Catalytic Properties of Alumina-Supported Ruthenium, Platinum, and Cobalt Nanoparticles towards the Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone

*Ilhem Rekkab-Hammoumraoui orcid  -  Laboratoire de Catalyse et Synthèse en Chimie Organique, Faculté des Sciences, , Algeria
Abderrahim Choukchou-Braham  -  Laboratoire de Catalyse et Synthèse en Chimie Organique, Faculté des Sciences, , Algeria
Received: 26 May 2017; Revised: 17 Jul 2017; Accepted: 18 Jul 2017; Published: 2 Apr 2018; Available online: 22 Jan 2018.
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A series of metal-loaded (Ru, Pt, Co) alumina catalysts were evaluated for the catalytic oxidation of cyclohexane using tertbutylhydroperoxide (TBHP) as oxidant and acetonitrile or acetic acid as solvent. These materials were prepared by the impregnation method and then characterized by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), H2 chemisorption, Fourier Transformed Infrared Spectroscopy (FTIR), High-Resolution Transmission Electron Microscopy (HRTEM), and X-ray Diffraction (XRD). All the prepared materials acted as efficient catalysts. Among them, Ru/Al2O3 was found to have the best catalytic activity with enhanced cyclohexane conversion of 36 %, selectivity to cyclohexanol and cyclohexanone of 96 % (57.6 mmol), and cyclohexane turnover frequency (TOF) of 288 h-1. Copyright © 2018 BCREC Group. All rights reserved

Received: 26th May 2017; Revised: 17th July 2017; Accepted: 18th July 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018

How to Cite: Rekkab-Hammoumraoui, I., Choukchou-Braham, A. (2018). Catalytic Properties of Alumina-Supported Ruthenium, Platinum, and Cobalt Nanoparticles towards the Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone. Bulletin of Chemical Reaction Engineering & Catalysis, 13(1): 24-36 (doi:10.9767/bcrec.13.1.1226.24-35)


Keywords: Cyclohexane oxidation, Alumina, TBHP, Metal.
Funding: Algerian Ministry of Higher Education and Scientific Research

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  1. Sheldon, R.A. (1981) Metal-catalyzed Epoxidation of Olefins with Hydroperoxides, in Aspects of Homogeneous Catalysis, R. Ugo (Ed.); Reidel, Dordrecht, Volume 4, pp. 3-70.
  2. Hao, J., Liu, B., Cheng, H., Wang, Wang, Q.J., Cai, S., Zhao, F. (2009). Cyclohexane Oxidation on A Novel Ti70Zr10Co20 Catalyst Containing Quasicrystal. Chemical Communications, 23: 3460-3462.
  3. Sato, K., Aoki, M., Noyori, R. (1998). A "Green" Route to Adipic Acid: Direct Oxidation of Cyclohexenes with 30 Percent Hydrogen Peroxide. Science, 281: 1646-1647.
  4. Cavani, F., Centi, G., Perathoner, S., Trifiro, F. (2009). Sustainable Industrial Processes, WILEY-VCH Verlag GmbH & Co, KGaA, Weinheim.
  5. Zhou, L., Xu, J., Miao, H., Wang, F., Li, X. (2005). Catalytic Oxidation of Cyclohexane to Cyclohexanol and Cyclohexanone over Co3O4 Nanocrystals with Molecular Oxygen. Applied Catalysis A: General, 292: 223-228.
  6. Chen, C., Xu, J., Zhang, Q., Ma, H., Miao, H., Zhou, L. (2009). Direct Synthesis of Bifunctionalized Hexagonal Mesoporous Silicas and Its Catalytic Performance for Aerobic Oxidation of Cyclohexane. The Journal of Physical Chemistry C, 113: 2855-2860.
  7. Deng, Y., Ma, Z., Wang, K., Chen, J. (1999). Clean Synthesis of Adipic Acid by Direct Oxidation of Cyclohexene with H2O2 over Peroxytungstate-Organic Complex Catalysts. Green Chemistry, 1: 275-276.
  8. Thomas, J.M., Raja, R. (2006). Innovations in Oxidation Catalysis Leading to A Sustainable Society. Catalysis Today, 117: 22-31.
  9. Guo, C.C., Chu, M.F., Liu, Q., Liu, Y., Guo, D.C., Liu, X.Q. (2003). Effective Catalysis of Simple Metalloporphyrins for Cyclohexane Oxidation with Air in the Absence of Additives and Solvents. Applied Catalysis A: General, 246: 303-309.
  10. Burda, C., Chen, X., Narayanan, R., El-Sayed, M.A. (2005). Chemistry and Properties of Nanocrystals of Different Shapes. Chemical Reviews, 105: 1025-1102.
  11. Wang, C., Chen, L., Qi, Z. (2013). One-pot Synthesis of Gold Nanoparticles Embedded in Silica for Cyclohexane Oxidation. Catalysis Science & Technology, 3: 1123-1128.
  12. Wu, P., Xiong, Z., Loh, K.P., Zhao, X.S. (2011). Selective Oxidation of Cyclohexane over Gold Nanoparticles Supported on Mesoporous Silica Prepared in the Presence of Thioether Functionality. Catalysis Science & Technology, 1: 285-294.
  13. Bradley, J.S. In: Schmidt G., editor. (1994). Clusters and Colloids from Theory to Applications, VCH, Weinheim, Germany.
  14. Liu, X., Conte, M., Sankar, M., He, Q., Murphy, D.M., Morgan, D., Jenkins, R.L., Knight, D., Whiston, K., Kiely, C.J., Hutchings, G.J. (2015). Liquid Phase Oxidation of Cyclohexane Using Bimetallic Au-Pd/MgO Catalysts. Applied Catalysis A: General, 504: 373-380.
  15. Mahdavi, V., Hasheminasab, H.R. (2015). Liquid-phase Efficient Oxidation of Cyclohexane over Cobalt Promoted VPO Catalyst Using Tert-butylhydroperoxide. Journal of the Taiwan Institute of Chemical Engineers, 51: 53-62.
  16. Makgwane, P.R., Ray, S.S. (2014). Efficient Room Temperature Oxidation of Cyclohexane over Highly Active Hetero-mixed WO3/V2O5 Oxide Catalyst. Catalysis Communications, 54: 118-123.
  17. Bellifa, A., Choukchou-Braham, A., Kappenstein, C., Pirault-Roy, L. (2014). Preparation and Characterization of MTiX for the Catalytic Oxidation of Cyclohexane. RSC Advances, 4: 22374-22379.
  18. Hayati, F., Chandren, S., Hamdan, H., Nur, H. (2014). The Role of Ti and Lewis Acidity in Manganese Oxide Octahedral Molecular Sieves Impregnated with Titanium in Oxidation Reactions. Bulletin of Chemical Reaction Engineering & Catalysis, 9: 28-38.
  19. Carabineiro, S.A.C., Martins, L.M., Avalos-Borja, M., Buijnsters, J.G., Pombeiro, A.J.L., Figueiredo, J.L. (2013). Gold Nanoparticles Supported on Carbon Materials for Cyclohexane Oxidation with Hydrogen Peroxide. Applied Catalysis A: General, 467: 279-290.
  20. Huang, G., Shen, L., Luo, Z.C., Hu, Y.D., Guo, Y.A., Wei, S.J. (2013). Use of A Boehmite Immobilized Cobalt Tetra(4-carboxyl) Phenylporphyrin Catalyst for the Aerobic Oxidation of Cyclohexane to Ketone and Alcohol. Catalysis Communications, 32: 108-112.
  21. Lu, X.H., Yuan, H.X., Lei, J., Zhang, J.L., Yu, A.A., Zhou, D., Xia, Q.H. (2012). Selective Oxidation of Cyclohexane to KA-oil with Oxygen over Active Co3O4 in A Solvent-free System. Indian Journal of Chemistry, 51A: 420-427.
  22. Bernas, A., Kumar, N., Laukkanen, P., Vayrynen, J., Salmi, T., Murzin, D.Y. (2004). Influence of Ruthenium Precursor on Catalytic Activity of Ru/Al2O3 Catalyst in Selective Isomerization of Linoleic Acid to Cis-9,trans-11- and Trans-10,cis-12-conjugated Linoleic Acid. Applied Catalysis A: General, 267: 121-133.
  23. Perkas, N., Minh, D.P., Gallezot, P., Gedanken, A., Besson, M. (2005). Platinum and Ruthenium Catalysts on Mesoporous Titanium and Zirconium Oxides for the Catalytic Wet Air Oxidation of Model Compounds. Applied Catalysis B: Environmental, 59: 121-130.
  24. Bergeret, G., Gallezot, P. (1997). In: Handbook of Heterogeneous Catalysis. Wiley-VCH, Weinheim.
  25. Coloma, F., Sepulveda-Escribano, A., Fierro, J.L., Rodriguez- Reinoso, F. (1997). Gas Phase Hydrogenation of Crotonaldehyde over Pt/Activated Carbon Catalysts: Influence of the Oxygen Surface Groups on the Support. Applied Catalysis A: General, 150: 165-183.
  26. Rekkab-Hammoumraoui, I., Choukchou-Braham, A., Pirault-Roy, L., Kappenstein, C. (2011). Catalytic Oxidation of Cyclohexane to Cyclohexanone and Cyclohexanol by Tert-Butyl Hydroperoxide over Pt/oxide Catalysts. Bulletin of Materials Science, 34: 1127-1135.
  27. Kumar, R., Sithambaram, S., Suib, S.L. (2009). Cyclohexane Oxidation Catalyzed by Manganese Oxide Octahedral Molecular Sieves-Effect of Acidity of the Catalyst. Journal of Catalysis, 262: 304-313.
  28. Bellifa, A., Lahcene, D., Tchenar, Y.N., Choukchou-Braham, A., Bachir, R., Bedrane, S., Kappenstein, C. (2006). Preparation and Characterization of 20 wt.% V2O5-TiO2 Catalyst Oxidation of Cyclohexane. Applied Catalysis A: General, 305: 1-6.
  29. Zhao, R., Wang, Y., Guo, Y., Guo, Y., Liu, X., Zhang, Z., Wang, Y., Zhan, W., Lu, G. (2006). A Novel Ce/AlPO-5 Catalyst for Solvent-free Liquid Phase Oxidation of Cyclohexane by Oxygen. Green Chemistry, 8: 459-466.
  30. Wangcheng, Z., Guanzhong, L., Yanglong, G., Yun, G., Yanqin, W., Yunsong, W., Zhigang, Z., Xiaohui, L. (2008). Synthesis of Cerium-doped MCM-48 Molecular Sieves and Its Catalytic Performance for Selective Oxidation of Cyclohexane. Journal of Rare Earths, 26: 515-522.
  31. Lu, G., Zhao, R., Qian, G., Qia, Y., Wang, X., Suo, J. (2004). A Highly Efficient Catalyst Au/MCM-41 for Selective Oxidation Cyclohexane Using Oxygen. Catalysis Letters, 97: 115-118.
  32. Li, H., She, Y., Wang, T. (2012). Advances and Perspectives in Catalysts for Liquid-phase Oxidation of Cyclohexane. Frontiers of Chemical Science and Engineering, 6: 356-368.
  33. Liu, Y., Tsunoyama, H., Akita, T., Xie, S., Tsukuda, T. (2011). Aerobic Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters on Hydroxyapatite: Size Effect in the Sub-2 nm Regime. ACS Catalysis, 1: 2-6.
  34. Rekkab-Hammoumraoui, I., Benabadji-Soulimane, R., El Korso-Hamza Reguig, S., Choukchou-Brabam, A., Bachir, R. (2010). Preparation and Characterization of X wt-%Ru/Al2O3 Catalysts for Cyclohexane Oxidation Using Tert-butyl Hydroperoxide. Research Journal of Pharmaceutical, Biological and Chemical Sciences, 1: 240-239.
  35. Sooknoi, T., Limtrakul, J., (2002). Activity Enhancement by Acetic Acid in Cyclohexane Oxidation Using Ti-containing Zeolite Catalyst. Applied Catalysis A: General, 233: 227-237.
  36. Adam, F., Wong, J., Ng, E. (2013). Fast Catalytic Oxidation of Phenol over Iron Modified Zeolite L Nanocrystals. Chemical Engineering Journal, 214: 63-67.
  37. Arends, I.W.C.E., Sheldon, R.A. (2001). Activities and Stabilities of Heterogeneous Catalysts in Selective Liquid Phase Oxidations: Recent Developments. Applied Catalysis A: General, 212: 175-187.
  38. Fraile, J.M., Garcia, J.I., Mayoral, J.A., Vispe, E. (2001). Effect of the Reaction Conditions on the Epoxidation of Alkenes with Hydrogen Peroxide Catalyzed by Silica-Supported Titanium Derivatives. Journal of Catalysis, 204: 146-156.
  39. Busca, G., Finocchio, E., Ramis, G., Ricchiardi, G. (1996). On the Role of Acidity In Catalytic Oxidation. Catalysis Today, 32: 133-143.
  40. Conte, M., Liu, X., Murphy, D.M., Whiston, K., Hutchings, G.J. (2012). Cyclohexane Oxidation Using Au/MgO: An Investigation of the Reaction Mechanism. Physical Chemistry Chemical Physics, 14: 16279-16285.
  41. Yuan, H.X., Xia, Q.H., Zhan, H.J., Lu, X.H., Su, K.X. (2006). Catalytic Oxidation of Cyclohexane to Cyclohexanone and Cyclohexanol by Oxygen in A Solvent-free System over Metal-containing ZSM-5 Catalysts. Applied Catalysis A: General, 304: 178-184.
  42. Kharkova, T.V., Arest-Yakubovich, I.L., Lipes, V.V. (1989). Kinetic Model of the Liquid-phase Oxidation of Cyclohexane. I. Homogeneous Proceedings of the Process. Kinetics and Catalysis, 30: 954-958.
  43. Loncarevic, D., Krstic, J., Bankovic, P., Anic, S., Cupic, Z. (2007). Temperature Dependence of Catalytic Cyclohexane Partial Oxidation in A Polytetrafluoroethylene Reactor. Russian Journal of Physical Chemistry A., 81: 1398-1401.
  44. Akhrem, A.A., Metelitsa, D.I., Skurko, M.E., (1975). Chemical Model of the Enzyme System for Hydroxylating Cyclohexane. Bioorganic Chemistry, 4: 307-316.
  45. Larsen, R.G., Saladino, A.C., Hunt, T.A., Mann, J.E., Xu, M., Grassian, V.H., Larsen, S.C. (2001). A Kinetic Study of the Thermal and Photochemical Partial Oxidation of Cyclohexane with Molecular Oxygen in Zeolite Y. Journal of Catalysis, 204: 440-449.
  46. Mahajani, S.M., Sharma, M.M., Sridhar, T. (1999). Uncatalyzed Oxidation of Cyclohexene. Chemical Engineering Science, 54: 3967-3976.
  47. Suresh, A.K., Sridhar, T., Potter, O.E. (1988). Autocatalytic Oxidation of Cyclohexane-Modeling Reaction Kinetics. AlChE Journal, 34: 69-80.
  48. Wang, J., Zhao, H., Zhang, X., Liu, R., Hu, Y. (2008). Oxidation of Cyclohexane Catalyzed by TS-1 in Ionic Liquid with Tert-butyl-hydroperoxide. Chinese Journal of Chemical Engineering, 16: 373-375.
  49. Selvam, P., Mohapatra, S.K. (2004). Synthesis, Characterization and Catalytic Properties of Mesoporous TiHMA Molecular Sieves: Selective Oxidation of Cycloalkanes. Microporous and Mesoporous Materials, 73: 137-149.
  50. Liu, X., He, J., Yang, L., Wang, Y., Zhang, S., Wang, W., Wang, J. (2010). Liquid-phase Oxidation of Cyclohexane to Cyclohexanone over Cobalt-Doped SBA-3. Catalysis Communications, 11: 710-714.
  51. Dapurkar, S.E., Sakthivel, A., Selvam, P. (2004). Mesoporous VMCM-41: Highly Efficient and Remarkable Catalyst for Selective Oxidation of Cyclohexane to Cyclohexanol. Journal of Molecular Catalysis A: Chemical, 223: 241-250.
  52. Wu, P., Bai, P., Loh, K.P., Zhao, X.S. (2010). Au Nanoparticles Dispersed on Functionalized Mesoporous Silica for Selective Oxidation of Cyclohexane. Catalysis Today, 158: 220-227.
  53. Aboelfetoh, E.F., Fechtelkord, M., Pietschnig, R. (2010). Structure and Catalytic Properties of MgO-supported Vanadium Oxide in the Selective Oxidation of Cyclohexane. Journal of Molecular Catalysis A: Chemical, 318: 51-59.
  54. Silva, F.P., Jacinto, M.J., Landers, R., Rossi, L.M. (2011). Selective Allylic Oxidation of Cyclohexene by a Magnetically Recoverable Cobalt Oxide Catalyst. Catalysis Letters, 141: 432-437

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