COPPER CHROMITE CATALYSTS
419
a peak associated with CO adsorption on Cu+1 sites reached
a maximum after the 573 K pretreatment, and XRD pat-
terns also provided evidence for a Cu+1 phase (CuCrO2),
although they also showed a continuous increase in the Cu0
phase as reduction temperature increased. Consequently,
8. Mehta, S., Simmons, G. W., Klier, K., and Herman, R. G., J. Catal. 57,
339 (1979).
9. Monnier, J. R., Hanrahan, M. J., and Apai, G., J. Catal. 92, 119 (1985).
10. Makarova, O. V., Yur’eva, T. M., Kustova, G. N., Ziborov, A. V.,
Plyasova, L. M., Miyukova, T. P., Davydora, L. P., and Zaikovskii,
V. I., Kinet. Catal. 34, 683 (1993).
Cu+1 sites correlate with activity and appear to be involved 11. Imura, A., Inoue, Y., and Yasumori, I., Bull. Chem. Soc. Jpn. 56, 2203
(1983).
in the catalytic process, as proposed by previous workers,
12. Capece, F. M., Castro, V. D., Furlani, C., Mattogno, G., Fragale, C.,
Gargano, M., and Rossi, M., J. Elec. Spec. Rel. Phenom. 27, 119 (1982).
13. Nishimura, E., Inoue, Y., and Yasumori, I., Bull. Chem. Soc. Jpn. 48,
but the presence of Cu0 sites is probably also required, thus
providing one explanation for the maximum in activity that
occurs as a function of reduction temperature. Selectivity to
803 (1975).
furfural alcohol ranged from 35–70% , significant deactiva- 14. Stroupe, J. D., J. Am. Chem. Soc. 71, 569 (1949).
15. Yurchenko, E. N., Boronin, A. I., Ziborov, A. V., Korolkova, O. G.,
tion occurred, and reaction orders on furfural and H2 were
near unity after correction for deactivation. A straightfor-
ward Langmuir–Hinshelwood model described these data
well. In contrast to furfural, little deactivation was observed
during crotonaldehyde hydrogenation, a lower apparent
activation energy was observed, and the dependency on
the organic reactant was near zero order, although that on
H2 was still near first order. IR spectra taken under re-
action conditions indicated the presence of adsorbed cro-
Zubritskaya, N. G., and Playasova, L. M., Kinet. Catal. 33, 401 (1990).
16. Ma, J., Rodriguez, N. M., Vannice, M. A., and Baker, R. T. K., to be
published.
17. Na, B.-K., Walters, A. B., and Vannice, M. A., Appl. Spect. 140, 585
(1993).
18. Venter, J. J., and Vannice, M. A., Appl. Spec. 42, 1096 (1988).
19. Fanning, P. E., and Vannice, M. A., Carbon 31, 721 (1993).
20. Venter, J. J., and Vannice, M. A., Carbon 26, 889 (1988).
21. Davydov, A. A., “Infrared Spectroscopy of Adsorbed Species on the
Surface of Transition Metal Oxides,” Wiley, London, 1990.
tonaldehyde, provided evidence for an unsaturate alkox- 22. Choi, K. I., and Vannice, M. A., J. Catal. 131, 22 (1991).
23. Dandekar, A., Ph.D. thesis, Pennsylvania State University, in progress.
24. Sen, B., and Vannice, M. A., J. Catal. 115, 65 (1989).
25. Socrates, G., “Infrared Characteristic Group Frequencies,” Wiley,
ide intermediate, and detected no butyraldehyde. A simple
Langmuir–Hinshelwood reaction sequence incorporating
this intermediate gave an excellent fit of the data, along
Chichester, 1980.
with physically meaningful values for enthalpies and en-
tropies of adsorption that imply weak adsorption for both
crotonaldehyde and hydrogen.
26. Nakanishi, K., “Infrared Absorption Spectroscopy,” Holden-Day, San
Francisco, 1977.
27. Leon y Leon, C. A., and Vannice, M. A., Appl. Catal. 69, 269 (1991).
28. Chinchen, G. C., Hay, C. M., Vandervell, M. D., and Waugh, K. C.,
J. Catal. 103, 79 (1987).
ACKNOWLEDGMENT
29. Winter, E. R. S., J. Catal. 19, 32 (1970).
30. Kapteijn, F., Rodriguez-Mirasol, J., and Moulijn, J. A., Appl. Catal. B:
Environ. 9, 25 (1996).
31. Kaufmann, A., and Adams, J. C., J. Am. Chem. Soc. 45, 3029 (1923).
32. Elderfield, R. C. (Ed.), “Heterocyclic Compounds,” Vol. 1, p. 161,
Wiley, New York, 1950.
Support for this project was provided by the National Science Founda-
tion under Grant CTS-9415335.
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