Active species and fundamentals of their creation in Co-containing catalysts for efficient propane dehydrogenation to propylene.

[Display omitted] • Metallic Co0 species in situ formed are suggested to be the main active sites for PDH. • CoO x but not Co0 is responsible for the formation of undesired products. • Transformation of CoO x to Co0 depends on the strength of CoO x -support interactions. • Co/Silicalite-1 showed the C 3 H 6 space time yield of 1.50 kg·h−1·kg cat −1 at 550 °C. Although Co-containing catalysts show attractive performance in the non-oxidative propane dehydrogenation to propylene (PDH), their tailored development is hindered by the ambiguity in the kind of active sites (Co0 or Co2+O x) responsible for selective and unselective pathways. Herein, we demonstrate that supported CoO x species expends its lattice oxygen through oxidation of C 3 H 8 to CO 2 /C 3 H 6 and are accordingly transformed into Co0 species. The latter are decisive for the selective dehydrogenation of propane to propylene with high activity. The ability of CoO x to in situ form Co0 is affected by metal-oxide-support interactions (MOSI). In addition to the kind of support, defective OH groups (OH nests) in ZSM-5-type zeolites seem to be relevant for the MOSI effect. In comparison with previous studies highlighting the importance of the size of CoO x species and their acidity for coke formation, we could not establish any direct correlation. Nevertheless, the presence of CoO x seems to be relevant for this undesired reaction because the formation of coke is hindered when CoO x species are transformed to Co0 species. Catalyst acidic sites are responsible for cracking reactions. Thus, the derived mechanistic insights reveal the nature of active sites both for selective and unselective pathways and provide fundamentals for catalyst development. From an industrial viewpoint, the developed Co/Silicalite-1 (Co/S-1) catalyst with the weakest MOSI and accordingly highest fraction of Co0 showed the space time yield of propylene formation of 1.50 kg·h−1·kg cat −1 at 67 % equilibrium propane conversion and propylene selectivity of 95.3 % and the Co-related TOF value of 0.145 s−1 at 550 °C. These both activity values exceed those of the state-of-the-art Co-containing catalysts. The productivity of Co/S-1 is comparable or even higher than that of industrially relevant Pt- or Cr-containing catalysts. [ABSTRACT FROM AUTHOR]