Activation of ethane in Zn-exchanged zeolites: a theoretical study

A theoretical study of the mechanism of ethane dehydrogenation catalysed by Zn-doped zeolites was undertaken. The catalyst was modelled by the ring cl uster [Al2Si2O4H8](2-) coordinated with the Zn2+ ion. The results obtained indicate that the reaction proceeds via a mechanism starting from the "alky l'' rupture of the ethane C-H bond (C2H5delta--Hdelta+), and the zinc catio n acts as an acceptor of the alkyl group. The catalytic cycle for the "alky l'' activation consists of three elementary steps: (i) rupture of ethane C- H bond on the Zndelta+-Odelta- pair; (ii) formation of ethene from the alky l group bound to Zn; and (iii) formation of dihydrogen from the Bronsted pr oton and hydrogen bound to Zn. The computed activation energies for these t hree steps are 18.4, 53.4 and 20.5 kcal mol(-1), respectively. The alternat ive mechanism starting from the "carbenium'' activation (C2H5delta+-Hdelta- ), with the zinc cation abstracting the hydride ion, is unfavourable becaus e of the high activation barrier for the first step (67.6 kcal mol(-1)).