Abstract
The reaction routes of 1,2-dichloroethane dechlorination to ethylene on discrete nanoclusters that served as models of the active sites of supported Cu-Pt catalysts were calculated. Two reaction pathways were predicted. The first route corresponds to sequential elimination of the chlorine atoms from 1,2-dichloroethane; this is a three-stage reaction that occurs via two stable intermediates (stepwise mechanism). The limiting stage is the stage that corresponds to the dissociation of the first C-Cl bond. The second channel corresponds to a simultaneous one-stage elimination of two chlorine atoms (direct mechanism). Both reaction routes are thermodynamically possible, but the stepwise process is more probable, in contrast to the process on monometallic Cu catalysts. For the stepwise process, the vibrational spectra of stable intermediates were calculated for identification of the latter. A set of spectral data characteristic for the stepwise mechanism were determined. The three-step molecular mechanism suggested for 1,2-dichloroethane dechlorination to ethylene is compared with several kinetic schemes known from the literature. Possible modifications of the reaction route that forms ethane and monochloroethane are analyzed.
Similar content being viewed by others
References
V. I. Avdeev, V. I. Kovalchuk, G. M. Zhidomirov, and J. L. d’Itri, J. Struct. Chem., 48, Supplement, S160–S170 (2007).
J. H. Sinfelt, Bimetallic Catalysts: Discoveries, Concepts and Applications, Wiley, New York (1983).
V. Ponec and G. C. Bond, Catalysis by Metals and Alloys, Elsevier, Amsterdam (1995).
L. N. Zanaveskin, V. A. Aver’yanov, and Yu. A. Treger, Usp. Khim., 65, 667–675 (1996).
L. S. Vadlamannati, V. I. Kovalchuk, and J. L. d’Itri, Catal. Lett., 58, 173–178 (1999).
L. S. Vadlamannati, D. R. Luebke, V. I. Kovalchuk, and J. L. d’Itri, Stud. Surf. Sci. Catal., 130A, 233–238 (2000).
P. P. Kulkarni, V. I. Kovalchuk, and J. L. d’Itri, Appl. Catal. B, 36, 299–309 (2002).
D. R. Luebke, L. S. Vadlamannati, V. I. Kovalchuk, and J. L. d’Itri, ibid., 35, 211–217 (2002).
V. Yu. Borovkov, D. R. Luebke, V. I. Kovalchuk, and J. L. d’Itri, J. Phys. Chem. B, 107, 5568–5574 (2003).
V. I. Kovalchuk and J. L. d’Itri, Appl. Catal. A, 171, 13–25 (2004).
R. G. Parr and W. Yang, Density-Functional Theory of Atoms and Molecules, Oxford University Press, New York (1989).
M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., GAUSSIAN, Revision A.11, Pittsburgh, PA (2001).
T. Zambelli, J. Wintterlin, J. Trost, and G. Ertl, Science, 273, 1688–1696 (1996).
S. Dahl, A. Logadottir, R. C. Egeberg, et al., Phys. Rev. Lett., 83, 1814–1817 (1999).
W. A. de Heer, Rev. Mod. Phys., 65, 611–676 (1993).
V. I. Avdeev, V. I. Kovalchuk, G. M. Zhidomirov, and J. L. d’Itri, Surf. Sci., 583, 46–59 (2005).
S. Glasstote, J. K. Laidler, and H. Eyring, The Rate of Processes, New York (1941).
T. B. Scoggins and J. M. White, J. Phys. Chem. B, 103, 9663–9672 (1999).
T. Shimanouchi, Tables of Molecular Vibrational Frequencies, Consolidated Vol. I, National Bureau of Standards (1972), pp. 1–160.
V. Ponec, Appl. Catal. A, General, 222, 31–45 (2001).
Author information
Authors and Affiliations
Corresponding author
Additional information
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 48, Supplement, pp. S180–S192, 2007.
Original Russian Text Copyright © 2007 by V. I. Avdeev, V. I. Kovalchuk, G. M. Zhidomirov, and J. L. d’Itri
Rights and permissions
About this article
Cite this article
Avdeev, V.I., Kovalchuk, V.I., Zhidomirov, G.M. et al. DFT analysis of the mechanism of 1,2-dichloroethane dechlorination on supported Cu-Pt bimetallic catalysts. J Struct Chem 48 (Suppl 1), S171–S183 (2007). https://doi.org/10.1007/s10947-007-0160-3
Received:
Issue Date:
DOI: https://doi.org/10.1007/s10947-007-0160-3