caa a22 4500 463239725 CHVBK 20180405153309.0 cr unu---uuuuu 170326e20070101xx s 000 0 eng 10.1007/s10947-007-0159-9 doi (NATIONALLICENCE)springer-10.1007/s10947-007-0159-9 Models of active sites in supported Cu metal catalysts in 1,2-dichloroethane dechlorination. DFT analysis [Elektronische Daten] [V. Avdeev, V. Kovalchuk, G. Zhidomirov, J. d'Itri] 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. Springer Science+Business Media, Inc., 2007 1,2-dichloroethane nationallicence dechlorination nationallicence Cu catalysts nationallicence active sites nationallicence reaction mechanism nationallicence DFT calculations nationallicence Avdeev V. G. K. Boreskov Institute of Catalysis, Novosibirsk aut Kovalchuk V. Pittsburgh University, USA aut Zhidomirov G. G. K. Boreskov Institute of Catalysis, Novosibirsk aut d'Itri J. Pittsburgh University, USA aut Journal of Structural Chemistry Springer US 48(2007-01-01), S160-S170 0022-4766 48<S160 2007 48 10947 https://doi.org/10.1007/s10947-007-0159-9 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10947-007-0159-9 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Avdeev V. G. K. Boreskov Institute of Catalysis, Novosibirsk aut NATIONALLICENCE 700 1- Kovalchuk V. Pittsburgh University, USA aut NATIONALLICENCE 700 1- Zhidomirov G. G. K. Boreskov Institute of Catalysis, Novosibirsk aut NATIONALLICENCE 700 1- d'Itri J. Pittsburgh University, USA aut NATIONALLICENCE 773 0- Journal of Structural Chemistry Springer US 48(2007-01-01), S160-S170 0022-4766 48<S160 2007 48 10947 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer