Stable Cobalt–Zeolite Propane‐Dehydrogenation Catalysts Enabled by Reaction‐Driven Reconstruction

Cobalt-based catalysts have emerged as promising substitutes for Pt- and Cr-based propane dehydrogenation (PDH) catalysts. However, controlling the distribution of Co species and achieving stable active centers remains challenging. Here, we report that reaction-driven reconstruction of metallic cobalt (Co⁰) species within pure silica MFI zeolite (S-1) into CoO_x clusters within silanol nests during PDH yields efficient and durable performance. Atomically dispersed CoO_x clusters exhibit exceptional durability and high propylene space-time yield (STY), maintaining an ultrahigh propylene STY of 17.2 mmol_C3H6 g_cat ^-1 h^-1 for over 260 h under industrially relevant conditions, surpassing previous cobalt-based PDH catalysts. Moreover, the catalyst operates stably at 520 °C for 170 h with near-equilibrium propane conversions. Comprehensive characterizations indicate the dynamic evolution process from the silanol nests effectively capturing and stabilizing Co⁰ species within S-1 zeolite, thereby promoting the dynamic formation of CoO_x clusters during the PDH process. We also demonstrate that stable Co─O active centers formed by this unique anchoring strategy improve catalyst stability by suppressing coke formation and promoting efficient propane dehydrogenation.