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Bimetallic Co–Ni/TiO2 catalysts for selective hydrogenation of cinnamaldehyde

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Abstract

Bimetallic Co–Ni catalysts in the composition range Co(1−x)Nix with x = 0.0, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8 and 1.0, with total metal loading of 15% w/w and supported on TiO2-P25, have been prepared by chemical reduction of the metal acetates by glucose in aqueous alkaline medium and characterized by XRD, TEM, TPR, XPS and H2-TPD techniques. Selective hydrogenation of cinnamaldhyde (CAL) to hydrocinnamaldehyde (HCAL), cinnamyl alcohol (COL) and hydrocinnamyl alcohol (HCOL) has been investigated at 20 bar pressure, in the temperature range 120–140 °C. Co/Ni crystallite sizes in the range 6.0 ± 1 nm are observed by TEM. TPR and XPS results indicate the formation of nanoscale Co–Ni alloys, which tend to weaken M–H bond strength, as revealed by H2-TPD measurements. Ni/TiO2 displays very high conversion of CAL (86.9%) with high selectivity (78.7%) towards HCAL formation at 140 °C. Co/TiO2, on the other hand, exhibits relatively lower CAL conversion (55%) and higher selectivity (61.3%) for COL formation at the same temperature. However, bi-metallic Co–Ni catalysts in the composition range x = 0.3–0.6 display very high conversion (> 98%) due to alloy formation and weakening of M–H bonds. Bimetallic Co0.7Ni0.3 catalyst displays high conversion of CAL (98.1%) and high selectivity (82.9%) towards HCOL. Overall CAL hydrogenation activity at 140 °C, when expressed as TOF, displays a maximum value at the composition Co0.5Ni0.5. Activity and selectivity patterns have been rationalized based on the reaction pathways observed on the catalysts and the influence of Co–Ni alloy formation and M–H bond strength. Thus, a synergetic effect, originating from an appropriate composition of base metal catalysts and reaction conditions, could result in hydrogenation activity comparable with noble metal based catalysts.

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References

  1. P. Gallezot, D. Richard, Catal. Rev. Sci. Eng. 40, 81 (1998)

    Article  CAS  Google Scholar 

  2. A. Giroir-Fendler, D. Richard, P. Gallezot, in Studies in Surface Science and Catalysis, vol. 41, ed. by J. Barrault, C. Bouchoule, D. Duprez, C. Montassier, M. Guisnet, G. Pérot (Elsevier, Amsterdam, 1988), pp. 171–178

    Google Scholar 

  3. M.G. Prakash, R. Mahalakshmy, K.R. Krishnamurthy, B. Viswanathan, Catal. Today 263, 105 (2016)

    Article  CAS  Google Scholar 

  4. W. Yu, Y. Wang, H. Liu, W. Zheng, J. Mol. Catal. A 112, 105 (1996)

    Article  CAS  Google Scholar 

  5. B. Coq, P.S. Kumbhar, C. Moreau, P. Moreau, M.G. Warawdekar, J. Mol. Catal. 85, 215 (1993)

    Article  CAS  Google Scholar 

  6. B. Coq, P.S. Kumbhar, C. Moreau, P. Moreau, F. Figueras, J. Phys. Chem. 98, 10180 (1994)

    Article  CAS  Google Scholar 

  7. R. Basale, Ph.D. Thesis, (Tech. Univ. Eindhoven, Netherland, 2013)

  8. P. Mäki-Arvela, L.P. Tiainen, M. Lindblad, K. Demirkan, N. Kumar, R. Sjöholm, T. Ollonqvist, J. VäyrynenSalmi, DYu. Murzin, Appl. Catal. A 241, 271 (2003)

    Article  Google Scholar 

  9. X. Yuan, J. Zheng, Q. Zhang, S. Li, Y. Yang, J. Gong, AIChE J. 60, 1036 (2012)

    Google Scholar 

  10. E. Asedegbega-Nieto, B. Bachiller-Baeza, A. Guerrero-Ruíz, I. Rodriguez-Ramos, Appl. Catal. A 300, 120 (2006)

    Article  CAS  Google Scholar 

  11. H. Noller, W.M. Lint, J. Catal. 85, 25 (1984)

    Article  CAS  Google Scholar 

  12. S.A. Ananthan, V. Narayanan, Int. J. Chem. 3, 55 (2011)

    Article  CAS  Google Scholar 

  13. B.M. Reddy, G.M. Kumar, I. Ganesh, A. Khan, J. Mol. Catal. A: Chem. 247, 80 (2006)

    Article  CAS  Google Scholar 

  14. L.I. Hui, M.A. Chun-Jing, L.I. He-Xing, Acta Chim. Sinica 64, 1947 (2006)

    Google Scholar 

  15. L.J. Malobela, J. Heveling, W.G. Augustyn, L.M. Cele, Ind. Eng. Chem. Res. 53, 13910 (2014)

    Article  CAS  Google Scholar 

  16. W. Lin, H. Chang, L. He, Y. Yu, F. Zhang, J. Catal. 303, 110 (2013)

    Article  CAS  Google Scholar 

  17. K.J.A. Raj, M.G. Prakash, T. Elangovan, B. Viswanathan, Catal. Lett. 142, 87 (2011)

    Google Scholar 

  18. M. Vasseem, N. Tripathy, G. Khang, Y. Halm, RSC. Adv. 3, 9698 (2013)

    Article  Google Scholar 

  19. H.B. Boubaker, M. Mhamdi, E. Marceau, S. Khaddar-Zine, A. Ghorbel, M. Che, Y.B. Taarit, F. Villain, Microporous Mesoporous Mater. 93, 62 (2006)

    Article  Google Scholar 

  20. R. Li, X. Ren, H. Ma, X. Feng, Z. Lin, X. Li, C. Hu, B. Wang, J. Mater. Chem. A 2, 5724 (2014)

    Article  CAS  Google Scholar 

  21. R.J. Isaifan, H.A.E. Dole, E. Obeid, L. Lizarraga, P. Vernoux, E.A. Baranova, Electrochem. Solid-State Lett. 15, E14 (2012)

    Article  CAS  Google Scholar 

  22. K. Takanabe, K. Nagaoka, K. Nariai, K. Aika, J. Catal. 232, 268 (2005)

    Article  CAS  Google Scholar 

  23. M.M. Van Schooneveld, C. Campos-Cuerva, J. Pet, J.D. Meeldijk, J. van Rijssel, A. Meijerink, B.H. Erne, F.M.F. de Groot, J. Nanopart. Res. 14, 991 (2012)

    Article  Google Scholar 

  24. X.B. Zhang, Y.J. Zhang, F. Chen, Y.Z. Xiang, B. Zhang, L.Y. Xu, T.R. Zhang, Reac. Kinet. Mech. Cat. 115, 283 (2015)

    Article  CAS  Google Scholar 

  25. D. Golodnitsky, N.V. Gudin, G.A. Volyanuk, J. Electrochem. Soc. 147(11), 4156 (2000)

    Article  CAS  Google Scholar 

  26. X. You, X. Wang, Y. Ma, J. Liu, W. Liu, X. Xu, H. Peng, C. Li, W. Zhou, P. Yuan, X. Chen, Chem. Cat. Chem. 6, 3377 (2014)

    CAS  Google Scholar 

  27. M. Phongaksorn, S. Tungkamani, N. Dharmasaroja, T. Chamni, R. Chuvareec, N. Kanjanabat, N. Siri-Nguanc, Chem. Eng. Trans. 43, 925 (2015)

    Google Scholar 

  28. X. Hu, G.X. Lu, J. Mol. Catal. A 261, 43 (2007)

    Article  CAS  Google Scholar 

  29. L.W. Chen, C.K.S. Choong, Z.Y. Zhong, L. Huang, Z. Wang, J.Y. Lin, Int. J. Hydrog Energy 37, 16321 (2012)

    Article  CAS  Google Scholar 

  30. H. Woo, R. Srinivasan, L. Rice, R. De Angelis, P. Reucroft, J. Mol. Catal. 59, 83 (1990)

    Article  CAS  Google Scholar 

  31. I. Tatsumi, E. Koichi, A. Hiromichi, Appl. Catal. 30, 225 (1987)

    Article  Google Scholar 

  32. P.C. Das, N.C. Pradhan, A.K. Dalai, N.N. Bakshi, Catal. Lett. 98, 153 (2004)

    Article  CAS  Google Scholar 

  33. H. Luo, H. Li, H.L. Zhuang, Chem. Lett. 5, 404 (2001)

    Article  Google Scholar 

  34. L. Wei, C. Xianian, L. Jin, Y. Ying, Z. Yongfu, H. Zhaolong, Y. Zhengzhou, Adv. Malts. Res. 430, 917 (2012)

    Google Scholar 

  35. W. Lin, H. Chang, L. He, Y. Yu, F. Zhang, J. Catal. 303, 110 (2013)

    Article  CAS  Google Scholar 

  36. D. Xu, W. Li, H. Duan, Q. Ge, H. Xu, Catal. Lett. 102, 229 (2005)

    Article  CAS  Google Scholar 

  37. N.S. McIntyre, M.G. Cook, Anal. Chem. 47, 2208 (1975)

    Article  CAS  Google Scholar 

  38. H.L. Skriver, N.M. Rosengaard, Phys. Rev. B 46, 7157 (1992)

    Article  CAS  Google Scholar 

  39. S. Velu, S. Gangwal, Solid State Ion. 177, 803 (2006)

    Article  CAS  Google Scholar 

  40. A.G. Boudjahem, S. Monteverdi, M. Mercy, D. Ghanbaja, M.M. Bettahar, Catal. Lett. 84, 115 (2002)

    Article  CAS  Google Scholar 

  41. J. Liu, C. Li, F. Wang, S. He, H. Chen, Y. Zhao, M. Wei, D.G. Evans, X. Duan, Catal. Sci. Technol. 3, 2627 (2013)

    Article  CAS  Google Scholar 

  42. Y. Nitta, K. Ueno, T. Imanaka, Appl. Catal. 56, 9 (1989)

    Article  CAS  Google Scholar 

  43. C. Rudof, B. Dragoi, A. Ungureanu, A. Chirieac, S. Royer, A. Nastroc, E. Dumitriu, Catal. Sci. Technol. 4, 179 (2014)

    Article  Google Scholar 

  44. U.K. Singh, M.A. Vannice, J. Catal. 199, 73 (2001)

    Article  CAS  Google Scholar 

  45. L. Pauling, Proc. R. Soc. A 196, 343 (1949)

    Article  CAS  Google Scholar 

  46. O. Beeck, Faraday. Soc. Discuss. 8, 118 (1950)

    Article  Google Scholar 

  47. J.H. Sinfelt, Science 195, 641 (1977)

    Article  CAS  Google Scholar 

  48. F. Delbecq, P. Sautet, J. Catal. 152, 217 (1995)

    Article  CAS  Google Scholar 

  49. C.S. Fadley, D.A. Shirley, 3rd materials research symposium—electronic density of states. Nov. 3–6, 1969, Gaithersburg, MD

  50. G. Blyholder, D. Shihabi, J. Catal. 46, 91 (1977)

    Article  CAS  Google Scholar 

  51. T. Bligaard, J.K. Nørskov, in Chemical Bonding at Surfaces and Interfaces, 1st Edn., ed. by A. Nilsson, L.G.M. Petterson, J.K. Nørskov (Elsevier, Amsterdam, 2008)

    Google Scholar 

  52. T.M. Huynh, U. Armbruster, L.H. Nguyen, D.A. Nguyen, A. Martin, J. Sustain. Bioenergy Syst. 5, 151 (2015)

    Article  CAS  Google Scholar 

  53. M. Zhao, T.L. Church, A.T. Harris, Appl. Catal. B 101, 522 (2011)

    Article  CAS  Google Scholar 

  54. Y. Wang, M. Chen, Z. Yang, T. Liang, S. Liu, Z. Zhou, X. Li, Appl. Catal A. Gen. 550, 214 (2018)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are thankful to the Department of Science and Technology, Govt. of India, for establishing the research facilities at the National Centre for Catalysis Research for carrying out this work and IIT Madras for providing infrastructure support.

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Authors and Affiliations

  1. National Centre for Catalysis Research (NCCR), Indian Institute of Technology, Madras, Chennai, 600036, India

    Saranya Ashokkumar, Krishnamurthy K. Ramaswamy & Viswanathan Balasubramanian

  2. Department of Chemistry, A V C College, Mayiladuthurai, 609305, India

    Saranya Ashokkumar & Vivekanandan Ganesan

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  1. Saranya Ashokkumar
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  3. Krishnamurthy K. Ramaswamy
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Correspondence to Viswanathan Balasubramanian.

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Ashokkumar, S., Ganesan, V., Ramaswamy, K.K. et al. Bimetallic Co–Ni/TiO2 catalysts for selective hydrogenation of cinnamaldehyde. Res Chem Intermed 44, 6703–6720 (2018). https://doi.org/10.1007/s11164-018-3517-7

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