SSZ‐13 Zeolite with Isolated Co ²⁺ Sites as an Efficient and Durable Catalyst System for Non‐Oxidative Ethane Dehydrogenation

Abstract

Abstract Non‐oxidative dehydrogenation of ethane (EDH) is an attractive method for on‐purpose ethene production, but achieving high activity and, especially, durability with catalysts based on earth‐abundant metals remains challenging. Herein, we introduce the Co/SSZ‐13 system with exclusively divalent cobalt (Co 2+ ) ions that meets the above requirements. The use of complementary characterization techniques enabled us to reveal two Co 2+ species: Co 2+ ─Z 2 located in the six‐membered‐ring windows and [Co(OH)] + ─Z in the eight‐membered‐ring windows, with Z representing a charged zeolite framework site. A quantitative correlation between the rate of ethene formation and the site population establishes Co 2+ ─Z 2 as the active species. In situ X‐ray absorption spectroscopy confirms their structural and electronic stability under high‐temperature reaction conditions. The optimized 0.9Co/SSZ‐13 (0.9Co) catalyst showed highly durable operation over 200 dehydrogenation/oxidative regeneration cycles at 600–650°C lasting for 150 h with industrially relevant productivity. In this regard, it outperforms almost all previously developed catalysts even those with platinum as an active component. The obtained results uncover the atomic‐level origins of EDH activity/durability of the Co/SSZ‐13 system and highlight the critical role of metal site location in designing highly active, selective, and durable catalysts for on‐purpose ethene production.