Identification of the driving forces in methanol-to-olefin conversion by modeling the zeolite cage and contents

The rapidly increasing demand of oil-based chemicals calls for the development of new technologies based on other natural sources. Among these emerging alternatives, the methanol-to-olefin process (MTO) in acidic zeolites is one of the most promising. However, unraveling the reaction mechanism of such an extremely complex catalytic process like MTO conversion has been a challenging task from both experimental and theoretical viewpoint. For over 30 years the actual mechanism has been one of the most discussed topics in heterogeneous catalysis.[1] Instead of plainly following direct routes,[2-3] the MTO process has experimentally been found to proceed through a hydrocarbon pool mechanism, in which organic reaction centers act as cocatalysts inside the zeolite pores, adding a whole new level of complexity to this issue.[4-5] Therefore, a more detailed understanding of the elementary reaction steps can be obtained with the complementary assistance of theoretical modeling. In this work, a complete supramolecular complex of both the zeolite framework and the co-catalytic hydrocarbon pool species is modeled through state-of-the-art quantum chemical techniques [6-7]. This approach provides a more detailed understanding of the crucial interactions between the zeolite framework and its contents, which form the driving forces for successful methanol-to-olefin conversion. [1] Stocker, M., Microporous Mesoporous Mater. 29 (1999) 3. [2] Song, W.G., Marcus, D.M., Fu, H., Ehresmann, J.O., Haw, J.F., J. Am. Chem. Soc. 124 (2002) 3844. [3] Lesthaeghe, D., Van Speybroeck, V., Marin, G.B., Waroquier, M., Angew. Chem. Int. Ed. 45 (2006) 1714. [4] Dessau, R. M., J. Catal. 99 (1986) 111. [5] Dahl, I.M., Kolboe, S., Catal. Lett. 20 (1993) 329. [6] Lesthaeghe, D., De Sterck, B., Van Speybroeck, V., Marin, G.B., Waroquier, M., Angew. Chem. Int. Ed. 46 (2007) 1311. [7] McCann, D.M., Lesthaeghe, D., Kletnieks, P.W., Guenther, D.R., Hayman, M.J., Van Speybroeck, V., Waroquier, M., Haw, J.F. Angew. Chem. Int. Ed. 47 (2008) 5179.