Journal of Chemical Sciences

, Volume 127, Issue 4, pp 701–709 | Cite as

Studies on ethylbenzene dehydrogenation with CO2 as soft oxidant over Co3O4/COK-12 catalysts



Oxidative dehydrogenation of ethylbenzene to styrene has been studied over Co3O4 supported on mesoporous silica (COK-12) with CO2 as soft oxidant in a fixed bed reactor at atmospheric pressure in the temperature range of 723 to 923K. While COK-12 has been prepared by self-assembly method using long chain ionic surfactant i.e., P123 as template, cobalt oxide supported on COK-12 catalysts with variable Co content have been synthesised by simple wet impregnation technique. All the catalysts were characterized by N2 adsorption - desorption, XRD, FT-IR, TPR, UV-Vis and XPS techniques. XRD and pore size distribution studies indicate the intactness of mesoporous structure of SiO2 even after incorporation of Co3O4. Presence of Co3O4 crystallites were observed beyond 5 wt% Co loading. High ethylbenzene conversion and stable styrene yields have been observed over 3% Co3O4/COK-12 catalyst due to the presence of large number of active Co3O4 catalytic sites. Enhancement in the activity has been observed with CO2 as soft oxidant than with N2 as diluent. This is because of the fact that the liberated H2 reacts with CO2 in the form of reverse water gas shift reaction.

Graphical Abstract

3 weight% Co3O4 on COK-12 catalyst exhibits good and stable activity in the oxidative dehydrogenation of ethyl benzene to styrene due to the presence of smaller Co3O4 particles.


Co3O4/COK-12 ethylbenzene dehydrogenation CO2 soft oxidant styrene 



The authors thank Department of Science & Technology (DST), New Delhi, India for sanctioning a project (DST/IS-STAC/CO2-SR-136/12(C))under CO2 sequestration scheme. PR and AN acknowledge Council of Scientific and Industrial Research (CSIR), New Delhi, India for the award of CSIR fellowship.


  1. 1.
    Brydson J A 1999 In Plastic Materials 7th ed. Published by (Oxford: Butterworth-Heinemann)Google Scholar
  2. 2.
    Rao K N, Reddy B M, Abhishek B, Seo Y H, Jiang N and Park S E 2009 Appl. Catal. B: Environ. 91 649CrossRefGoogle Scholar
  3. 3.
    Li C, Miao C, Nie Y, Yue Y, Gu S, Yang W, Hua W, Gao Z and Chin 2010 J. Catal. 31 993Google Scholar
  4. 4.
    Oliveira A C, Fierro J L G, Valentini A, Nobre P S S and Rangel M C 2003 Catal. Today 686 49CrossRefGoogle Scholar
  5. 5.
    Balasamya R J, Khurshida A, Al-Ali A A S, Atanda L A, Sagata K, Asamoto M, Yahiro H, Nomura K, Sano T, Takehira K and Al-Khattaf S S 2010 Appl. Catal. A: Gen. 390 225CrossRefGoogle Scholar
  6. 6.
    Sun A, Qin Z, Chen S and Wang J 2004 J. Mol. Catal. A: Chem. 210 189CrossRefGoogle Scholar
  7. 7.
    Lima C L, Campos O S, Oliveira A C, De Sousa F F, Filho J M, Neto P L, Correia A N, Sabadia G Q, Nogueira I M, Pinheiro G S and Oliveira A C 2011 Appl. Catal. A: Gen. 395 53CrossRefGoogle Scholar
  8. 8.
    Batista A H M, De Sousa F F, Honorato S B, Ayala A P, Filho J M, De Sousa F W, Pinheiro A N, De Araujo J C S, Nascimento R F, Valentini A and Oliveira A C 2010 J. Mol.Catal. A: Chem. 315 86CrossRefGoogle Scholar
  9. 9.
    Delgado J J, Chen X, Tessonnier J P, Schuster M E, Del Rio E, Schlogl R and Su D S 2010 Catal. Today 150 49CrossRefGoogle Scholar
  10. 10.
    Ansari M B and Park S E 2012 Energy Environ. Sci. 5 9419CrossRefGoogle Scholar
  11. 11.
    Sugino M, Shimada H, Turuda T, Miura H, Ikenaga N and Suzuki T 1995 Appl. Catal. A: Gen. 121 125CrossRefGoogle Scholar
  12. 12.
    Mimura N and Saito M 2000 Catal. Today 55 173CrossRefGoogle Scholar
  13. 13.
    Wang S and Zhu Z H 2004 Energy Fuels 18 1126CrossRefGoogle Scholar
  14. 14.
    Carja G, Nakamura R, Aida T and Niiyama H 2003 J. Catal. 218 104CrossRefGoogle Scholar
  15. 15.
    Badstube T, Papp H, Dziembaj R and Kustrowski P 2000 Appl. Catal. A: Gen. 204 153CrossRefGoogle Scholar
  16. 16.
    Li H, Yue Y, Miao C, Xie Z, Hua W and Gao Z 2007 Catal. Comm. 8 1317CrossRefGoogle Scholar
  17. 17.
    Li X H, Ying X W and Ke C 2005 Catal. Lett. 105 223CrossRefGoogle Scholar
  18. 18.
    Freire R M, Pinheiro A L, Oliveira A C, De Sousa F F, Ayala A P, Filho J M, Freire P T C and Oliveira A C 2009 Appl. Catal. A: Gen. 359 165CrossRefGoogle Scholar
  19. 19.
    Meima G R and Menon P G 2001 Appl. Catal. A: Gen. 212 239CrossRefGoogle Scholar
  20. 20.
    Burri D R, Choi K M, Sujandi D S H, Jiang N, Burri A and Park S E 2008 Catal.Today 131 173CrossRefGoogle Scholar
  21. 21.
    Burri D R, Choi K M, Han D S, Koo J B and Park S E 2006 Catal. Today 115 242CrossRefGoogle Scholar
  22. 22.
    Burri D R, Choi K M, Han S C, Burri A and Park S E 2007 J. Mol. Catal. A: Chem. 269 58CrossRefGoogle Scholar
  23. 23.
    Liao S J, Chen T, Miao C X, Yang W M, Xie Z K and Chen Q L 2008 Catal. Commun. 9 1817CrossRefGoogle Scholar
  24. 24.
    Sekine Y, Watanabe R, Matsukata M and Kikuchi E 2008 Catal. Lett. 125 215CrossRefGoogle Scholar
  25. 25.
    Jiang N, Han D S and Park S E 2009 Catal. Today 141 344CrossRefGoogle Scholar
  26. 26.
    Reddy B M, Lee S C, Han D S and Park S E 2009 Appl. Catal. B: Environ. 87 230CrossRefGoogle Scholar
  27. 27.
    Reddy B M, Jin H, Han D S and Park S E 2008 Catal. Lett. 124 357CrossRefGoogle Scholar
  28. 28.
    Ohishi Y, Kawabata T, Shishido T, Takaki K, Zhang Q, Wang Y and Takehira K 2005 J. Mol. Catal. A: Chem. 230 49CrossRefGoogle Scholar
  29. 29.
    Mathew T, Malwadkar S, Shivanand P, Sharanappa N, Sebastian C P, Satyanarayana C V V and Bokade V V 2003 Cat. Lett. 91 217CrossRefGoogle Scholar
  30. 30.
    Eduardo G and Alexander M 2004 Appl. Catal. A: Gen. 258 99CrossRefGoogle Scholar
  31. 31.
    Alexander M, Marıa E. Troconis, Eduardo G, Cesar Moran, Jorge Sanchez, Angel G and Jackeline Q 2006 Appl. Catal A: Gen. 310 199CrossRefGoogle Scholar
  32. 32.
    Xiao-Feng Guo, Joong-Ho Kim and Geon-Joong Kim 2011 Catal. Today 164 336CrossRefGoogle Scholar
  33. 33.
    Atanda L A, Balasamy R J, Khurshid A, Al-Ali A A S, Sagata K, Asamoto M, Yahiro H, Nomura K, Sanod T, Takehira K and Al-Khattaf S S 2011 Appl. Catal A: Gen 396 107CrossRefGoogle Scholar
  34. 34.
    Liu B S, Rui G, Chang R Z and Au C T 2008 Appl. Catal. A: Gen. 335 88CrossRefGoogle Scholar
  35. 35.
    Qiao Y, Miao C, Yue Y, Xie Z, Yang W, Hua W and Gao Z 2009 Micro. Meso. Mater. 119 150CrossRefGoogle Scholar
  36. 36.
    Carja G, Kameshima Y and Okada K 2008 Micro. Meso. Mater. 115 541CrossRefGoogle Scholar
  37. 37.
    Burri D R, Choi K M, Lee J H, Han D S and Park S E 2007 Catal. Commun. 8 43CrossRefGoogle Scholar
  38. 38.
    Zhao D, Feng J, Huo Q, Melosh N, Fredrickson G H, Chmelka B F and Stucky G D 1998 Science 279 548CrossRefGoogle Scholar
  39. 39.
    Kresge C T, Leonowicz M E, Roth W J, Vartuli J C and Beck J S 1992 Nature 359 710CrossRefGoogle Scholar
  40. 40.
    Jammaer J, Aerts A, Haen J D, Seob J W and Martens J A 2009 J. Mater. Chem. 19 8290CrossRefGoogle Scholar
  41. 41.
    Wang L, Mingming Z., Miao Z., Sha G and Liang C 2013 Energy Fuels 27 2209CrossRefGoogle Scholar
  42. 42.
    Jammaer J, van Erp T S, Aerts A, Kirschhock C E and Martens 2011 J. Am. Chem. Soc. 133 13737CrossRefGoogle Scholar
  43. 43.
    Wei D, Yao N and Haller G L 1999 Stud. Surf. Sci. Catal. 121 239Google Scholar
  44. 44.
    Oliveira A C, Essayem N, Tuel A, Clacens J M and Taarit Y B 2008 Stud. Surf. Sci. Catal. 174 1239Google Scholar
  45. 45.
    Wang J and Liu Q 2005 Micro. Meso. Mater. 83 225CrossRefGoogle Scholar
  46. 46.
    Gonzalez O, Perez H, Navarro P, Almeida L C, Pacheco J G and Montes M 2009 Catal. Today 148 140CrossRefGoogle Scholar
  47. 47.
    Wang C, Lim S, Du G, Loebicki C Z, Li N, Derrouiche S and Haller G L 2009 J. Phys. Chem. C 113 14863CrossRefGoogle Scholar
  48. 48.
    Taghavimoghaddam J, Knowles G P and Chaffee A L 2012 J. Mol Cat. A: Chem. 358 79CrossRefGoogle Scholar
  49. 49.
    Gregg S J and Sing K S W 1982 In Adsorption Surface Area and Porosity (London: Academic Press)Google Scholar
  50. 50.
    Tsoncheva T, Ivanova L, Minchev C and Froba M 2009 J. Colloid Interface Sci. 333 277CrossRefGoogle Scholar
  51. 51.
    Li J, Xu X, Hao Z and Zhao W 2008 J. Por. Mat. 15 163CrossRefGoogle Scholar
  52. 52.
    Szegedi A, Popova M and Minchev C 2009 J. Mater. Sci. 44 6710CrossRefGoogle Scholar
  53. 53.
    Li H, Wang S, Liang F and Li J 2006 J. Mol. Catal. A: Gen. 244 33CrossRefGoogle Scholar
  54. 54.
    Suvanto S and Pakkanen T A 2000 J. Mol. Catal. A: Gen. 164 273CrossRefGoogle Scholar
  55. 55.
    Szegedi A, PopovaM and Minchev C 2009 J. Mater. Sci. 44 6710CrossRefGoogle Scholar
  56. 56.
    Katsoulidis A P, Petrakis D E, Armatas G S, Trikalitis P N and Pomonis P J 2006 Micropor. Mesopor. Mater. 92 71CrossRefGoogle Scholar
  57. 57.
    Samuel P D, Anderson L P, Tiago P B, Antoninho V, Josue M F and Oliveira A C 2011 J. Mol Cat. A: Chem. 348 1CrossRefGoogle Scholar
  58. 58.
    Nogueira I M, Sabadia G Q, Moreira A A, Josue M and Oliveira A C 2011 J. Mol. Cat. A: Chem. 351 81CrossRefGoogle Scholar
  59. 59.
    Atanda L, Al-Yassir N and Al-Khattaf S 2011 Chem. Eng. J. 171 1387CrossRefGoogle Scholar
  60. 60.
    Ramudu P, Anand N V, Ramesh babu G, Mural Dhar G, Sai Prasad P S, David Raju B and RamaRao K S 2014 Ind. J. Chem., Sec. A 53A 493Google Scholar
  61. 61.
    Zhao D, Huo Q, Feng J, Chmelka B F and Stucky G D 1998 J. Am Chem. Soc. 8 120 6024CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2015

Authors and Affiliations

    • 1
    • 1
    • 1
    • 2
    • 1
    • 1
    • 1
    Email author
  1. 1.Catalysis LaboratoryIndian Institute of Chemical TechnologyHyderabadIndia
  2. 2.Chemical Engineering DepartmentGayatri Vidya Parishad College of EngineeringVisakhapatnamIndia

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