Mixed-valence Co0/IIOₓ clusters on silicalite-1 facilitate propane dehydrogenation to propene

Understanding the nature of active sites in heterogeneous catalysts and how to create them purposefully opens up the possibility of tailored catalyst design. Here we report mixed-valence subnanometre CoOx clusters, consisting of a few metallic Co⁰ atoms on top of Co²⁺, bound to a silicalite-1 support through lattice oxygen atoms as active species for non-oxidative propane dehydrogenation (PDH) to propene. Compared with commercial-like PtSn/Al₂O₃ and K-CrOx/Al₂O₃ catalysts also tested in the present study, as well as other state-of-the-art Pt- or Co-containing PDH catalysts, this system showed high on-stream stability, propene productivity and selectivity at close-to-equilibrium propane conversion. Moreover, it showed durability in a series of PDH/regeneration cycles between 500 and 550 °C. The performance of this catalyst system is industrially attractive in terms of propene production costs, as suggested by our initial techno-economic assessment.