Effect of the addition of Sn to zirconia on the acidic properties of the sulfated mixed oxide

Abstract

Zirconium hydroxide, tin hydroxide and the mixed hydroxide of tin and zirconium (1:9) have been prepared, sulfated with a 0.1 Maqueous H₂SO₄ solution and calcinated at 873 K. The chemical composition of these solids has been characterized by chemical analysis, differential thermal analysis (DTA), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX–) scanning transmission electron microscopy (STEM), and their structural and textural properties have been studied by BET surface area and XRD techniques. The nature of the acid sites (Brønsted or Lewis) was characterized by in situ IR study of pyridine adsorption and desorption and their amount was found to depend on the sulfate content. Catalytic properties have been studied for the isomerization reaction of n-butane to isobutane, in the 423 to 523 K range and for propan-2-ol conversion, in the 373 to 473 K range. Addition of Sn to ZrO₂ (SnO₂:ZrO₂=1:9) led to a solid solution and enhanced slightly (ca. 30%) the weak acid features of ZrO₂ and removed the basic properties of pure SnO₂ which was shown to convert propan-2-ol to acetone. Upon sulfation of ZrO₂, SnO₂–ZrO₂[1:9] and SnO₂, the acidity of the oxides was sharply enhanced. SO₄^2-/SnO₂, which was inactive for the isomerization reaction, was only 60% less active than SO₄^2-/ZrO₂ for propan-2-ol dehydration. This shows that sulfation of SnO₂ generates acid sites of moderate strength. The presence of only 10% of SnO₂ in ZrO₂ decreased the reaction rates per SO₄^2- by a factor of six for the initial n-butane isomerization reaction and by a factor of seven for the propan-2-ol dehydration to propene and diisopropyl ether. It is suggested that the presence of Sn decreases the electron acceptor properties of Zr and thus its acidity strength. Since the rate per sulfated species of both reactions decreased in the same proportion, one may consider that on SO₄^2-/ZrO₂ and SO₄^2-/SnO₂–ZrO₂ samples there is no site of moderate strength able to dehydrate propan-2-ol without isomerising n-butane.

References

1. K. Tanabe, M. Misono, Y. Ono and H. Hattori, Stud. Surf. Sci. Catal., 1989, 51, 199.
2. K. Arata, Adv. Catal., 1990, 37, 165.
3. K. Tanabe, H. Hattori and T. Yamaguchi, Crit. Rev. Surf. Chem., 1990, 1, 1.
4. T. Yamaguchi, Appl. Catal., 1990, 61, 1.
5. A. Corma and A. Martinez, Catal. Rev. Sci. Eng., 1993, 35, 483.
6. M. Hino and K. Arata, J. Chem. Soc., Chem. Commun., 1979, 1148, 1980, 851.
7. T. Yamaguchi, K. Tanabe and Yao Chin Kung, Mater. Chem. Phys., 1986, 7, 67.
8. T. Yamaguchi, T. Jin and K. Tanabe, J. Phys. Chem., 1986, 90, 3148.
9. T. Yamaguchi, T. Jin, T. Ishida and K. Tanabe, Mater. Chem. Phys., 1987, 17, 3.
10. J. R. Sohn and H. W. Kim, J. Mol. Catal., 1989, 52, 361.
11. K. I. Mukaida, T. Miyoshi and T. Satoh, in Acid–base Catalysis I, ed. K. Tanabe, H Hattori, T. Yamaguchi and T. Tanaka, Kodansha, Tokyo, 1989, p. 361.
12. F. R. Chen, G. Coudurier, J. F. Joly and J. C. Védrine, in ACS Symp. Ser., 1991, 36, 878.
13. J. M. Parera, Catal. Today, 1992, 15, 481.
14. F. R. Chen, G. Coudurier, J. F. Joly and J. C. Védrine, J. Catal., 1993, 143, 616.
15. F. Babou, B. Bigot, G. Coudurier, Ph. Sautet and J. C. Védrine, Stud. Surf. Sci. Catal., 1994, 90, 519.
16. C. Morterra, G. Cerrato, F. Pinna, M. Signoretto and G. Strukul, J. Catal., 1994, 149, 181.
17. Z. Gao, J. M. Chen, W. M. Hua and Y. Tang, Stud. Surf. Sci. Catal, 1994, 90, 507.
18. F. Babou, G. Coudurier and J. C. Védrine, J. Catal., 1995, 152, 341.
19. K. Arata and M. Hino, React. Kinet. Catal. Lett., 1984, 25, 143.
20. M. Hino, S. Kobayashi and K. Arata, React. Kinet. Catal. Lett., 1981, 18, 491.
21. A. Kayo, T. Yamaguchi and K. Tanabe, J. Catal., 1983, 83, 99.
22. G. W. Wang, H. Hattori and K. Tanabe, Chem. Lett., 1983, 277.
23. H. Matsuhashi, M. Hino and K. Arata, Appl. Catal., 1990, 59, 205.
24. T. C. Luy, J. C. Yori, A. A. Castro and J. M. Parera, React. Kinet. Catal. Lett., 1988, 36, 275.
25. T. Ishida, T. Yamaguchi and K. Tanabe, Chem. Lett., 1988, 1869.
26. C. Guo, Z. Yu, Z. Qian, J. Huang and Y. Xu, Stud. Surf. Sci. Catal., 1994, 90, 543.
27. F. Lónyi, J. Valyon, J. Engelhardt and F. Mizukami, J. Catal., 1996, 160, 279.
28. J. R. Sohn, H. J. Jang, M. Y. Park, E. H. Park and S. E. Park, J. Mol. Catal., 1994, 93, 149.
29. K. Tanabe, Bull. Chem. Soc. Jpn., 1974, 47, 1064.
30. H. A. Benesi and B. H. C. Windquist, Adv. Catal., 1978, 27, 97.
31. K. Tanabe, M. Misono, Y. Ono and H. Hattori, Stud. Surf. Sci. Catal., 1989, 51, 108.
32. T. Seiyama, Metal Oxides and Their Catalytic Actions, Kodansha, Tokyo, 1978.
33. T. Kataoka and J. A. Dumesic, J. Catal., 1986, 112, 66.
34. H. H. Kung, J. Solid State Chem., 1984, 52, 191.
35. M. Itoh, H. Hattori and K. Tanabe, J. Catal., 1974, 35, 225.
36. H. Hattori, M. Itoh and K. Tanabe, J. Catal., 1975, 38, 172.
37. H. Hattori, M. Itoh and K. Tanabe, J. Catal., 1976, 41, 46.
38. I. C. V. Odenbrand, M. G. J. Brandin and G. Busca, J. Catal., 1992, 135, 505.
39. Z. Liu, J. Tabora and R. J. Davis, J. Catal., 1994, 149, 117.
40. H. J. M. Bosman, E. C. Kruissink, J. van der Spoel and F. van den Brink, J. Catal., 1994, 148, 660.
41. J. B. Miller, S. E. Rankin and E. I. Ko, J. Catal., 1994, 148, 682.
42. S. M. Maurer, D. Ng and E. I. Ko, Catal. Today, 1993, 16, 319.
43. K. Arata, S. Akutagawa and K. Tanabe, Bull. Chem. Soc. Jpn., 1976, 49, 390.
44. Y. Hirashima, K. Nishiwaki, A. Miyakoshi, H. Tsuiki, A. Veno and H. Nakabayashi, Bull. Chem. Soc. Jpn., 1988, 61, 1945.
45. J. A. Navio, M. Macias, F. J. Marchena, J. M. Campelo and J. M. Marinas, in New Frontiers in Catalysis, ed. L. Guczi, F. Solymosi and P. Tétényl, Akedémia Kiado, Budapest, 1993, p. 2597.
46. P. D. L. Mercera, J. G. van Ommen, E. B. Doesburg, A. J. Burgraaf and J. R. H. Ross, Appl. Catal., 1990, 57, 127.
47. R. Srivinasan, R. A. Keogh, D. R. Milburn and B. H. Davis, J. Catal., 1995, 153, 123.
48. J. P. Chen and R. T. Yang, J. Catal., 1993, 139, 277.
49. F. Babou, B. Bigot and Ph. Sautet, J. Phys. Chem., 1993, 97, 11501.
50. T. Jin, T. Yamaguchi and K. Tanabe, J. Phys. Chem., 1986, 90, 4794.
51. R. J. Gillepsie and E. A. Robinson, Can. J. Chem., 1962, 40, 644.
52. P. A. Giguère and R. Savoie, Can. J. Chem., 1963, 41, 287.
53. R. J. Gillespie and E. A. Robinson, Can. J. Chem., 1963, 41, 2074.
54. M. Henry, PhD Thesis, University of Paris VI, 1988.
55. W. J. Mortier, J. Catal., 1978, 55, 138.
56. R. T. Sanderson, Chemical Bonds and Bond Energies, Academic Press, New York, 2nd edn., 1976.
57. F. Babou, G. Coudurier and J. C. Védrine, J. Chim. Phys., 1995, 92, 1457.
58. F. Babou, PhD Thesis, University of Lyon I, 1994, no. 88–94.
59. A. Ouqour, G. Coudurier and J. C. Védrine, J. Chem. Soc., Faraday Trans., 1993, 89, 3151.