Graphene Oxide Nano-Sheets-Supported Co(II)-d-Penicillamine as a Green and Highly Selective Catalyst for Epoxidation of Styrene

  • Sajjad KeshipourEmail author
  • Mehran Kulaei
  • Fatemeh Ahour
Research Paper


A new efficient heterogeneous catalyst was introduced for the epoxidation of styrene. The catalyst was obtained from functionalization of graphene oxide nano-sheets with d-penicillamine, and then complexation of graphene oxide functionalized d-penicillamine with Co(II). High yield and excellent selectivity were achieved for the epoxidation of styrene using the synthesized catalyst in solvent-free conditions at 50 °C using H2O2 as a green oxidant during 2 h. The reaction has some advantages such as solvent-free and mild reaction conditions, high yield, excellent selectivity, green oxidant and short reaction conditions. Also, the recovered catalyst is applicable for 6 times without decrease in yield.

Graphical Abstract


Graphene oxide Nano-sheets Epoxidation Styrene oxide d-Penicillamine Heterogeneous catalyst 



We gratefully acknowledge financial support from the Research Council of Urmia University.


  1. Allen MJ, Tung VC, Kaner RB (2009) Honeycomb carbon: a review of graphene. Chem Rev 110:132–145CrossRefGoogle Scholar
  2. Avinash MB, Subrahmanyam KS, Sundarayya Y, Govindaraju T (2010) Covalent modification and exfoliation of graphene oxide using ferrocene. Nanoscale 2:1762–1766CrossRefGoogle Scholar
  3. Cetinkaya Y, Metin Ö, Balci M (2016) Reduced graphene oxide supported nickel–palladium alloy nanoparticles as a superior catalyst for the hydrogenation of alkenes and alkynes under ambient conditions. RSC Adv 6:28538–28542CrossRefGoogle Scholar
  4. Chen J, Yao B, Li C, Shi G (2013) An improved Hummers method for eco-friendly synthesis of graphene oxide. Carbon 64:225–229CrossRefGoogle Scholar
  5. Cui P, Lee J, Hwang E, Lee H (2011) One-pot reduction of graphene oxide at subzero temperatures. Chem Commun 47:12370–12372CrossRefGoogle Scholar
  6. Doornbos D, Faber JS (1964) Studies on metal complexes of drugs; d-penicillamine and N-acetyl-d-penicillamine. Pharm Weekble 99:289–309Google Scholar
  7. Dreyer DR, Todd AD, Bielawski CW (2014) Harnessing the chemistry of graphene oxide. Chem Soc Rev 43:5288–5301CrossRefGoogle Scholar
  8. Gómez-Martínez M, Baeza A, Alonso DA (2017) Graphene oxide-supported oxime palladacycles as efficient catalysts for the Suzuki–Miyaura cross-coupling reaction of aryl bromides at room temperature under aqueous conditions. Catalysts 7:94–110CrossRefGoogle Scholar
  9. Gu Q, Han D, Shi L, Sun Q (2012) Styrene epoxidation with hydrogen peroxide over calcium oxide catalysts prepared from various precursors. J Nat Gas Chem 21:452–458CrossRefGoogle Scholar
  10. Gupta RK, Alahmed ZA, Yakuphanoglu F (2013) Graphene oxide based low cost battery. Mater Lett 112:75–77CrossRefGoogle Scholar
  11. Ionescu R, Pavel OD, Birjega R, Zavoianu R, Angelescu E (2010) Epoxidation of cyclohexene with H2O2 and acetonitrile catalyzed by Mg–Al hydrotalcite and cobalt modified hydrotalcites. Catal Lett 134:309–317CrossRefGoogle Scholar
  12. Kakran M, Sahoo NG, Bao H, Pan Y, Li L (2011) Functionalized graphene oxide as nanocarrier for loading and delivery of ellagic acid. Curr Med Chem 18:4503–4512CrossRefGoogle Scholar
  13. Kaminska I, Das MR, Coffinier Y, Niedziolka-Jonsson J, Sobczak J, Woisel P, Lyskawa J, Opallo M, Boukherroub R, Szunerits S (2012) Reduction and functionalization of graphene gxide sheets using biomimetic dopamine derivatives in one step. ACS Appl Mater Interfaces 4:1016–1020CrossRefGoogle Scholar
  14. Keshipour S, Adak K (2016) Pd(0) supported on N-doped graphene quantum dot modified cellulose as an efficient catalyst for the green reduction of nitroaromatics. RSC Advances 6:89407–89412CrossRefGoogle Scholar
  15. Keshipour S, Kalam Khalteh N (2016) Oxidation of ethylbenzene to styrene oxide in the presence of cellulose-supported Pd magnetic nanoparticles. Appl Organometal Chem 30:653–656CrossRefGoogle Scholar
  16. Keshipour S, Shaabani A (2014) Copper(I) and palladium nanoparticles supported on ethylenediamine-functionalized cellulose as an efficient catalyst for the 1,3-dipolar cycloaddition/direct arylation sequence. Appl Organometal Chem 28:116–119CrossRefGoogle Scholar
  17. Keshipour S, Shojaei S, Shaabani A (2013) Palladium nano-particles supported on ethylenediaminefunctionalized cellulose as a novel and efficient catalyst for the Heck and Sonogashira couplings in water. Cellulose 20:973–980CrossRefGoogle Scholar
  18. Keshipour S, Ahmadi F, Seyyedi B (2017) Chitosan modified Pd(II)-d-penicillamine; Preparation, characterization, and catalyst application. Cellulose 24:1455–1462CrossRefGoogle Scholar
  19. Kirm I, Medina F, Rodriguez X, Cesteros Y, Sueiras Salagre P (2004) Epoxidation of styrene with hydrogen peroxide using hydrotalcites as heterogeneous catalysts. J Appl Catal A 272:175–185CrossRefGoogle Scholar
  20. Laha SC, Kumar R (2001) Selective epoxidation of styrene to styrene oxide over TS-1 using urea–hydrogen peroxide as oxidizing agent. J Catal 204:64–70CrossRefGoogle Scholar
  21. Liu J, Wang F, Qi S, Gu Z, Wu G (2013) Highly selective epoxidation of styrene over gold–silica catalysts via one-pot synthesis: synthesis, characterization, and catalytic application. New J Chem 37:769–774CrossRefGoogle Scholar
  22. Loh KP, Bao QL, Ang PK, Yang JX (2010a) The chemistry of grapheme. J Mater Chem 20:2277–2289CrossRefGoogle Scholar
  23. Loh KP, Bao QL, Eda G, Chhowalla M (2010b) Graphene oxide as a chemically tunable platform for optical applications. Nat Chem 2:1015–1024CrossRefGoogle Scholar
  24. Lomeda JR, Doyle CD, Kosynki DV, Hwang WF, Tour JM (2008) Diazonium functionalization of surfactant-. wrapped chemically converted graphene sheets. J Am Chem Soc 130:16201–16206CrossRefGoogle Scholar
  25. Mandelli D, Avan Vliet MC, Sheldon RA, Schuchardt U (2001) Alumina-catalyzed alkene epoxidation with hydrogen peroxide. Appl Catal A 219:209–2013CrossRefGoogle Scholar
  26. Mitchell D, Koenig TM (1995) Synthesis of R- and S- fluoxetine, norfluoxetine and related compounds from styrene oxide. Synth Commun 25:1231–1238CrossRefGoogle Scholar
  27. Neises B, Steglich W (1985) Esterification of carboxylic acids with dicyclohexylcarbodiimide/4-dimethylaminopyridine: tert-butyl ethyl fumarate. Org Synth 63:183CrossRefGoogle Scholar
  28. Pillai UR, Sahle-Demessie E, Varma RS (2002) Selective oxidation of styrene to acetophenone in presence of ionic liquids. Tetrahedron Lett 43:2909–2911CrossRefGoogle Scholar
  29. Su DS, Perathoner S, Centi G (2013) Nanocarbons for the development of advanced catalysts. Chem Rev 113:5782–5816CrossRefGoogle Scholar
  30. Ueno S, Yamaguchi K, Yoshida K, Ebitani K, Kaneda K (1998) Hydrotalcite catalysis: heterogeneous epoxidation of olefins using hydrogen peroxide in the presence of nitriles. Chem Commun 3:295–296CrossRefGoogle Scholar
  31. Upare PP, Yoon JW, Kim MY, Kang HY, Hwang DW, Hwang YK, Kung HH, Chang JS (2013) Chemical conversion of biomass-derived hexose sugars to levulinic acid over sulfonic acid-functionalized graphene oxide catalysts. Green Chem 15:2935–2943CrossRefGoogle Scholar
  32. Wang HX, Zhou KG, Xie YL, Zeng J, Chai NN, Li J, Zhang HL (2011) Photoactive graphene sheets prepared by “click” chemistry. Chem Commun 47:5747–5749CrossRefGoogle Scholar
  33. Xie J, Yang X, Xu X, Yang C (2017) Microwave synthesis of reduced graphene oxide-supported platinum nanocomposite with high electrocatalytic activity for methanol oxidation. Int J Electrochem Sci 12:466–474CrossRefGoogle Scholar
  34. Yang X, Wang Y, Huang X, Ma Y, Huang Y, Yang R, Duana H, Chen Y (2011) Multi-functionalized graphene oxide based anticancer drug-carrier with dual-targeting function and pH-sensitivity. J Mater Chem 21:3448–3454CrossRefGoogle Scholar
  35. Zhang DH, Li HB, Lia GD, Chen JS (2009) Magnetically recyclable Ag-ferrite catalysts: general synthesis and support effects in the epoxidation of styrene. Dalton Trans 47:10527–10533CrossRefGoogle Scholar
  36. Zhang X, Wang G, Yang M, Luan Y, Dong W, Dang R (2014) Synthesis of a Fe3O4–CuO@meso-SiO2 nanostructure as a magnetically recyclable and efficient catalyst for styrene epoxidation. Catal Sci Technol 4:3082–3089CrossRefGoogle Scholar
  37. Zhang WH, He PP, Wu S, Xu J, Li Y, Zhang G, Wei XY (2016) Graphene oxide grafted hydroxyl-functionalized ionic liquid: a highly efficient catalyst for cycloaddition of CO2 with epoxides. Appl Catal A 509:111–117CrossRefGoogle Scholar

Copyright information

© Shiraz University 2017

Authors and Affiliations

  • Sajjad Keshipour
    • 1
    Email author
  • Mehran Kulaei
    • 1
  • Fatemeh Ahour
    • 1
  1. 1.Department of Nanochemistry, Nanotechnology Research CentreUrmia University, G. C.UrmiaIran

Personalised recommendations