Propane Dehydrogenation Over Reduced CeO ₂ and CeZrO ₂

Resumen

ABSTRACT The on‐purpose generation of propylene via propane dehydrogenation (PDH) operates at industrial scale using supported transition metal catalysts of Pt and Cr. To overcome limitations associated with the high cost and elevated CO 2 footprint of Pt mining, and with the high toxicity of the Cr systems, bulk non‐noble metal oxides such as ZrO 2 and TiO 2 have been recently reported to catalyze the PDH reaction when activated in reducing atmospheres. CeO 2 , in contrast, despite its greater reducibility, has been deemed PDH inactive. Here, we demonstrate that CeO 2 and CeZrO 2 catalyze efficiently the PDH reaction, provided that deep, bulk‐level degree of reduction is promoted. By combination of structural and chemical characterization, kinetic studies, and DFT modelling, we show that PDH proceeds through low‐energy pathways that are unlocked only at these high levels of reduction. Incorporation of suitable amounts of Zr in CeZrO 2 formulations reduces undesired side reactions and hinders the surface area losses that are otherwise observed in H 2 at high temperature in pure CeO 2 systems, maximizing the catalyst specific activity. These findings broaden the set of non‐noble metal oxides that can function as nontoxic, low cost, and environmentally friendly alkane dehydrogenation catalysts.