Theoretical Study of the Double-Bond Isomerization of 1-Hexene to cis-2-Hexene over ZSM-5 Zeolite

We investigated the double-bond isomerization reaction of 1-hexene to cis-2-hexene on the surface of ZSM-5 zeolite using density functional theory with a 54T cluster model simulating the local structures of zeolite materials. We found that the double-bond isomerization proceeded by a mechanism that did not involve the bifunctional (acid-base) nature of the zeolite active sites but exclusively involved the acid sites. According to this mechanism, 1-hexene is the first physically adsorbed onto the zeolite acid site resulting in the formation of a pi-complex, and then the acidic proton of the zeolite transfers to a carbon atom of the double bond of the physisorbed 1-hexene. The other carbon atom of the double bond of the physisorbed 1-hexene bonds with the host oxygen and yields a stable alkoxy intermediate. Thereafter, the host oxygen abstracts a hydrogen atom from the C6H13 fragment and the C - O bond of the alkoxy intermediate is broken, which restores the zeolite active site and yields physisorbed cis-2-hexene. The proposed reaction pathway competes with the bifunctional pathway. The rate-determining step is the decomposition of the alkoxy intermediate with an activation energy of 134. 64 kJ . mol(-1). The calculated apparent activation energy for the isomerization reaction is 59. 37 kJ . mol(-1), which is in good agreement with the reported experimental value. These results well explain the energetic aspects during the double-bond isomerization and extend the understanding of the nature of zeolite active sites.