Oligomerization of Light Olefins Catalyzed by Brønsted-Acidic Metal–Organic Framework-808

Sulfated metal–organic framework-808 (S-MOF-808) exhibits strong Brønsted-acidic character which makes it a potential candidate for the heterogeneous acid catalysis. Here, we report the isomerization and oligomerization reactions of light olefins (C3–C6) over S-MOF-808 at relatively low temperatures and ambient pressure. Different products (dimers, isomers, and heavier oligomers) were obtained for different olefins, and effective C–C coupling was observed between isobutene and isopentene. Among the substrates investigated, facile oligomerization occurred very specifically for the structures with an α-double bond and two substituents at the second carbon atom of the main carbon chain. The possible oligomerization mechanism of light olefins was discussed based on the reactivity and selectivity trends. Moreover, the deactivation and regeneration of S-MOF-808 were investigated. The catalyst deactivates via two mechanisms which predominance depends on the substrate and reaction conditions. Above 110 °C, a loss of acidic sites was observed due to water desorption, and the deactivated catalyst could be regenerated by a simple treatment with water vapor. For C5 substrates and unsaturated ethers, the oligomers with increased molecular weight caused deactivation via blocking of the active sites, which could not be readily reversed. These findings offer the first systematic report on carbocation-mediated olefin coupling within MOFs in which the Brønsted acidity is associated with the secondary building units of the MOF itself and is not related to any guest substance hosted within its pore system.