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Models of active sites in supported Cu metal catalysts in 1,2-dichloroethane dechlorination. DFT analysis

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Abstract

It is suggested that a set of discrete Cu nanoclusters satisfying the conditions of structural and electron stability should be used as models of active sites on supported metal catalysts. The close-packed Cu20 tetrahedral nanocluster that satisfies these two conditions was taken as a base model of active sites on supported copper catalysts. Theoretical analysis of two possible mechanisms of C-Cl bond dissociation of 1,2-dichloroethane on copper catalysts was performed by the density functional theory method. The first mechanism involves sequential splitting of C-Cl bonds in the molecule in three stages with further stabilization of chloroalkyl intermediates (stepwise mechanism). All these stages are activated. The limiting stage is the one that corresponds to dissociation of the first C-Cl bond with an activation energy of E# = 34.3 kcal/mol. The second mechanism corresponds to the simultaneous elimination of two chlorine atoms from 1,2-dichloroethane with liberation of ethylene in the gas phase; this is a one-stage process with an activation energy of E# = 26.1 kcal/mol (direct mechanism). A comparison of the two reaction routes shows that the direct mechanism is most probable on copper catalysts.

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Authors and Affiliations

  1. G. K. Boreskov Institute of Catalysis, Novosibirsk

    V. I. Avdeev & G. M. Zhidomirov

  2. Pittsburgh University, USA

    V. I. Kovalchuk & J. L. d’Itri

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  1. V. I. Avdeev
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  2. V. I. Kovalchuk
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  3. G. M. Zhidomirov
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  4. J. L. d’Itri
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Correspondence to V. I. Avdeev.

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__________

Translated from Zhurnal Strukturnoi Khimii, Vol. 48, Supplement, pp. S169–S179, 2007.

Original Russian Text Copyright © 2007 by V. I. Avdeev, V. I. Kovalchuk, G. M. Zhidomirov, and J. L. d’Itri

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Avdeev, V.I., Kovalchuk, V.I., Zhidomirov, G.M. et al. Models of active sites in supported Cu metal catalysts in 1,2-dichloroethane dechlorination. DFT analysis. J Struct Chem 48 (Suppl 1), S160–S170 (2007). https://doi.org/10.1007/s10947-007-0159-9

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  • DOI: https://doi.org/10.1007/s10947-007-0159-9

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