013). Effect of synthesis method on solvation and exfoliation of graphite oxide. Carbon, 52: 171-180.
  64. Elazab, H.A. (2019). Optimization of the Catalytic Performance of Pd/Fe3O4 Nanoparticles Prepared via Microwave-assisted Synthesis for Pharmaceutical and Catalysis Applications, Biointerface Research in Applied Chemistry, 9(1): 3794-3799.
  65. Elazab, H.A. (2019). Investigation of Microwave-assisted Synthesis of Palladium Nanoparticles Supported on Fe3O4 as an Efficient Recyclable Magnetic Catalysts for Suzuki Cross – Coupling, The Canadian Journal of Chemical Engineering, 97(5): 225-234.
  66. Zakaria, F., Radwan, M.A., Sadek, M.A., Elazab, H.A. (2018). Insulating material based on shredded used tires and inexpensive polymers for different roofs. International Journal of Engineering and Technology (UAE), 7(4):1983-1988.
  67. Nasser, R., Radwan, M.A., Sadek, M.A., Elazab, H.A. (2018). Preparation of insulating material based on rice straw and inexpensive polymers for different roofs. International Journal of Engineering and Technology (UAE), 7(4): 1989-1994.
  68. Ghobashy, M., Gadallah, M., El-Idreesy, T.T., Sadek, T.T., Elazab, H.A. (2018). Kinetic Study of Hydrolysis of Ethyl Acetate using Caustic Soda. International Journal of Engineering and Technology (UAE), 7(4): 1995-1999.
  69. Radwan, M.A., Rashad, M.A., Sadek, M.A., Elazab, H.A. (2019). Synthesis, Characterization and Selected Application of Chitosan-Coated Magnetic Iron Oxide nanoparticles. Journal of Chemical Technology and Metallurgy, 54(2): 303-310.

No citation recorded.