Supported Zirconium Hydride Catalysts for Ethylene Oligomerization

The US Shale Gas Boom has prompted an expansion of ethane cracking capacity that has produced an abundant supply of ethylene. Ethylene oligomerization seeks to upgrade this feedstock to more value-added products though controlled carbon chain growth. Although reports of zirconium-based catalysts for this class of chemistry exist, these catalysts are typically homogeneous and require activation by a pyrophoric cocatalyst, making their industrial implementation challenging. Supported zirconium hydrides are a class of heterogeneous catalyst that are activated in the presence of hydrogen and have yet to be applied to ethylene oligomerization, despite their reported activity for other carbon-carbon bond forming reactions. Herein, we report the synthesis and detailed characterization of these materials and confirm the presence of surface zirconium hydride species. The resulting material is shown to be an active oligomerization catalyst. The presence of the surface hydride species is shown to be integral to this activity.