Selective dimerization of ethene to 2-butene on Zn2+-containing ZSM-5 zeolite (Zn2+/ZSM-5) at 296-523 K has been discovered. The intermediate but-3-en-1-ylzinc species is identified with 13C CP/MAS NMR and Fourier transform infrared spectroscopy. The density functional theory study of two alternative dimerization pathways reveals that the intermediate is formed with the involvement of the saturated bridged dimeric Zn-(CH2)4-O species. It is also shown that ethene conversion to 2-butene increases with the increase in the quantity of Brønsted acid sites in Zn2+/ZSM-5 zeolite; however, the selectivity of the reaction decreases. The results obtained are of potential interest for developing industrially relevant Zn-containing zeolite catalysts for the selective conversion of ethene to 2-butene.

The reactivity theories and characterization studies for metal-containing zeolites are often focused on probing the metal sites. We present a detailed computational study of the reactivity of Zn-modified BEA zeolite towards C-H bond activation of the methane molecule as a model system that highlights the importance of representing the active site as the whole reactive ensemble integrating the extra-framework Zn_EF²⁺ cations, framework oxygens (O_F²⁻), and the confined space of the zeolite pores. We demonstrate that for our model system the relationship between the Lewis acidity, defined by the probe molecule adsorption energy, and the activation energy for methane C-H bond cleavage performs with a determination coefficient R² = 0.55. This suggests that the acid properties of the localized extra-framework cations can be used only for a rough assessment of the reactivity of the cations in the metal-containing zeolites. In turn, studying the relationship between the activation energy and pyrrole adsorption energy revealed a correlation, with R² = 0.80. This observation was accounted for by the similarity between the local geometries of the pyrrole adsorption complexes and the transition states for methane C-H bond cleavage. The inclusion of a simple descriptor for zeolite local confinement allows transferability of the obtained property-activity relations to other zeolite topologies. Our results demonstrate that the representation of the metal cationic species as a synergistically cooperating active site ensembles allows reliable detection of the relationship between the acid properties and reactivity of the metal cation in zeolite materials.