Photocatalytic Oxidative Dehydrogenation of Propane for Selective Propene Production with TiO₂

Oxidative dehydrogenation of propane (ODHP) as an exothermic process is a promising method to produce propene (C₃H₆) with lower energy consumption in chemical industry. However, the selectivity of the C₃H₆ product is always poor because of overoxidation. Herein, the ODHP reaction into C₃H₆ on a model rutile(R)-TiO₂(110) surface at low temperature via photocatalysis has been realized successfully. The results illustrate that photocatalytic oxidative dehydrogenation of propane (C₃H₈) into C₃H₆ can occur efficiently on R-TiO₂(110) at 90 K via a stepwise manner, in which the initial C-H cleavage occurs via the hole coupled C-H bond cleavage pathway followed by a radical mediated C-H cleavage to the C₃H₆ product. An exceptional selectivity of ∼90% for C₃H₆ production is achieved at about 13% propane conversion. The mechanistic model constructed in this study not only advances our understanding of C-H bond activation but also provides a new pathway for highly selective ODHP into C₃H₆ under mild conditions.