Dispersion and reduction behavior of CuO/α-Fe₂O₃ systems

Abstract

The dispersion and reduction behaviors of CuO/α-Fe₂O₃ samples have been studied by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) and temperature programmed reduction (TPR). XRD and XPS results show that the dispersion capacity of CuO on α-Fe₂O₃ is about 13.7 Cu²⁺ nm^-2 (α-Fe₂O₃). At low copper loading, highly dispersed surface copper oxide is the main species, and crystalline CuO evidently appears after the Cu loading exceeds the dispersion capacity. For Cu XPS spectra, the intensity ratio of satellite peaks (I_sat) to the principal peaks (I_pp) shows that the highly dispersed Cu²⁺ ions simultaneously exist as tetrahedrally and octahedrally coordinated states in the low Cu loading samples, and the octahedrally coordinated surface Cu species is the predominant species in high Cu loading samples, which is in basic agreement with the prediction of the incorporation model proposed previously (Y. Chen and L. F. Zhang, Catal. Lett., 1992, 12, 51). The BET surface area of α-Fe₂O₃ support in all the samples remains constant, indicating that the calcination process has not induced an evident change to the surface of α-Fe₂O₃ support. TPR results indicate that the reduction peaks at about 473 and 493 K correspond to the reduction of the octahedrally and tetrahedrally coordinated surface copper oxide species, respectively, and the reduction peak at about 563 K is ascribed to the reduction of crystalline CuO. In addition, the influence of the different calcination temperatures on the interaction between CuO and α-Fe₂O₃ has also been investigated by XRD, TPR and XPS, and the results show that the calcination temperature can affect the extent of interaction, and a new compound, CuFe₂O₄, formed as the CuO/α-Fe₂O₃ sample was calcined at 1123 K.

References

1. C. L. Thomas, Catalytic Processes and Proven Catalysts, Academic Press, New York, 1976, p. 198.
2. L. Hodges, Environmental Pollution, Holt, Rinehart and Winston, New York, 1972.
3. R. Behara, Appl. Catal., 1985, 16, 15.
4. B. Strohmeier, D. E. Leiden, R. S. Field and D. M. Hercules, J. Catal., 1985, 94, 514.
5. G. Ertl, R. Hierl, H. Knozinger, N. Thiele and H. P. Urbach, Appl. Surf. Sci., 1980, 5, 49.
6. R. Hierl, H. Knozinger and H. P. Urbach, J. Catal., 1981, 69, 475.
7. M. Barber, P. K. Sharpe and J. C. Vickerman, J. Catal., 1976, 41, 240.
8. H. Lumbeck and J. Voitlander, J. Catal., 1969, 132, 117.
9. R. M. Friedman, J. J. Freeman and F. W. Lytle, J. Catal., 1978, 55, 10.
10. M. Shelef, M. A. Z. Wheeler and H. C. Yao, Surf. Sci., 1975, 47, 697.
11. F. E. Massoth, Adv. Catal., 1978, 27, 265.
12. S. F. Tikhov, V. A. Sadykov, G. N. Kryukova, E. A. Paukshtis, V. V. Popovskii, T. G. Starostina, G. V. Kharlamov, V. F. Anufrienko, V. F. Poluboyarov, V. A. Razdobarov, N. N. Bulgakov and A. V. Kalinkin, J. Catal., 1992, 134, 506.
13. M. Lo. Jacono, A. Cimino and M. Inversi, J. Catal., 1982, 76, 320; W. P. Dow and T. J. Huang, J. Catal., 1996, 160, 155, 171.
14. Th. Simons, E. Vrheijen, Ph. A. Batist and G. C. A. Schuit, Adv. Chem. Ser., 1968, no. 76, vol. 2, 261.
15. K. Weissermet and H. J. Arpe, Industrial Organic Chemistry, Verlag Chemie, Weinheim, 1978, p. 297.
16. K. Weissermel and H. J. Arpe, Industrial Organic Chemistry, Verlag Chemie, Weinheim, 1978, p. 36.
17. S. R. Morrison, The Chemical Physics of Surfaces, Plenum, New York, 1977, p. 361.
18. M. Niwa, M. Sano, H. Yamada and Y. Murakami, J. Catal., 1995, 151, 285; H. Yamada, M. Niwa and Y. Murakami, Appl. Catal., A, 1993, 96, 113.
19. L. Dong, K. Chen and Y. Chen, J. Solid State Chem., 1997, 129, 30.
20. Y. C. Xie and Y. Q. Tang, Adv. Catal., 1990, 37, 1.
21. P. Mikusik, T. Juska, J. Novakova, L. Kubelkova and B. Wichterlova, J. Chem. Soc., Faraday Trans. 1, 1981, 77(5), 1179.
22. G. C. Bond, J. P. Zurita and S. Flamerz, Appl. Catal., 1986, 27, 353.
23. M. Wu and D. M. Hercules, J. Phys. Chem., 1979, 83(15), 2003.
24. L. Dong and Y. Chen, J. Chem. Soc., Faraday Trans., 1996, 92(22), 4589.
25. D. C. Frost, A. Ishitani and C. A. McDowell, Mol. Phys., 1972, 24, 861.
26. A. F. Wells, Structural Inorganic Chemistry, Oxford University Press, 1984, p. 539.
27. M. Niwa, H. Yamada and Y. Murakami, J. Catal., 1992, 134, 331.
28. Powder diffraction file, Sets 25–26, published by the JCPDS, printed in USA International Centre for Diffraction Data, 1601 Park Lane, Swarthmore, Pennsylvania 19801, USA, 1984, P101, no. 25–283.