Skip to main content

Aerobic oxidation of ethylbenzene to acetophenone over mesoporous ceria–cobalt mixed oxide catalyst

Abstract

Mesoporous ceria–cobalt (Ce0.9Co0.1O2, Ce0.8Co0.2O2, and Ce0.7Co0.3O2) mixed oxides, ceria (CeO2), and cobalt oxide (Co3O4) catalysts were prepared through modified template-assisted method and employed in oxidation of ethylbenzene with molecular oxygen (O2) without solvent and additives. Prepared catalysts were characterized by various physicochemical characterization techniques. The XRD results showed the formation of solid solutions in cobalt-doped ceria samples. The XPS results indicated the presence of more Ce3+ ions and surface adsorbed oxygen. H2-TPR profiles revealed a remarkable improvement in the redox behavior of ceria with the doping of cobalt into the ceria lattice. TEM and N2 adsorption studies showed mesoporous nature of materials. Among the prepared catalysts, Ce0.9Co0.1O2 showed far better activity for oxidation of ethylbenzene with 60% conversion and 87% selectivity toward acetophenone. This is attributed to facile redox behavior, more surface adsorbed oxygen species, and larger surface area of the catalyst and considered as crucial factors to improve the catalytic activity.

Graphical abstract

Mesoporous ceria–cobalt (Ce0.9Co0.1O2) mixed oxide efficiently catalyzed the aerobic oxidation of ethylbenzene to acetophenone without solvent with good conversion and selectivity.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Scheme 1
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Scheme 2

References

  1. 1.

    A.K. Suresh, M.M. Sharma, T. Sridhar, Ind. Eng. Chem. Res. 39, 3958 (2000)

    CAS  Article  Google Scholar 

  2. 2.

    R.A. Sheldon, J.K. Kochi, Metal-Catalyzed Oxidations of Organic Compounds (Academic Press, Cambridge, 1981), p. 108

    Google Scholar 

  3. 3.

    T. Punniyamurthy, S. Velusamy, J. Iqbal, Chem. Rev. 105, 2329 (2005)

    CAS  PubMed  Article  Google Scholar 

  4. 4.

    S.S. Shannon, Science 309, 1824 (2005)

    Article  Google Scholar 

  5. 5.

    P. Zhang, H. Lu, Y. Zhou, L. Zhang, Z. Wu, S. Yang, S. Dai, Nat. Commun. 6, 8446 (2015)

    CAS  PubMed  Article  Google Scholar 

  6. 6.

    T. Liu, H. Cheng, L. Sun, F. Liang, C. Zhang, Z. Ying, W. Lin, F. Zhao, Appl. Catal. A 512, 9 (2016)

    CAS  Article  Google Scholar 

  7. 7.

    M.S. Hamdy, A. Ramanathan, T. Maschmeyer, U. Hanefeld, J.C. Jansen, Chem. Eur. J. 12, 1782 (2006)

    CAS  PubMed  Article  Google Scholar 

  8. 8.

    V. Chaudhary, S. Sharma, Catal. Today 375, 601 (2021)

  9. 9.

    X. Hu, X. Sun, Q. Song, Y. Zhu, Y. Long, Z. Dong, Green Chem. 22, 742 (2020)

    CAS  Article  Google Scholar 

  10. 10.

    H.J. Sanders, H.F. Keag, H.S. McCulloug, Ind. Eng. Chem. 45, 2 (1953)

    CAS  Article  Google Scholar 

  11. 11.

    J.Y. Qi, H.X. Ma, X.J. Li, Z.Y. Zhou, M.C.K. Choi, A.S.C. Chan, Q.Y. Yang, Chem. Commun. 11, 1294–1295 (2003)

    Article  CAS  Google Scholar 

  12. 12.

    C. Ricca, F. Labat, N. Russo, C. Adamo, E. Sicilia, J. Phys. Chem. C 118, 12275 (2014)

    CAS  Article  Google Scholar 

  13. 13.

    J. Liu, R. Meng, P. Jian, R. Jian, ACS Sustain Chem. Eng. 8(45), 16791 (2020)

    CAS  Article  Google Scholar 

  14. 14.

    J. Qin, Z. Fu, Y. Liu, X. He, D. Zhang, W. Wu, Y. Wang, X. Gong, X. Deng, H. Wu, Y. Zou, N. Yu, D. Yin, Chin. J. Catal. 32, 1342 (2011)

    CAS  Article  Google Scholar 

  15. 15.

    C. Lu, Z. Fu, Y. Liu, F. Liu, Y. Wu, J. Qin, X. He, D. Yin, J. Mol. Catal. A: Chem. 331, 106 (2010)

    CAS  Article  Google Scholar 

  16. 16.

    P. Zhang, Y. Gong, H. Li, Z. Chen, Y. Wang, Nat. Commun. 4, 1593 (2013)

    PubMed  Article  CAS  Google Scholar 

  17. 17.

    J. Long, H. Liu, S. Wu, S. Liao, Y. Li, ACS Catal. 3, 647 (2013)

    CAS  Article  Google Scholar 

  18. 18.

    D.H. Shen, L.T. Ji, Z.G. Liu, W.B. Sheng, C.C. Guo, J. Mol. Catal. A: Chem. 379, 15 (2013)

    CAS  Article  Google Scholar 

  19. 19.

    W.-F. Xu, W.-J. Chen, D.-C. Li, B.-H. Cheng, H. Jiang, Ind. Eng. Chem. Res. 58(10), 3969 (2019)

    CAS  Article  Google Scholar 

  20. 20.

    M. Liu, Z. Xiao, J. Dai, W. Zhong, Q. Xu, L. Mao, D. Yin, Chem. Eng. J. 313, 1382 (2017)

    CAS  Article  Google Scholar 

  21. 21.

    X. Lin, Z. Nie, L. Zhang, S. Mei, Y. Chen, B. Zhang, R. Zhu, Z. Liu, Green Chem. 19, 2164 (2017)

    CAS  Article  Google Scholar 

  22. 22.

    S. Pendem, R. Singuru, C. Sarkar, B. Joseph, J. Lee, D.B. Shinde, Z. Lai, J. Mondal, ACS Appl. Nano Mater. 1(9), 4836 (2018)

    CAS  Article  Google Scholar 

  23. 23.

    L. Gao, W. Zhuge, X. Feng, W. Sun, X. Sun, G. Zheng, New J. Chem. 43, 8189 (2019)

    CAS  Article  Google Scholar 

  24. 24.

    S. Jie, X. Lin, Z. Chao, Z. Liu, Mater. Chem. Phys. 214, 239 (2018)

    CAS  Article  Google Scholar 

  25. 25.

    B.M. Reddy, L. Katta, G. Thrimurthulu, Chem. Mater. 22, 467 (2010)

    CAS  Article  Google Scholar 

  26. 26.

    S.K. Megarajana, S. Rayalu, Y. Teraoka, N. Labhsetwar, J. Mol. Catal. A: Chem. 385, 112 (2014)

    Article  CAS  Google Scholar 

  27. 27.

    J. Luo, M. Meng, J. Yao, X. Li, Y. Zha, X. Wang, T. Zhang, Appl. Catal. B 87, 92 (2009)

    CAS  Article  Google Scholar 

  28. 28.

    B.M. Reddy, G.K. Reddy, L. Katta, J. Mol. Catal. A: Chem. 404–405, 167 (2015)

    Google Scholar 

  29. 29.

    L. Katta, P. Sudarsanam, G. Thrimurthulu, B.M. Reddy, Appl. Catal. B 101, 101 (2010)

    CAS  Article  Google Scholar 

  30. 30.

    J. Xiong, X. Mei, J. Liu, Y. Wei, Z. Zhao, Z. Xie, J. Li, Appl. Catal. B 251, 247 (2019)

    CAS  Article  Google Scholar 

  31. 31.

    J. Xiong, Q. Wu, X. Mei, J. Liu, Y. Wei, Z. Zhao, D. Wu, J. Li, ACS Catal. 8, 7915 (2018)

    CAS  Article  Google Scholar 

  32. 32.

    J. Xiong, Y. Wei, Y. Zhang, P. Zhang, Q. Yu, X. Mei, X. Liu, Z. Zhao, J. Liu, ACS Catal. 10, 7123 (2020)

    CAS  Article  Google Scholar 

  33. 33.

    P.R.G.N. Reddy, B.G. Rao, T.V. Rao, B.M. Reddy, Appl. Petrochem. Res. 10, 67 (2020)

    CAS  Article  Google Scholar 

  34. 34.

    B.G. Rao, P. Sudarsanam, A. Rangaswamy, B.M. Reddy, Catal. Lett. 145, 1436 (2015)

    Article  CAS  Google Scholar 

  35. 35.

    S. Ramana, B.G. Rao, P. Venkataswamy, A. Rangaswamy, B.M. Reddy, J. Mol. Catal. A: Chem. 415, 113 (2016)

    CAS  Article  Google Scholar 

  36. 36.

    B.M. Reddy, G. Trimurthulu, P. Saikia, P. Bharali, J. Mol. Catal. A: Chem. 275, 67 (2007)

    Article  CAS  Google Scholar 

  37. 37.

    P. Venkataswamy, K.N. Rao, D. Jampaiah, B.M. Reddy, Appl. Catal. B 162, 122 (2015)

    CAS  Article  Google Scholar 

  38. 38.

    N.D. Wasalathanthri, T.M. SantaMaria, D.A. Kriz, S.L. Dissanayake, C.H. Kuo, S. Biswas, S.L. Suib, Appl. Catal. B 201, 543 (2017)

    CAS  Article  Google Scholar 

  39. 39.

    G. Zhou, P.R. Shah, R.J. Gorte, Catal. Lett. 120, 191 (2008)

    CAS  Article  Google Scholar 

  40. 40.

    S.P. Wang, T.Y. Zhang, Y. Su, S.R. Wang, S.M. Zhang, B.L. Zhu, S.H. Wu, Catal. Lett. 121, 71 (2008)

    Article  Google Scholar 

  41. 41.

    B.G. Rao, P. Sudarsanam, P.R.G. Nallappareddy, M.Y. Reddy, T.V. Rao, B.M. Reddy, Res. Chem. Intermed. 44, 6151 (2018)

    CAS  Article  Google Scholar 

  42. 42.

    B.G. Rao, D. Jampaiah, P. Venkataswamy, B.M. Reddy, Chem. Sel. 1, 6681 (2016)

    Google Scholar 

  43. 43.

    D. Terribile, A. Trovarelli, J. Llorca, C. de Leitenburg, G. Dolcetti, Catal. Today 43, 79 (1998)

    CAS  Article  Google Scholar 

  44. 44.

    O.H. Laguna, F.R. Sarria, M.A. Centeno, J.A. Odriozola, J. Catal. 276, 360 (2010)

    CAS  Article  Google Scholar 

  45. 45.

    S. Mahmoodi, M.R. Ehsani, S.M. Ghoreishi, J. Ind. Eng. Chem. 16, 923 (2010)

    CAS  Article  Google Scholar 

  46. 46.

    W.Y. Hernandez, M.A. Centeno, F.R. Sarria, J.A. Odriozola, J. Phys. Chem. C 113, 5629 (2009)

    CAS  Article  Google Scholar 

  47. 47.

    B.G. Rao, D. Jampaiah, P. Venkataswamy, B.M. Reddy, ChemistrySelect 1, 6681 (2016)

    Article  CAS  Google Scholar 

  48. 48.

    P. Sudarsanam, B. Hillary, D.K. Deepa, M.H. Amin, B. Mallesham, B.M. Reddy, S.K. Bhargava, Catal. Sci. Technol. 5, 3496 (2015)

    CAS  Article  Google Scholar 

  49. 49.

    J.C. Fuggle, M. Campagna, Z. Zolnierek, R. Lasser, A. Platau, Phys. Rev. Lett. 45, 1597 (1980)

    CAS  Article  Google Scholar 

  50. 50.

    D. Devaiah, T. Tsuzuki, T. Boningari, P.G. Smirniotis, B.M. Reddy, RSC Adv. 5, 30275 (2015)

    Article  CAS  Google Scholar 

  51. 51.

    B.G. Rao, P. Sudarsanam, B. Mallesham, B.M. Reddy, RSC Adv. 6, 95252 (2016)

    CAS  Article  Google Scholar 

  52. 52.

    H. Zhang, F. Gu, Q. Liu, J. Gao, L. Jia, T. Zhu, Y. Chen, Z. Zhong, F. Su, RSC Adv. 4, 14879 (2014)

    CAS  Article  Google Scholar 

  53. 53.

    C. Bozo, N. Guilhaume, J. Herrmann, J. Catal. 203, 393 (2001)

    CAS  Article  Google Scholar 

  54. 54.

    J. Fan, X.D. Wu, X.D. Wu, Q. Liang, R. Ran, D. Weng, Appl. Catal. B 81, 38 (2008)

    CAS  Article  Google Scholar 

  55. 55.

    J. Liu, J. Li, R. Meng, P. Jian, L. Wang, J. Colloid Interface Sci. 551, 261 (2019)

    CAS  PubMed  Article  Google Scholar 

  56. 56.

    C. Liu, H. Xian, Z. Jiang, L. Wang, J. Zhang, L. Zheng, Y. Tan, X. Li, Appl. Catal. B 176–177, 542 (2015)

    Article  CAS  Google Scholar 

  57. 57.

    J. Liu, R. Meng, J. Li, P. Jian, L. Wang, R. Jian, Appl. Catal. B 254, 214 (2019)

    CAS  Article  Google Scholar 

  58. 58.

    C. Lee, Y. Jeon, S. Hata, J. Park, R. Akiyoshi, H. Saito, Y. Teraoka, Y.G. Shul, H. Einaga, Appl. Catal. B 191, 157 (2016)

    CAS  Article  Google Scholar 

  59. 59.

    S. Damyanova, C.A. Perez, M. Schmal, J.M.C. Bueno, Appl. Catal. A 234, 271 (2002)

    CAS  Article  Google Scholar 

  60. 60.

    H. Li, C.Y. Wu, Y. Li, J. Zhang, Environ. Sci. Technol. 45, 7394 (2011)

    CAS  PubMed  Article  Google Scholar 

  61. 61.

    S. Mandala, C. Santra, K.K. Bando, O.O. James, S. Maityc, D. Mehtad, B. Chowdhury, J. Mol. Catal. A 378, 47 (2013)

    Article  CAS  Google Scholar 

  62. 62.

    S. Li, X. Li, H. Wu, X. Sun, F. Gu, L. Zhang, H. He, L. Li, ACS Appl. Mater. Interfaces 11, 23957 (2019)

    CAS  PubMed  Article  Google Scholar 

  63. 63.

    M. Machida, D. Kurogi, T. Kijima, Chem. Mater. 12, 3165 (2000)

    CAS  Article  Google Scholar 

  64. 64.

    B. Murugan, A.V. Ramaswamy, D. Srinivas, C.S. Gopinath, V. Ramaswamy, Chem. Mater. 17, 3983 (2005)

    CAS  Article  Google Scholar 

  65. 65.

    I. Hermans, P.A. Jacobs, J. Peeters, J. Mol. Catal. A: Chem. 251, 221 (2006)

    CAS  Article  Google Scholar 

Download references

Acknowledgements

Authors P.S and S.N thank University Grant Commission (UGC), New Delhi and K.Y thank Council of Scientific and Industrial Research (CSIR), New Delhi, for the research fellowships. Authors thank Director CSIR-IICT for permission to communicate this work (IICT/Pubs./2021/091), Dr N Lingaiah for TPR, and Dr K Manorama for XPS data.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Venkateshwar Rao Tumula.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Palli, S., Kamma, Y., Silligandla, N. et al. Aerobic oxidation of ethylbenzene to acetophenone over mesoporous ceria–cobalt mixed oxide catalyst. Res Chem Intermed (2021). https://doi.org/10.1007/s11164-021-04604-6

Download citation

Keyword

  • Ethylbenzene
  • Aerobic oxidation
  • CeO2–Co3O4 mixed oxide catalysts
  • Cobalt-doped ceria
  • Ceria solid solutions
  • Acetophenone