The enhancing effect of Co2+ on propane non-oxidative dehydrogenation over supported Co/ZrO2 catalysts.

[Display omitted] • Co/ZrO 2 catalysts with single Co2+ are efficient for C 3 H 8 dehydrogenation to C 3 H 6. • 1Co/ZrO 2 performed durable over multiple dehydrogenation/regeneration cycles. • 1Co/ZrO 2 showed higher activity than a commercial analogue of K-CrO x /Al 2 O 3. • The high activity results from a synergy effect between Co2+ and Zr cus. • Recombination of surface H species is the rate-limiting step in C 3 H 6 formation. Due to the increased production of shale gas containing propane, the share of non-oxidative propane dehydrogenation (PDH) in the large-scale production of propene is expected to continue to grow. There are, however, some ecofriendly and cost shortcomings associated with the currently applied Cr- or Pt-containing catalysts. Against this background, we present here Co/ZrO 2 alternatives and reveal the fundamentals affecting their activity, which can be used for purposeful catalyst design. Co2+ species homogeneously distributed within the lattice of ZrO 2 significantly increase the activity of coordinatively unsaturated Zr4+ for the PDH reaction. The increase is caused by accelerating both the cleavage of CH bonds in propane and the recombination of surface H species, with the latter reaction being the rate-limiting step. The best-performing catalyst outperformed an analogue of commercial K-CrO x /Al 2 O 3 in terms of the rate of propene formation and demonstrated durable performance over a series of 10 PDH/regeneration cycles under industrially relevant conditions. It also outperformed most previously developed Co-containing catalysts in terms of propene productivity. The space–time yield of propene formation achieved at 57 % equilibrium propane conversion at 550 °C was 0.71 kg·h−1·kg cat -1. [ABSTRACT FROM AUTHOR]